Hair dyeing composition containing super-efficient high-water-property multi-layer emulsion system and preparation method of hair dyeing composition

Abstract

The present invention relates to a composition for hair dyeing comprising a multilayer gel emulsion comprising a hair dyeing formulation, and a method for preparing the same. The multilayer gel emulsion includes from about 0.5% to about 4.0% by weight of a cosmetically acceptable emulsified fat, a cosmetically acceptable nonionic surfactant, a water soluble suspension polymer, and at least 80% by weight of water.

Description

[0001] This application is a divisional application of Chinese Patent Application No. 202180020743.3 with a filing date of March 11, 2021. Background Art

[0002] Early hair coloring compositions, especially the vehicles for two-part oxidative coloring systems, contained high levels of organic solvents in combination with low HLB (hydrophilic / lipophilic balance) surfactants. Typically, the water content of the dye matrix was less than 30% by weight. When mixed with a developer containing an oxidizing agent (usually hydrogen peroxide) and a high percentage of water, the surfactant would precipitate out of solution in the form of a gel. This gel was an acceptable carrier for the dye and the developer active substances because it allowed the dye to quickly penetrate into the hair while providing sufficient viscosity and rheological properties so that the composition remained in place on the consumer's hair without dripping during a processing time of up to 1 hour or longer.

[0003] High organic solvent / low water hair coloring vehicles were very easy to manufacture because they dominated the permanent hair dye market throughout the 1980s. A significant drawback of these types of compositions was the inefficiency of the dye system. When compared to more advanced hair coloring systems with higher water content, high organic solvent / low water hair dyes could use up to twice (by weight %) the amount of dye precursors to achieve the same level of coloring and gray coverage.

[0004] Hair coloring systems with higher water content have become more popular because alkali-swellable polymers have become commercially available and are now stable in hydrogen peroxide. Materials sold under the trademarks Aculyn TM and Structure TM can be added to the developer portion of a permanent hair coloring system and maintain their integrity over an extended shelf life. Under acidic pH conditions, the polymer will remain uncrosslinked, keeping the composition thin and easy to pour. Once mixed with the dye portion, which typically has an alkaline pH, the increase in pH will cause the mixture to thicken immediately. Using anionic polymers in this way will allow formulators to create a dye phase with a higher level of water and little to no surfactant, solvent, or other materials that contribute to the viscosity and structure of the mixture.

[0005] When starting with a dye phase that already has a certain viscosity, U.S. Patent No. 7,419,510 describes a composition in which a conventional water-soluble anionic polymer is used in the dye phase. The developer requires a specific concentration of secondary ethoxylated fatty alcohols within the desired HLB range. When combined, a highly aqueous dye system is maintained, resulting in an appropriate mixture viscosity and flow properties.

[0006] The water content of the hair dyeing systems of many professional hair dye brands is higher than that of high organic solvent / low water hair dyes. However, these systems can use 10 - 20% by weight of fatty alcohols and emulsifiers to produce heavy crèmes and cream / gel colorants. These are most suitable for bowl and brush applications.

[0007] Embodiments of hair dyeing systems with a higher water content use dye precursors more effectively, although there is a degree of variability depending on the exact composition and desired results. In addition to the effective use of dye precursors, these hair dyeing systems can be milder, provide less staining, and are less likely to cause adverse reactions to the product user compared to conventional compositions. SUMMARY OF THE INVENTION

[0008] To improve hair dye efficiency, gray coverage, and color depth, provided herein are compositions for hair dyeing and covering gray that contain a multi-layer gel emulsion (gel MLE), the multi-layer gel emulsion comprising: (a) a hair dye formulation; (b) at least two cosmetically acceptable emulsifying fats; (c) a cosmetically acceptable non-ionic surfactant; (d) a water-soluble suspending polymer; and (e) water.

[0009] For example, the multi-layer gel emulsion (gel MLE) can contain: (a) a hair dye formulation; (b) at least two cosmetically acceptable emulsifying fats in an amount of about 0.5% to about 4.0% by weight; (c) a cosmetically acceptable non-ionic surfactant; (d) a water-soluble suspending polymer; and (e) at least 80% by weight of water. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 is a polarized light micrograph of a hair dye formulation in a light brown shade according to the present invention.

[0011] Figure 2 is a polarized light micrograph of a hair dye formulation in a light brown shade without emulsifying fat.

[0012] Figure 3 is a polarized light micrograph of a hair dye formulation in a black shade according to the present invention.

[0013] Figure 4It is a polarized light microscopic image of a hair dye formulation with a black hue that does not contain emulsified fat. Detailed Description

[0014] The present invention provides a composition for hair dyeing and covering gray hair, which further improves the efficiency of a highly aqueous medium by comprising, in addition to a cosmetically acceptable water-soluble suspension polymer, a low level of a cosmetically acceptable emulsified fat and a cosmetically acceptable nonionic surfactant to produce a multi-layer gel emulsion (gel MLE or gel network).

[0015] The cosmetically acceptable emulsified fat is a combination of at least two fat materials having a suitable HLB range of from about 4 to about 9, or from about 5 to about 9, to allow the formation of a multi-layer gel emulsion. In particular, the gel MLE with a high water content provides improved stability and effectiveness in delivering the hair dye components to the hair. Considering the water content in the system, the present invention relates to an oil-in-water emulsion.

[0016] Due to the sensitivity of dyes to oxidation, it can be challenging to stabilize hair dyes while optimizing the carrier efficiency. However, using a multi-layer gel emulsion, properties including consumer-pleasing aesthetics such as texture, reduced staining, and improved product stability during storage (i.e., reduced premature oxidation) can be achieved. It is believed that the emulsified fat can form a bilayer and can be used in the composition for hair dyeing to reduce or prevent dye staining of the skin or other surfaces, provide enhanced protection against premature oxidation of the colorant, improve the stability of the dye, and maximize the delivery of the dye to the hair. During the application of the hair dyeing composition or product, the mechanical action disrupts the sheer-thinning structure of the multi-layer gel emulsion (gel MLE), thus allowing for effective and controlled delivery of the active substances within the hair fiber and providing enhanced color delivery, gray coverage, and reduced skin / scalp staining.

[0017] The MLE can have a liquid crystal structure or a gel lamellar network structure. Liquid crystal MLEs have been described, for example, in U.S. Patent No. