FR3138313A1 - SYSTEMS, METHODS AND KITS FOR ALTERING HAIR COLOR - Google Patents

Abstract

SYSTEMS, METHODS AND KITS FOR ALTERING 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 composite -dye. The disclosure also relates to methods of modifying hair color using the systems, as well as kits comprising the systems. Figure for the abstract: none

Description

SYSTEMS, METHODS AND KITS FOR ALTERING HAIR COLOR

The present disclosure relates to systems, methods and kits for modifying hair color.

CONTEXT

Consumers wish to use cosmetic compositions to improve the appearance of keratinous substrates such as hair, for example, by modifying 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 to improve the appearance of hair involve chemical treatment of the hair. For example, the process of changing hair color may involve coloring the hair by depositing an artificial color onto the hair that provides a different shade or color to the hair.

Traditional hair coloring processes include permanent and semi-permanent or temporary hair coloring. Permanent hair color compositions use oxidation dye precursors, which are also known as primary intermediates or couplers. These oxidation dye precursors are colorless or weakly colored compounds which, when combined with oxidizing products, give rise to colored complexes through a process of oxidative condensation. Permanent hair color compositions also contain ammonia or other alkalizing agents that cause the hair shaft to swell, allowing small oxidative dye molecules to penetrate the cuticle and cortex before the oxidative condensation process. is finished. The larger color 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 chosen from acidic (anionic), basic (cationic) or neutral direct dyes which are deposited on the hair fiber to give color to the hair.

However, we know that traditional hair coloring compositions have drawbacks. For example, oxidative hair coloring processes typically cause damage to hair, such as making it brittle, dry, rough and/or brittle, and/or irritation to the scalp or skin due to the use of peroxide. hydrogen and alkaline agents required to achieve permanent coloring of hair fibers.

Semi-permanent or temporary hair color compositions can provide 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 may also cause irritation to the skin and/or scalp. Additionally, semi-permanent or temporary hair dyes are usually not capable of providing the same shine or variety of shades as permanent hair coloring compositions.

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

The present inventors have now surprisingly discovered hair coloring processes using a microtube-dye composite that results in improved color deposition and more vibrant hair colors.

SUMMARY

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 less damage to the hair than traditional hair coloring processes. .

In various embodiments, the disclosure relates to systems for modifying hair color comprising (a) a pretreatment composition comprising at least one amine 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 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 compounds may be selected from non-surfactant amine compounds, and the dye may be selected from synthetic or natural direct dyes.

In some embodiments, the amine compounds are selected from non-surfactant amine 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 to approximately 2,500, such as ranging from approximately 50 to approximately 10,000, from approximately 50 to approximately 8,000, from approximately 50 to approximately 6,000, from approximately 50 to approximately 4,000, from approximately 50 to approximately 3,000, from approximately 50 approximately to approximately 2,000, approximately 100 to approximately 10,000, approximately 100 to approximately 7,500, approximately 100 to approximately 5,000, or approximately 100 to approximately 2,500.

In certain embodiments, the amine-based compounds are chosen 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 that, 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 C2-polyalkyleneimines C8 or C2-C5 branched or unbranched. In some embodiments, a polyethyleneimine may be chosen. For example, a polyethyleneimine having a molecular weight ranging from about 100 to about 5000, from about 100 to about 3500, from about 100 to about 2500 or from about 100 to about 2000 may be chosen.

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, ranging from about 2 to 7 approximately, from 2 approximately to 6 approximately, from 2 approximately to 5 approximately or from 2 approximately to 4 approximately.

In at least one embodiment, the disclosure relates to systems comprising (a) a pretreatment composition comprising at least one non-surfactant amine compound having a molecular weight ranging 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, in which the pretreatment composition and/or the coloring composition each have a pH ranging from approximately 2 to 7 approximately, such as from approximately 2 to approximately 6, from approximately 2 to approximately 5 or from approximately 2 to approximately 4.

The disclosure relates to methods of treating hair, for example by changing hair color, by applying systems according to the disclosure to hair. In various embodiments, the methods include (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) can be repeated one or more times, with the same pretreatment and/or coloring composition(s) or pretreatment composition(s) and/or coloring composition(s). or different coloring(s).

In various embodiments, the methods may further include allowing the pretreatment and/or coloring compositions to sit on the hair for a possible dwell period, e.g., up to about 60 minutes, such as 2 minutes. about 50 minutes or 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 a possible application period, but before the step of applying the coloring composition, which may include air drying the hair or drying the hair with a hair dryer or helmet, optionally with heat. The drying step in various embodiments may include drying the hair after the step of applying the pretreatment composition (optionally after a setting period) without rinsing or otherwise removing the pretreatment composition. hair before hair drying.

Kits for modifying hair color comprising the systems according to the disclosure are also disclosed. In various embodiments, the kits include (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

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

, , Figures 2A-2C are graphs demonstrating a change in ΔE (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, then coloring compositions according to exemplary embodiments of the disclosure having variable pH values. These graphs show that systems according to the disclosure having lower pH of the pretreatment and/or coloring compositions surprisingly provide improved color deposition.

, Figures 3A-3B are graphs demonstrating a change in ΔE (y axis) of hair treated with systems comprising examples of pretreatment composition comprising a polyethyleneimine of different molecular masses then coloring compositions according to examples of embodiments of disclosure, or treated with coloring compositions only. These graphs show that pretreatment compositions including non-surfactant amine compounds with lower molecular weights provide surprisingly better color deposition.

There is a graph showing the percent change in ΔE (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 compound in the systems and methods according to the disclosure decreases, the ΔE increases surprisingly.

, Figures 4A-4B are graphs demonstrating a change in ΔE (y axis) of hair treated with systems and methods according to the disclosure including examples of pretreatment compositions according to the disclosure then by examples of coloring compositions according to the disclosure, with respect to the change in the ΔE of hair treated with pretreatment compositions having the same pH but including compounds which are not amine based, then by examples of coloring compositions according to the disclosure. These graphs show that pretreatment compositions comprising non-surfactant amine compounds provide surprisingly improved color deposition compared to pretreatment compositions comprising non-amine compounds, even at high pH values. pretreatment compositions are identical and/or the molecular masses of the pretreatment agents are similar.

DETAILED DESCRIPTION

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 better color deposition on the hair which gives it more vibrant and satisfying coloring.

Systems

It has been surprisingly and unexpectedly discovered that when hair is treated with a system comprising a pretreatment composition comprising at least one amine-based compound and a coloring composition comprising a microtube-dye composite, it is possible to obtain a better color deposit on the hair and a more vibrant hair color.

Pretreatment compositions

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.

The non-surfactant amine compounds useful in the pretreatment compositions according to 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, non-surfactant amine 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 8,000, from about 50 to about 8,000, from about 50 to about 8,000, 50 approximately to 7,000 approximately, 50 approximately to 6,000 approximately, 50 approximately to 5,000 approximately, 50 approximately to 4,000 approximately, 50 approximately to 3,000 approximately, 50 approximately to 2,000 approximately, 100 approximately to approximately 10,000, from approximately 100 to approximately 9,000, from approximately 100 to approximately 8,000, from approximately 100 to approximately 7,000, from approximately 100 to approximately 6,000, from approximately 100 to approximately 5,000, from approximately 100 to approximately 4 000 approximately, from approximately 100 to approximately 3,000 or from approximately 100 to approximately 2,000. In some embodiments, the non-surfactant amine compounds may have a molecular weight ranging from about 50 to about 7500, from about 50 to about 2500, from about 50 to about 1500, from about 100 to about 7 500 or so, from about 100 to about 2,500 or from about 100 to about 1,500.

In various embodiments, useful non-surfactant amine compounds have one or more nitrogen atoms in the main chain or backbone of the compound, i.e. at least one nitrogen atom other than as a part of a side chain attached to the main chain or backbone of the compound. It should be understood that such compounds may include nitrogen atom(s) in one or more side chains, but that 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 can be used. In some embodiments, the non-surfactant amine compound may comprise, consist essentially of, or consist of arginine.

In other embodiments, useful non-surfactant amine compounds contain one or more HN=C imine groups. For example, synthetic or natural polyamines can be chosen. In various embodiments, polyalkyleneimines such as branched or unbranched C2-C8 or C2-C5 polyalkyleneimines may be chosen. For example, the amine-based compounds can be chosen from polyethyleneimine, polypropyleneimine, poly(allylamine) and/or polyvinylamine. In at least one embodiment, the amine compound comprises a polyethyleneimine. As useful polyethyleneimines, mention may be made of 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 can also be used. In some embodiments, the non-surfactant amine compound may comprise, consist essentially of, or consist of a polyethyleneimine.

In other embodiments, polyamino acids may be chosen such as, for example, a polyarginine.

Optionally, the pretreatment compositions according to the disclosure may comprise several non-surfactant amine-based compounds. In embodiments where multiple non-surfactant amine 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 of about 5,000, less than about 3,000, or less than about 2,500.

The total amount of non-surfactant amine compounds can 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 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 approximately 0.001% to approximately 9%, from approximately 0.001% to approximately 8%, from approximately 0.001% to approximately 7%, from approximately 0.001% to approximately 6%, from approximately 0.001% to approximately 5%, approximately 0.001% to approximately 4%, approximately 0.001% to approximately 3%, approximately 0.001% to approximately 2.5%, approximately 0.001% to approximately 2%, approximately 0.001% to approximately 1.5%, from approximately 0.001% to approximately 1%, from approximately 0.001% to approximately 0.5%, from approximately 0.01% to approximately 25%, from approximately 0.01% to approximately 20%, from approximately 0.01% to approximately 15%, from approximately 0.01% to approximately 10%, from approximately 0.01% to approximately 9%, from approximately 0.01% to approximately 8% , from approximately 0.01% to approximately 7%, from approximately 0.01% to approximately 6%, from approximately 0.01% to approximately 5%, from approximately 0.01% to approximately 4%, d approximately 0.01% to approximately 3%, approximately 0.01% to approximately 2.5%, approximately 0.01% to approximately 2%, approximately 0.01% to approximately 1.5% , from approximately 0.01% to approximately 1%, from approximately 0.01% to approximately 0.5%, from approximately 0.1% to approximately 25%, from approximately 0.1% to approximately 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 approximately 0.1% to approximately 7%, from approximately 0.1% to approximately 6%, from approximately 0.1% to approximately 5%, from approximately 0.1% to approximately 4%, approximately 0.1% to approximately 3%, approximately 0.1% to approximately 2.5%, approximately 0.1% to approximately 2%, approximately 0.1% to approximately 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 compounds ranges from about 0.2% to about 25%, about 0.2% to about 20%, about 0. 2% to approximately 15%, approximately 0.2% to approximately 10%, approximately 0.2% to approximately 9%, approximately 0.2% to approximately 8%, approximately 0.2% to approximately 7%, from approximately 0.2% to approximately 6%, from approximately 0.2% to approximately 5%, from approximately 0.2% to approximately 4%, from approximately 0.2% to approximately 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 approximately 1%, from approximately 0.5% to approximately 25%, from approximately 0.5% to approximately 20%, from approximately 0.5% to approximately 15%, from approximately 0.5% to approximately 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 approximately 0.5% to approximately 5%, from approximately 0.5% to approximately 4%, from approximately 0.5% to approximately 3%, from approximately 0.5% to approximately 2.5% , from approximately 0.5% to approximately 2%, from approximately 0.5% to approximately 1.5% or from approximately 0.5% to approximately 1% by weight, relative to the total weight of the composition of pretreatment.

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.

Examples of non-aqueous solvents include, for example, glycerin, C _1-4 alcohols, organic solvents, fatty alcohols, fatty ethers, fatty esters, polyols, glycols, vegetable oils, oils minerals, liposomes, lamellar lipid materials, and mixtures thereof. As examples of organic solvents, non-limiting mention may be made of 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.

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, from about 75% to about 99.99% by weight, about 99.9% by weight, from about 75% to about 99%, from about 75% to about 98%, from about 75% to about 97%, from about 90% to about 99.9%, from approximately 90% to approximately 99%, from approximately 90% to approximately 98%, from approximately 90% to approximately 97%, from approximately 95% to approximately 99.9%, from approximately 95% to approximately 99 %, from about 95% to about 98% or from about 95% to about 97%, by weight, based on the total weight of the pretreatment composition.

In various embodiments, the systems include multiple pretreatment compositions, such as, for example, two or more pretreatment compositions. In such embodiments, the non-surfactant amine 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 compound has a molecular mass of less than about 10,000, such as less than about 8,000, less than about 6,000, less than 5,000 about, less than about 3,000 or less than about 2,500.

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

In various embodiments, the pretreatment composition(s) have a pH 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 or equal to approximately 3. For example, the pretreatment composition may have a pH ranging 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.

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

Coloring composition

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 colorant of the composite may include at least one anionic, cationic, nonionic, or natural colorant, as well as mixtures thereof.

The term "microtube" as used herein includes any tubular material having dimensions at micron level or below (the length of the tube being, for example, less than about 1 mm), including nanotubes, or may refer to tubular structures having an external 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.

Examples of non-limiting microtubes include, for example, halloysite microtubes (Al ₂ Si ₂ O ₅ (OH) ₄ ). Halloysite is in the form of small cylinders (nanotubes) which can, for example, have a wall thickness ranging from about 10 to about 15 atomic aluminosilicate sheets, an external diameter ranging from about 50 to about 60 nm , an internal diameter ranging from about 12 to about 20 nm and a length ranging from about 0.5 to about 10 μm, with an average length of about 1 μm. Their outer surface is composed primarily of -Si-O-Si- and their inner surface of -Al-OH, and as such, these surfaces are oppositely charged at approximately neutral pH. In various embodiments of the disclosure, the microtubes comprise, consist essentially of, or consist of halloysite.

The microtubes can 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 microtube loading methods (such as halloysite), for example as described in US Patent 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.

As an example, a hair coloring agent can be dissolved in a suitable solvent, such as water, a non-aqueous solvent, or a mixture thereof, to form a solution. The quantity of dye can be chosen so that it approaches or is at the limit of solubility of the dye 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 hair coloring agent. 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 can be added to the dye solution, for example, in powder form, to form a dispersion. The amount of microtube component may, for example, be chosen to give a microtube:dye weight ratio ranging from about 1:1 to about 5:1, such as from about 1:1 to about 4:1, about 1:1 to about 3:1, or from about 1.5:1 to about 2.5:1, such as about 2:1, which can improve the color.

The dispersion can 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. example, approximately 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 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 that at least minus 45°C, for example, about 50°C.

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 to facilitate the dissolution of the chosen dye, for example sodium carbonate.

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 can 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, 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, mono-n -propyl ether of diethylene glycol, mono-iso-propyl ether of ethylene glycol, mono-iso-propyl ether of diethylene glycol, mono-n-butyl ether of ethylene glycol, mono-t-butyl ether of ethylene glycol, mono-t-butyl diethylene glycol ether, 1-methyl-1-methoxybutanol, monomethyl propylene glycol ether, monoethyl propylene glycol ether, mono-t-butyl propylene glycol ether, mono-n-propyl ether propylene glycol, mono-iso-propyl ether of propylene glycol, monomethyl ether of dipropylene glycol, monoethyl ether of dipropylene glycol, mono-n-propyl ether of dipropylene glycol, and mono-iso-propyl ether of dipropylene glycol; 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbitan, acetin, diacetin, triacetin, sulfolane, acetone, and mixtures thereof.

In some embodiments, the solvent may include 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 choose the appropriate solvent and/or combination of solvents, and quantities thereof, in order to dissolve the useful hair coloring agents according to the disclosure.

In various embodiments, the internal and/or external surface of the microtube may be modified prior to loading with the hair coloring agent, which may facilitate the dye loading and/or hair coloring process. As an example, microtubes can be modified with an anionic surfactant such as sodium dodecyl sulfate, or can 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 (for example, at a weight ratio of approximately 1:1), optionally shaken and/or centrifuged, and optionally washed and/or dried, in order to produce microtubes modified with the anionic surfactant, having an increased net negative charge compared to unmodified microtubes.

In another embodiment, the microtubes can be made 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 amphiphilic molecules anionic 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 around 120°. Examples of non-limiting silane coupling agents include (3-glycidyloxypropyl)trimethoxy silane (GTMS), 3-aminopropyltriethoxy silane (APTES), hexamethyldisilazane (HMDS), and octadecyltrimethoxy silane (ODTMS). As an 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 a increased temperature, for example, greater than about 50°C or greater than about 75°C, such as about 85°C.

In yet another embodiment, the surface of the microtube may be selectively etched. For example, the inner surface of the halloysite lumen can be etched by treatment with acid, such as sulfuric acid, which can increase the diameter of the lumen. In one embodiment, the halloysite may be stirred in sulfuric acid (e.g., 1M) 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 processing can increase the loading capacity of microtubes by 2, 3, 4 times the pre-etching processing capacity or even more.

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 include, consist primarily of, or consist of natural hair coloring agents. In various embodiments, the compositions are free or substantially free of oxidative hair coloring agents.

The term "anionic hair coloring agent" is intended to mean any hair coloring agent comprising in its structure at least one CO ₂ R or SO ₃ R substituent, R indicating a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. As an example, anionic hair coloring agents can be selected from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic dyes anthraquinone acids, indigoid dyes, natural acid dyes and combinations thereof.

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

(II)

(III)

in which

R ₇ , R ₈ , R ₉ , R ₁₀ , R' ₇ , R' ₈ , R' ₉ and R' ₁₀ , which may be identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto;

nitro, nitroso;

R ^o —C(X)—X′—, R ^o —X′—C(X)—, R ^o —X′—C(X)—X″— with R ^o representing a hydrogen atom or a group alkyl or aryl; 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;

(O) ₂ S(O ⁻ )—, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;

(O)CO ⁻ —, M ⁺ with M ⁺ as defined previously;

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

R′″—S(O) ₂ —X′— with R′″ representing an alkyl group or an optionally substituted aryl group, X′ as defined above;

- (di)(alkyl)amino;

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

optionally substituted heteroaryl; preferably, a benzothiazolyl group;

cycloalkyl; in particular cyclohexyl;

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

or alternatively two contiguous groups R ₇ with R ₈ or R ₈ with R ₉ or R ₉ with R ₁₀ form together with a fused benzo group A′; and R′ ₇ with R′ ⁸ or R′ ₈ with R′ ₉ or R′ ₉ with R′ ¹⁰ jointly form a fused benzo group B′; with A′ and B′ optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) ₂ S(O—)—, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R ^o —C(X)—X′—; viii) R ^o —X′—C(X)— ; ix) R ^o —X′—C(X)—X″—; x) Ar—N═N— and xi) optionally substituted aryl(alkyl)amino; with M ⁺ , R ^o , X, X′, X″ and Ar previously defined; And

W represents a sigma 6 bond, an oxygen or sulfur atom, or a divalent radical i) —NR—, with R as defined previously, or ii) methylene —C(R _a )(R _b )—, with R _a and R _b , which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively, R _a and R _b form, with the carbon atom which supports them, a spirocycloalkyl; preferably, W represents a sulfur atom or R _a and R _b jointly form a cyclohexyl;

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

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, yellow food grade 3, acid purple 3, acid purple 7, acid purple 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.

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

In another exemplary embodiment, the anionic hair coloring agent can be chosen from the anionic azo pyrazolone dyes of formulas (IV) and (V):

(IV)

(V)

in which

R ₁₁ , R ₁₂ and R ₁₃ , which may be the same or different, represent a hydrogen or halogen atom, an alkyl group or —(O) ₂ S(O ⁻ ), M ⁺ with M ⁺ as defined previously;

R ₁₄ represents a hydrogen atom, an alkyl group or a —C(O)O— group, M+ with M as defined above;

R ₁₅ represents a hydrogen atom;

R ₁₆ represents an oxo group, in which case R′ ₁₆ is absent, or alternatively R ₁₅ with R ₁₆ jointly form a double bond;

R ₁₇ and R ₁₈ , which may be identical or different, represent a hydrogen atom or a group chosen from:

(O) ₂ S(O ⁻ )—, M ⁺ with M ⁺ as defined previously;

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

R ₁₉ and R ₂₀ jointly form either a double bond or a benzo D′ group, which is optionally substituted;

R′ ₁₆ , R′ ₁₉ and R′ ₂₀ , which may be identical or different, represent a hydrogen atom or an alkyl or hydroxyl group;

R ₂₁ represents a hydrogen atom or an alkyl or alkoxy group;

R _a and R _b , which may be identical or different, are as defined above, preferably, R _a represents a hydrogen atom and R _b represents an aryl group;

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;

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

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.

As a non-limiting example of a dye of formula (V), we can cite acid yellow 17.

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

(VI)

(VII)

in which

R₂₂,R₂₃,R₂₄,R₂₅,R₂₆, and R₂₇, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

- alkyl;

- hydroxyl, mercapto;

- alkoxy, alkylthio;

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

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

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;

(O) ₂ S(O ⁻ )—, M ⁺ with M ⁺ as defined previously;

Z' represents a hydrogen atom or an NR ₂₈ R ₂₉ group with R ₂₈ and R ₂₉ , which may be identical or different, representing a hydrogen atom or a group chosen from:

- alkyl;

- polyhydroxyalkyl such as hydroxyethyl;

aryl optionally substituted by one or more groups, more particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (O) ₂ S(O ⁻ )—, M ⁺ with M ⁺ as defined previously; iii) R ^o —C(X)—X′—, R ^o —X′—C(X)—, R ^o —X′—C(X)—X″— with R ^o , X, X′ and ″ as defined previously, preferably, R ^o represents an alkyl group;

cycloalkyl; for example, cyclohexyl;

Z represents a group chosen from hydroxyl and NR′ ₂₈ R′ ₂₉ , with R′ ₂₈ and R′ ₂₉ , which may be identical or different, representing the same atoms or groups as R ₂₈ and R ₂₉ as defined above;

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

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.

As another non-limiting example of a dye of formula (VII), we can cite acid black 48.

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

(VIII)

(IX)

in which

R ₃₀ , R ₃₁ and R ₃₂ , which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

- alkyl;

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

- hydroxyl, mercapto;

nitro, nitroso;

polyhaloalkyl;

R ^o —C(X)—X′—, R ^o —X′—C(X)—, R ^o —X′—C(X)—X′— with R ^o , as defined previously;

(O) ₂ S(O ⁻ )—, M ⁺ with M ⁺ as defined previously;

(O)CO ⁻ —, M ⁺ with M ⁺ as defined previously;

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;

heterocycloalkyl such as piperidino, piperazino or morpholino;

R _c and R _d , which may be identical or different, represent a hydrogen atom or an alkyl group;

W is as defined previously; for example W can represent a group —NH—;

ALK represents a linear or branched divalent ₁ -C ₆ alkylene group; more particularly, ALK represents a group —CH ₂ —CH ₂ —;

n is 1 or 2;

p represents an integer between 1 and 5 inclusive;

q represents an integer between 1 and 4 inclusive;

u is 0 or 1;

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

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 —SO ₂ —;

M′ represents a hydrogen atom or a cationic counterion;
which may be present or absent, represents a benzo group optionally substituted by one or more R ₃₀ groups as defined above;

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

As non-limiting examples of dyes of formula (VIII), we can cite acid brown 13 and acid orange 3.

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, of 2-piperidino-5 acid. -nitrobenzenesulfonic acid, 2(4′-N,N(2″-hydroxyethyl)amino-2′-nitro)anilineethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid and yellow EXT D&C 7.

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

(X)

in which

R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ , which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; in particular, an alkyl and benzyl group substituted by a group (O) _m S(O ⁻ )—, M with M ⁺ and m as defined above;

R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ , which may be identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- (di)(alkyl)amino;

- hydroxyl, mercapto;

nitro, nitroso;

R ^o —C(X)—X′—, R ^o —X′—C(X)—, R ^o —X′—C(X)—X″— with R ^o representing a hydrogen atom or a group alkyl or aryl; 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;

(O) ₂ S(O ⁻ )—, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;

(O)CO ⁻ —, M ⁺ with M ⁺ as defined previously;

or alternatively two contiguous groups R ₄₁ with R ₄₂ or R ₄₂ with R ₄₃ or R ₄₃ with R ₄₄ jointly form a fused benzo group: I′; with I′ optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) ₂ S(O ⁻ )—, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R ^o —C(X)—X′— ; viii) R ^o —X′—C(X)— ; ix) R ^o —X′—C(X)—X″— ; with M ⁺ , R ^o , X, X′ and X″ as defined previously;

it being understood that at least one of the rings G, H, I or I′ comprises at least one sulfonate radical (O) ₂ S(O ⁻ )— or a carboxylate radical —C(O)O—; for example sulfonate.

In a preferred embodiment of formula (X), R ₃₇ to R ₄₀ represent a hydrogen atom, and R ₄₁ to R ₄₄ , which may be identical or different, represent a hydroxyl group or (O) ₂ S(O ⁻ )—, M+ ; and when R ₄₃ with R ₄₄ together form a benzo group, it is preferably substituted by an (O) ₂ S(O ⁻ )— group.

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.

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

(XII)

in which

R ₄₅ , R ₄₆ , R ₄₇ and R ₄₈ , which may be identical or different, represent a hydrogen or halogen atom;

R ₄₉ , R ₅₀ , R ₅₁ and R ₅₂ , which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto;

nitro, nitroso;

(O) ₂ S(O ⁻ )—, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;

(O)CO ⁻ —, M ⁺ with M ⁺ as defined previously;

G represents an oxygen or sulfur atom or an NR _e group with R _e as defined above;

L represents an O ⁻ , M+ alkoxide; a thioalkoxide S ⁻ , M ⁺ or an NR _f group, with R _f representing a hydrogen atom or an alkyl group and M ⁺ as defined above; M ⁺ is in particular sodium or potassium;

L′ represents an oxygen or sulfur atom or an ammonium group; N ⁺ R _f R _g , with R _f and R _g , which may be identical 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) _m S(O ⁻ )—, M ⁺ with m and M ⁺ as defined above;

Q and Q′, which may be the same or different, represent an oxygen or sulfur atom; And

M ⁺ is as defined previously.

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.

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

(XII)

in which

R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ and R ₆₀ , which may be identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxyl, mercapto;

nitro, nitroso;

R ^o —C(X)—X′—, R ^o —X′—C(X)—, R ^o —X′—C(X)—X″— with R ^o representing a hydrogen atom or a group alkyl or aryl; 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;

(O) ₂ S(O ⁻ )—, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;

(O)CO ⁻ —, M ⁺ with M ⁺ as defined previously;

G represents an oxygen or sulfur atom or an NR _e group with R _e as defined above;

R _i and R _h , which may be identical or different, represent a hydrogen atom or an alkyl group;

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

As a non-limiting example of a dye of formula (XII), we can cite acid blue 74.

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

(XIII)

in which

R ₆₁ represents a hydrogen or halogen atom or an alkyl group;

R ₆₂ , R ₆₃ and R ₆₄ , which may be the same or different, represent a hydrogen atom or an (O) ₂ S(O ⁻ )— group, M ⁺ with M ⁺ representing a hydrogen atom or a counter -cationic ion;

or alternatively R ₆₁ with R ₆₂ , or R ₆₁ with R ₆₄ , jointly form a benzo group optionally substituted by one or more groups (O) ₂ S(O ⁻ )—, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;

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

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

Without limitation, examples of anionic hair coloring agents may be selected from (C.I. 45380) acid red 87 (formula XI); (C.I. 10316) sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid (formula IX); (C.I. 10383) acid orange 3 (formula VIII); (C.I. 13015) acid yellow 9/food yellow 2 (formula II); (C.I. 14780) direct red 45/food red 13 (formula II); (C.I. 13711) acid black 52 (formula II); (C.I. 13065) acid yellow 36 (formula II); (C.I. 14700) sodium salt of 1-hydroxy-2-(2′,4′-xylyl-5-sulfonatoazo)naphthalene-4-sulfonic acid/food red 1 (formula II); (C.I. 14720) acid red 14/food red 3/mordant blue 79 (formula II); (C.I. 14805) 4-hydroxy-3-[(2-methoxy-5-nitrophenyl)diaza]-6-(phenylamino)naphthalene-2-sulfonic acid/brown acid sodium salt 4 (formula II); (C.I. 15510) acid orange 7/orange pigment 17/solvent orange 4 (formula II); (C.I. 15985) food yellow 3/pigment yellow 104 (formula II); (C.I. 16185) acid red 27/food red 9 (formula II); (C.I. 16230) acid orange 10/food orange 4 (formula II); (C.I. 16250) acid red 44 (formula II); (C.I. 17200) acid red 33/food red 12 (formula II); (C.I. 15685) acid red 184 (formula II); (C.I. 19125) acid violet 3 (formula II); (C.I. 18055) 1-hydroxy-2-(4′-acetamidophenylazo)-8-acetamidonaphthalene-3,6-disulfonic acid sodium salt/acid violet 7/food red 11 (formula II); (C.I. 18130) acid red 135 (formula II); (C.I. 19130) acid yellow 27 (formula IV); (C.I. 19140) acid yellow 23/food yellow 4 (formula IV); (C.I. 20170) 4′-(sulfonato-2″,4″-dimethyl)bis(2,6-phenylazo)-1,3-dihydroxybenzene/acid orange 24 (formula II); (C.I. 20470) 1-amino-2-(4′-nitrophenylazo)-7-phenylazo-8-hydroxy-naphthalene-3,6-disulfonic acid sodium salt/black acid 1 (formula II); (C.I. 23266) (4-((4-methylphenyl)sulfonyloxy)phenylazo)-2,2′-dimethyl-4-((2-hydroxy-5,8-disulfonato)naphthylazo)biphenyl/acid red 111 (formula III) ; (C.I. 27755) food black 2 (formula II) (C.I. 25440) 1-(4′-sulfonatophenylazo)-4-((2″-hydroxy-3″-acetylamino-6″,8″-disulfonato)naphthylazo)-6 -sulfonatonaphthalene (tetrasodium salt)/food black 1 (formula II), (C.I. 42090) acid blue 9 (formula C.I. 62045) sodium salt of 1-amino-4-cyclohexylamino-9,10-anthraquinone-2-sulfonic acid/acid blue 62 (formula VI), (C.I. 62105) acid blue 78 (formula VI), (C.I. 14710) 4-hydroxy-3-((2-methoxyphenyl)azo)-1-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-β-hydroxyethylamino-3-nitrobenzenesulfonic acid (formula IX); (C.I. 42640) acid violet 49 (formula X); (C.I. 42080) acid blue 7 (formula X); (C.I. 58005) 1,2-dihydroxy-3-sulfoanthraquinone sodium salt/mordant red 3 (formula VI); (C.I. 62055) sodium salt of 1-amino-9,10-dihydro-9,10-dioxo-4-(phenylamino)2-anthracenesulfonic acid/acid blue 25 (formula VI); or (C.I. 14710) sodium salt of 4-hydroxy-3-((2-methoxyphenyl)azo)-1-naphthalenesulfonic acid/acid red 4 (formula II).

Among the non-limiting examples of cationic dyes we find the hydrazono cationic dyes of formulas (Va) and (V'a), the azo cationic dyes (VIa) and (VI'a) and the diazo cationic dyes (VIIa) below :

in which :

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

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

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

- 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 alkyl groups (C1-C8), hydroxyl or alkoxy(C1-C8)

- Ar'' is an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl, which are optionally substituted, preferably by one or more alkyl (C1-C8), hydroxyl, (di)(alkyl)( C1-C8)amino, alkoxy(C1-C8) or phenyl;

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

- or as a variant, the Ra substituent with a Het+ substituent and/or Rb with an Ar substituent and/or Ra with Rb form, together with the atoms which carry them, a (hetero)cycloalkyl;

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

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

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.

Non-limiting examples of non-ionic hydrophobic direct dyes can be chosen from HC blue no. 2, HC blue no. 4, HC blue no. 5, HC blue no. 6, HC blue no. 7, HC blue no. 8, blue HC no. 9, blue HC no. 10, blue HC no. 11, blue HC no. 12, blue HC no. 13, blue HC no. 15, blue HC no. 17, brown HC no. 1, brown HC No. 2, green HC No. 1, orange HC No. 1, orange HC No. 2, orange HC No. 3, orange HC No. 5, red HC BN, red HC No. 1, red HC No. 3, red HC no. 7, red HC no. 8, red HC no. 9, red HC no. 10, red HC no. 11, red HC no. 13, red HC no. 54, red HC no. 14, violet HC BS, HC Violet No. 1, HC Violet No. 2, HC Yellow No. 2, HC Yellow No. 4, HC Yellow No. 5, HC Yellow No. 6, HC Yellow No. 7, HC Yellow No. 8, HC yellow no. 9, HC yellow no. 10, HC yellow no. 11, HC yellow no. 12, HC yellow no. 13, HC yellow no. 14, HC yellow no. 15.

Natural hair coloring agents can also be chosen. As used herein, the term "natural" hair coloring agents includes dyes 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 dyes. Examples of natural hair coloring agents may be chosen, without limitation, from orceins, curcumin, indole derivatives such as isatin or indole-2,3-dione, indigoids including indigo, phthalocyanines and optionally complexed porphyrins. to a metal, glycosyl or glycosyl-free iridoids, chromene dyes, anthraquinone and naphthoquinone dyes such as lawsone or henna, juglone, spinulosin, chromene or chromane dyes, such as neoflavanols and neoflavones, flavanols and anthocyanidols. It is also possible to use extracts containing these natural dyes, for example, plant extracts or poultices containing said dyes. In some embodiments, the colorant comprises, consists essentially of, or consists of one or more natural colorants, preferably hydrophobic natural colorants. For example, the colorant may comprise, consist essentially of, 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 as from about 0.1°% to about 50°%, from about 0.1°% to about 45°%, from about 0.1°% to approximately 40°%, approximately 0.1°% to approximately 35°%, approximately 0.1°% to approximately 30°%, approximately 0 .1°% to approximately 25°% approximately 0.1°% to approximately 20°%, approximately 0.1°% to approximately 15°%, d 'approximately 0.1°% to approximately 10°%, from approximately 0.1°% to approximately 9°%, from approximately 0.1°% to approximately 8°%, from approximately 0.1°% to approximately 7°%, from approximately 0.1°% to approximately 6°%, from approximately 0.1°% to approximately 5°%, approximately 0.1°% to approximately 4°%, approximately 0.1°% to approximately 3°%, approximately 0.1°% to approximately 2°%, from approximately 0.1°% to approximately 1°%, from approximately 0.5°% to approximately 50°%, from approximately 0.5°% to approximately 45°%, approximately 0.5°% to approximately 40°%, approximately 0.5°% to approximately 35°% , from approximately 0.5°% to approximately 30°%, from approximately 0.5°% to approximately 25°%, from approximately 0.5°% to approximately 20°%, from approximately 0.5°% to approximately 15°%, from approximately 0.5°% to approximately 10°%, from approximately 0.5°% to approximately 9°%, from approximately 0.5°% to approximately 8°%, from approximately 0.5°% to approximately 7°%, from approximately 0, 5°% to approximately 6°%, from approximately 0.5°% to approximately 5°%, from approximately 0.5°% to approximately 4°%, d 'approximately 0.5°% to approximately 3°%, from approximately 0.5°% to approximately 2°%, from approximately 0.5°% to approximately 1°%, from approximately 1°% to approximately 50°%, from approximately 1°% to approximately 45°%, from approximately 1°% to approximately 40°% , from approximately 1°% to approximately 35°%, from approximately 1°% to approximately 30°%, from approximately 1°% to approximately 25°%, d 'approximately 1°% to approximately 20°%, from approximately 1°% to approximately 15°%, from approximately 1°% to approximately 10°%, from approximately 1°% to approximately 9°%, approximately 1°% to approximately 8°%, approximately 1°% to approximately 7°%, approximately 1°% °% to approximately 6°%, from approximately 1°% to approximately 5°%, from approximately 1°% to approximately 4°%, from approximately 1°% to approximately 3°%, or from approximately 1°% to approximately 2°% by weight, based on the total weight of the microtube before loading, including all subranges between these values.

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 about 35% to about 50%, about 40% to about 50%, about 30% to about 45%, about 35% to about 45%, or about 40% to about 45% by weight , based on the weight of the microtube before loading, including all subranges between these values.

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 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 approximately 0.1% to approximately 7.5%, from approximately 0.1% to approximately 5%, from approximately 0.1% to approximately 3.5%, from approximately 1% to approximately 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 subranges between these values.

The coloring composition usually includes a solvent, in which the microtube-dye composite may be dispersed. The solvent may be chosen from water, non-aqueous solvents or a mixture thereof. The solvent will advantageously be chosen so that it does not interfere with a deposition of the microtube-dye composite on the hair, and so 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.

Examples of non-aqueous solvents include, for example, glycerin, C _1-4 alcohols, organic solvents, fatty alcohols, fatty ethers, fatty esters, polyols, glycols, vegetable oils, oils minerals, liposomes, lamellar lipid materials, and mixtures thereof. As examples of organic solvents, non-limiting mention may be made of 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.

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, mono-n -propyl ether of diethylene glycol, mono-iso-propyl ether of ethylene glycol, mono-iso-propyl ether of diethylene glycol, mono-n-butyl ether of ethylene glycol, mono-t-butyl ether of ethylene glycol, mono-t-butyl diethylene glycol ether, 1-methyl-1-methoxybutanol, monomethyl propylene glycol ether, monoethyl propylene glycol ether, mono-t-butyl propylene glycol ether, mono-n-propyl ether propylene glycol, mono-iso-propyl ether of propylene glycol, monomethyl ether of dipropylene glycol, monoethyl ether of dipropylene glycol, mono-n-propyl ether of dipropylene glycol, and mono-iso-propyl ether of dipropylene glycol; 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbita, sorbitan, acetin, diacetin, triacetin, sulfolane, and mixtures thereof.

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 approximately 80% to 90% by weight, relative to the total weight of the coloring composition.

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 correctors, preservatives, humectants, oils, fragrances, etc.

In various embodiments, the coloring composition has a pH 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 ranging 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.

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 about 0.1 % to approximately 10%, approximately 0.1% to approximately 9%, approximately 0.1% to approximately 8%, approximately 0.1% to approximately 7%, approximately 0.1% to approximately about 6%, about 0.1% to about 5%, about 0.1% to about 4%, about 0.1% to about 3%, about 0.1% to about 2 %, from approximately 0.1% to approximately 1%, from approximately 0.5% to approximately 10%, from approximately 0.5% to approximately 9%, from approximately 0.5% to approximately 8%, from approximately 0.5% to approximately 7%, from approximately 0.5% to approximately 6%, from approximately 0.5% to approximately 5%, from approximately 0.5% to approximately 4%, approximately 0.5% to approximately 3%, approximately 0.5% to approximately 2%, approximately 0.5% to approximately 1%, approximately 1% to approximately 10%, approximately 1% to approximately approximately 9%, approximately 1% to approximately 8%, approximately 1% to approximately 7%, approximately 1% to approximately 6%, approximately 1% to approximately 5%, approximately 1% to approximately about 4%, about 1% to about 3%, or about 1% to about 2% by weight, based on the weight of the coloring composition, including all sub-ranges of these values.

It should 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 a dye, a second set of microtubes comprising halloysite may be loaded with a second dye, and the first and second sets of composites microtube-dye 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.

Processes

It has been discovered that by modifying the color of the hair using systems according to the disclosure, a better deposit and greater vibrancy of the color has been advantageously obtained, in a surprising and unexpected manner. 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 disclosed exhibit a surprisingly significant improvement in color deposition and vibrancy compared to using the microtube-dye composite alone.

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

In various methods according to the disclosure, the hair is first treated with the pretreatment composition, 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, 4 grams approximately per gram of hair, approximately 3 grams per gram of hair, approximately 2 grams per gram of hair or approximately 1 gram per gram of hair.

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 setting period, and the hair may then optionally be partially, completely or substantially completely dried, for example, with a hairdryer or helmet or dried at the air. Alternatively, the hair may be partially, completely or substantially completely dried, e.g. with a hair dryer or helmet or air dried, without removing the pretreatment composition from the hair, e.g. without rinsing the hair or without drying hair with a towel. Preferably, the hair is completely or substantially completely dried after a laying period without removing the pretreatment composition from the hair, the drying step optionally including the use of heat.

The methods further include a step of applying the coloring composition to the hair after application of the pretreatment composition to the hair and possibly drying, for example by massaging or combing the composition over the entire head of hair to ensure coverage. complete. 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 that up to approximately 5 grams per gram of hair, for example, up to approximately 4 grams per gram of hair, up to approximately 3 grams per gram of hair, up to approximately 2 grams per gram of hair or up to at approximately 1 gram per gram of hair.

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. A person skilled in the art will be able to determine an appropriate amount of exposure time for the coloring composition on the hair in order to obtain the desired effect.

After a desired exposure 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.

In various embodiments, the steps described above of applying a pretreatment composition to the hair, optionally applying the pretreatment composition to the hair during an application period, optionally removing the pretreatment composition from the hair hair, applying a coloring composition to the hair, optionally applying the coloring composition to the hair during an application period, and optionally removing the coloring composition from the hair can be repeated one or more times , with the same pretreatment and/or coloring composition(s) or different pretreatment and/or coloring composition(s).

Thus, by way of example only, a method according to the disclosure may comprise applying a pretreatment composition (1a) to the hair, leaving the pretreatment composition (1a) on the hair for a period of application, 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 period of installation, and elimination of the coloring composition (1b) from the hair.

Another example of a method according to the disclosure may comprise the application of a pretreatment composition (1a) to the hair, the fact of leaving the pretreatment composition (1a) on the hair for an application period, the elimination of the pretreatment composition (1a) of the hair, the application of a coloring composition (1b) to the hair, the fact of leaving the coloring composition (1b) on the hair during an application period, the elimination of the coloring composition (1b) of the hair, the application of the pretreatment composition (1a) to the hair a second time, the fact of leaving the pretreatment composition (1a) on the hair for an application period, the removing the pretreatment composition (1a) from the hair, applying the coloring composition (1b) to the hair a second time, leaving the coloring composition (1b) on the hair for an application 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.

Yet another example of a method according to the disclosure may comprise applying a pretreatment composition (1a) to the hair, leaving the pretreatment composition (1a) on the hair for an application period, removing of the pretreatment composition (1a) of the hair, applying a coloring composition (1b) to the hair, leaving the coloring composition (1b) on the hair for an application period, removing of the coloring composition (1b) of the hair, applying a pretreatment composition (2a) to the hair, leaving the pretreatment composition (2a) on the hair for an application period, removing of the pretreatment composition (2a) of the hair, applying the coloring composition (2b) to the hair, leaving the coloring composition (2b) on the hair for an application period and removing the hair coloring composition (2b), wherein the pretreatment compositions (1a) and (2a) are not identical and the hair coloring compositions (1b) and (2b) are not identical.

Another example of a non-limiting method according to the disclosure may comprise the application of a pretreatment composition (1a) to the hair, optionally drying the hair, the application of a coloring composition (1b) to the hair without eliminating all first the pretreatment composition (1a), optionally leaving the coloring composition (1b) on the hair for a laying period, and removing the pretreatment composition (1) and the coloring composition coloring (1b) of hair.

Kits

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

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) mutually separated in 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.

Various example embodiments of kits according to the disclosure include:

a first compartment or container which contains a pretreatment composition comprising at least one amine-based compound and optionally at least one solvent; And

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.

Other example embodiments of kits according to the disclosure include:

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

wherein the pretreatment composition has a pH less than or equal to approximately 7, such as approximately 2 to approximately 6; And

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

wherein the coloring composition has a pH less than or equal to approximately 7, such as approximately 2 to approximately 6.

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.

It should be understood that, in examples of kits according to the invention, the pretreatment composition(s) and coloring composition(s) may be described herein for various systems, processes and examples, e.g. example with regard to particular components and/or particular ranges thereof.

Thus, in certain 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 thickened gel or 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 considered. 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 mix with the pretreatment composition and/or the coloring composition , can be chosen.

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 for this one.

As used herein, the terms “comprising”, “having” and “including” (or “understand”, “have” and “include”) are used in their open, non-limiting sense.

The terms “un”, “une”, “le” and “la” are understood to include the plural and the singular.

The expression “and/or” must 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 without reference to the other. For example, “preventing and/or reducing” corrosion includes cases of preventing corrosion and reducing corrosion, as well as cases where corrosion is reduced but not prevented, etc.

As used herein, the expressions “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 chosen from A, B, C, D, from A + B, from A + B + C, among A + D, among A + C + D, etc., without limitation on the variations thereof. Thus, the components can be used individually or in any combination thereof.

Except in the functional examples, or unless otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions are understood to be modified in all circumstances by the term "approximately," meaning
to within +/- 5% of the number indicated.

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

In this document, all ranges provided are intended to include each specific range within the given ranges, as well as a combination of intermediate subranges. So a range of 1-5 specifically includes 1, 2, 3, 4, and 5, as well as subranges 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 for inferring a subrange, etc.

As used herein, "exempt" means that the component or property is not detectable using accepted methodologies, and "substantially" or "substantially" exempt means that the component or property, if detectable using accepted methodologies, is negligible.

It should be understood that the use of the terms "treat", "treated", "treatment" and variations thereof are not intended to be limiting, but are instead intended to simply indicate that a or more compositions is/are applied to the hair, 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 been subject to application of the pretreatment composition, and/or may have been subject to application and removal of pretreatment composition, for example, by rinsing or drying with a towel. As another example, hair which is "treated" with a coloring composition according to the disclosure may have been subject to application of the coloring composition, and/or may have been subject to a application and rinsing of the coloring composition. As yet another example, hair which is "treated" with a system according to the disclosure may have undergone application of the pretreatment composition and possible removal thereof, and further , may have been subject to application of the coloring composition and possible rinsing thereof.

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 less than about 50 nM/m , when added to deionized water in a concentration by weight of 0.5 to 1%.

The examples which follow serve to illustrate embodiments of the present disclosure without being of a limiting nature. It will be obvious to those skilled in the art that various modifications and variations can be made in the delivery system, compositions and processes of the invention without departing from the spirit or scope of the invention.

EXAMPLES

The implementation of various non-limiting embodiments of the disclosure is shown by means of the following examples.

In the examples, the change in hair color is evaluated with the L* a* b* system, using Colorshot MS, where the change is determined by evaluating the color of the hair after treatment compared to the color of the hair before treatment. The color change (ΔE) is defined by:

The greater the value of ΔE, the greater the color difference compared to the hair before treatment.

Example 1 – Microtube-dye composites

The procedures of Examples 1A and 1B below were followed to prepare microtube-dye composites having the dye loadings shown in Table 1.

Composite Dye filler H-C _(1.4) Halloysite-Curcumin 1.4% H-C ₍₃₎ Halloysite-Curcumin 3% H-I ₍₄₃₎ Halloysite-Indigo 43%

Example 1A – Halloysite-curcumin composites

Curcumin was completely dissolved in acetone (10 mg of dye per mL of acetone) and unmodified halloysite (dye:halloysite weight ratio ~2:1) was added with stirring. The dispersion was sonicated for approximately five minutes and then placed under vacuum and stirred overnight. After centrifugation for approximately five minutes at 5000 rpm, the supernatant was discarded and the sample was vacuum dried and crushed into a fine powder.

Example 1B – Halloysite-indigo composites

Indigo was completely dissolved in water (99.99% water with 0.01% sodium carbonate; 5 mg of dye per mL of solvent) and unmodified halloysite was added. (dye:halloysite weight ratio ~2:1) with stirring. The dispersion was sonicated for approximately five minutes and then placed under vacuum and stirred overnight. After centrifugation for approximately five minutes at 5000 rpm, the supernatant was discarded and the sample was vacuum dried and crushed into a fine powder.

Example 2 – Pretreatment Compositions

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

Pretreatment composition Amine compound Molecular weight pH Concentration 2A polyethyleneimine 800 3 3.33% 2B polyethyleneimine 1,300 3 0.5% 2C polyethyleneimine 1,300 3 3.33% 2D polyethyleneimine 1,300 3 10% 2E polyethyleneimine 1,300 7 3.33% 2 F polyethyleneimine 1,300 11 3.33% 2G polyethyleneimine 2,000 3 3.33% 2H polyethyleneimine 25,000 3 3.33% 2I arginine 174.2 3 3%

Example 3 – Coloring compositions

The color 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 necessary, to prepare aqueous compositions having the reported halloysite-dye composite concentrations and pH values.

Coloring composition Halloysite-dye composite pH Concentration 3A H-C _(1.4) 3 2.5% 3B H-C _(1.4) 7 2.5% 3C H-C _(1.4) 7 5% 3D H-C ₍₃₎ 7 2.5% 3E H-C ₍₃₎ 3 5% 3F H-C ₍₃₎ 7 5% 3G H-I ₍₄₃₎ 3 2.5% 3H H-I ₍₄₃₎ 3 5% 3I H-I ₍₄₃₎ 7 5%

Example 4 – Demonstration of the benefit of pretreatment

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

Example 4-1 – Color provided by systems comprising pretreatment compositions and coloring compositions (of the invention)

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.

System Pretreatment composition Coloring composition ΔE 4A 2C 3F 27.2 4B 2C 3A 15.9 4C 2E 3B 13.2 4D 2C 3H 43.1 4E 2C 3I 39.7 4F 2 F 3I 39.6 4G 2I 3D 21.2 4H 2A 3D 19.3 4I 2B 3D 20.4 4D 2D 3D 17.3

The process of treating hair with the 4A-4J systems of the invention took place as follows. First, samples of 90% gray virgin hair were rinsed with tap water at ~37°C (five times), applied a commercial shampoo, and lathered for 30 seconds or so, the sample was allowed to sit for about a minute and then rinsed with tap water for about 30 seconds. The sample was then allowed to air dry.

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

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

The color change for each sample was assessed by determining the ΔE of the hair color after treatment compared to that of the hair color before treatment. The ΔE for each of systems 4A-4J is presented in Table 4-1 and Figures 1A-1D.

Example 4-2 – Color imparted by coloring compositions without pretreatment (Comparison)

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

Composition Pretreatment composition Coloring composition ΔE 4A' - 3F 18.8 4B’ - 3A 12.3 4C’ - 3B 9.8 4D’ - 3H 40.4 4E’ - 3I 31.7 4F’ - 3I 31.7 4G’ - 3D 12.2

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

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

The color change for each sample was assessed by determining the ΔE of the hair color after treatment compared to that of the hair color before treatment. The ΔE for each of the comparative compositions 4A"-4J' is presented in Table 4-2 and in Figures 1A-1D.

As shown in Figures 1A-1D, hair treated with the systems of the invention 4A-4J shows a much greater color change relative to the hair color before treatment, when compared to the change in hair color treated with the comparative compositions 4A'-4G' not using a pretreatment composition according to the disclosure.

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 deposit and more vibrant colors compared to hair not pre-treated as described here.

Example 5 – Demonstration of the benefit of an acidic pH

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

Example 5-1 – Color provided by systems comprising acidic pretreatment compositions

The color provided to 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.

System Pretreatment composition pH pretreatment Coloring composition pH coloring ΔE 5A 2E 7 3B 7 13.2 5B 2C 3 3B 7 14.9 5C 2 F 11 3G 3 40.4 5D 2C 3 3G 3 43.1

The color change for each sample was assessed by determining the ΔE of the hair color after treatment compared to that of the hair color before treatment. The ΔE for hair treated with each of the 5A-5D systems is presented in Table 5-1 and Figures 2A-2B. As can be seen, the ΔE for hair treated with systems 5B and 5D (pretreatment compositions having a pH lower than 7) is greater than the ΔE for hair treated with systems 5A and 5C (identical systems but with compositions corresponding pretreatment having a pH of 7 or more).

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

Example 5-2 – Color provided by systems comprising acid coloring compositions

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

System Pretreatment composition pH pretreatment Coloring composition pH coloring ΔE 5E 2C 3 3I 7 39.7 5F 2C 3 3H 3 43.1

The color change for both samples was assessed by determining the ΔE of the post-treatment hair color compared to that of the pre-treatment hair color. The ΔE for hair treated with 5E-5F systems is presented in Table 5-2 and on the . As can be seen, the ΔE for hair treated with the 5F system (coloring composition having a pH less than 7) is greater than the ΔE for hair treated with the 5E system (identical system but with a coloring composition having a pH of 7).

Example 5-2 shows that disclosed systems having lower pH coloring compositions surprisingly provide greater color change than systems comprising higher pH coloring compositions.

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

Example 6 – Demonstration of the benefit of the molecular mass of the amine compound

The following Examples 6-1 and 6-2 show 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 4-1. Example 4-2.

Example 6-1 – Comparison of the color provided by systems comprising pretreatment compositions having a polyethyleneimine of different molecular weights

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 the comparative composition C2 was also evaluated, without a pretreatment step.

System Pretreatment composition Amine molecular mass pH pretreatment Coloring composition pH coloring ΔE 6A 2C 1,300 3 3B 7 14.9 C1 2H 25,000 3 3B 7 7 C2 - - - 3B 7 9.8

The color change for each sample was assessed by determining the ΔE of the hair color after treatment compared to that of the hair color before treatment. The ΔE for hair treated with systems 6A and C1 and composition C2 is presented in Table 6-1 and on the . As can be seen, the ΔE for hair treated with system C1 (pretreatment composition with a polyethyleneimine having a molecular mass of 25,000) is lower than that of hair treated either with system 6A (pretreatment composition with a polyethyleneimine having a molecular mass of 1,300) or with the coloring composition C2 without pretreatment.

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

Example 6-2 – Comparison of the color provided by systems comprising pretreatment compositions having a polyethyleneimine of different molecular weights

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

System Pretreatment composition Amine molecular mass pH pretreatment Coloring composition pH coloring ΔE 6B 2G 2,000 3 3D 7 15.5 6C 2A 800 3 3D 7 19.3 C3 - - - 3D 7 12.2

The color change for each sample was assessed by determining the ΔE of the hair color after treatment compared to that of the hair color before treatment. The ΔE for hair treated with each of systems 6A-6C and composition C3 is presented in Table 6-2 and on the . As can be seen, the ΔE for hair treated with system 6B (pretreatment composition with a polyethyleneimine having a molecular mass of 2,000) is lower than that of hair treated with system 6C (pretreatment composition with a polyethyleneimine having a molecular weight of 2,000). a molecular mass of 800), but is higher than that of hair treated with the coloring composition C3 without pretreatment.

Example 6-2 shows that disclosed systems comprising pretreatment compositions having non-surfactant amine compounds with lower molecular weight surprisingly provide greater color change than systems comprising compositions pretreatment having amine-based compounds with a higher molecular mass.

As shown in the , which presents the percent change in ΔE of hair treated with systems comprising pretreatment compositions comprising non-surfactant amine-based compounds and then by coloring compositions according to the disclosure, as the molecular weight of the non-surfactant amine compound decreases, the ΔE increases surprisingly. 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.

Example 7 – Demonstration of the benefit of amine-based pretreatment compounds

The following Examples 7-1 and 7-2 show 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.

Example 7-1 – Comparison of the color provided by systems comprising pretreatment compositions having amine-based compounds with the color provided by pretreatment compositions having no amine-based compounds

The color provided to the hair by 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.

System Pretreatment composition Molecular mass of the agent pH pretreatment Coloring composition pH coloring ΔE 7A 2C 1,300 3 3F 7 27.2 C4 AA* 60.05 3 3F 7 18.2 C6 - - - 3F 7 18.8

*AA is a 1% aqueous solution of acetic acid (molecular weight 60.05) with a pH of 3

The color change for each sample was assessed by determining the ΔE of the hair color after treatment compared to that of the hair color before treatment. The ΔE for hair treated with each of systems 7A and C4 and composition C6 is presented in Table 7-1 and on the . As can be seen, the ΔE for hair treated with system 7A (pretreatment composition with an amine-based compound having a molecular mass of 1,300) is higher than that of hair treated with either system C4 (composition pretreatment with a non-amine-based compound having a molecular mass of 60.05) or with the coloring composition C6 without pretreatment. Notably, the ΔE of hair treated with acetic acid as a pretreatment agent was lower than that of hair treated with composition C6 without pretreatment.

Example 7-1 thus shows that the systems according to the disclosure comprising pretreatment compositions having amine-based compounds surprisingly provide a greater color change than the systems comprising pretreatment compositions having compounds based on amine. not being amine based, even at the same pH.

Example 7-2 – Comparison of the color provided by systems comprising pretreatment compositions having amine-based compounds with the color provided by pretreatment compositions having no amine-based compounds

The color provided to the hair by 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 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.

System Pretreatment composition Molecular mass of the agent pH pretreatment Coloring composition pH coloring ΔE 7B 2C 1,300 3 3C 7 16.4 C5 YOUR* 1701.2 3 3C 7 5.4 C7 - - - 3C 7 6.8

*TA is a 3% aqueous solution of tannic acid (molecular mass 1701.2) with a pH of 3

The color change for each sample was assessed by determining the ΔE of the hair color after treatment compared to that of the hair color before treatment. The ΔE for hair treated with each of systems 7B and C5 and composition C7 is presented in Table 7-2 and on the . As can be seen, the ΔE for hair treated with system 7B (pretreatment composition with an amine-based compound having a molecular mass of 1,300) is higher than that of hair treated with either system C5 (composition pretreatment with a non-amine-based compound having a molecular mass of 1,701.2) or with the coloring composition C7 without pretreatment. Notably, the ΔE of hair treated with tannic acid as a pretreatment agent was lower than that of hair treated with composition C7 without pretreatment.

Example 7-2 shows that disclosed systems comprising pretreatment compositions having lower pH surprisingly provide greater color change than systems comprising pretreatment compositions having non-based compounds. amine, even when the pretreatment agents are of the same molecular mass and the pretreatment compositions have the same pH.

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

The above examples show that the systems, methods and kits according to the disclosure surprisingly and unexpectedly provide an improvement in color deposition on hair compared to those which do not conform to the disclosure.

Claims (10)

Process for modifying hair color 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 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, relative to 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, relative to the total weight of the coloring composition. A method according to claim 1, wherein at least one non-surfactant amine compound has a molecular weight of less than about 10,000, preferably ranging from about 50 to about 10,000, more preferably ranging from about 50 to about 7,500 , more preferably ranging from about 100 to about 5,000, most preferably ranging from about 100 to about 2,500. Process according to claim 1 or claim 2, in which the at least one non-surfactant amine-based compound is chosen from synthetic and/or natural polyamines, preferably polyalkyleneimines, more preferably C2-C8 polyalkyleneimines, most preferably, a polyethyleneimine. 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 ranging from about 2 to about 7, ranging 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. Method according to any one of claims 1 to 4, in which the microtube-fuel composite comprises a halloysite-dye composite comprising at least one coloring agent, preferably chosen from anionic hair coloring agents, cationic hair coloring agents , non-ionic hair coloring agents and natural hair coloring agents. Method according to any one of claims 1 to 5, comprising a step of drying the hair after application of the pretreatment composition to the hair and before application of the coloring composition to the hair, in which the pretreatment composition is optionally removed from the hair by rinsing before drying the hair. Method according to any one of claims 1 to 6, in which steps (a) and/or (b) are repeated one or more times. 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 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, relative to the total weight of the pretreatment composition; And
in which the pH of the pretreatment composition is approximately 7 or less, preferably ranging from approximately 2 to approximately 7, more preferably ranging from approximately 2 to approximately 6, even more preferably ranging from approximately 2 to approximately 5, ranging so preferred among all from approximately 2 to approximately 4; And
(b) a coloring composition comprising at least one microtube-dye composite and at least one solvent,
in which, 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 approximately 8%, most preferably from approximately 1% to approximately 7% by weight, relative to the total weight of the coloring composition, and
in which the pH of the coloring composition is approximately 7 or less, preferably ranging from approximately 2 to approximately 7, more preferably ranging from approximately 2 to approximately 6, even more preferably ranging from approximately 2 to approximately 5, ranging so preferred among all from approximately 2 to approximately 4. A system according to claim 8, wherein the at least one non-surfactant amine compound has a molecular weight of less than about 10,000, preferably ranging from about 50 to about 10,000, more preferably ranging from about 50 to 7 500 approximately, more preferably ranging from approximately 100 to approximately 5,000, most preferably ranging from approximately 100 to approximately 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, nonionic hair coloring agents and natural hair coloring agents. Kit to modify hair color including:
(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 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, relative to the total weight of the pretreatment composition; And
in which the pH of the pretreatment composition is approximately 7 or less, preferably ranging from approximately 2 to approximately 7, more preferably ranging from approximately 2 to approximately 6, even more preferably ranging from approximately 2 to approximately 5, ranging so preferred among all from approximately 2 to approximately 4; And
(b) a second container containing a coloring composition comprising at least one microtube-dye composite and at least one solvent,
in which, 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 approximately 8%, most preferably from approximately 1% to approximately 7% by weight, relative to the total weight of the coloring composition, and
in which the pH of the coloring composition is approximately 7 or less, preferably ranging from approximately 2 to approximately 7, more preferably ranging from approximately 2 to approximately 6, even more preferably ranging from approximately 2 to approximately 5, ranging so preferred among all from approximately 2 to approximately 4.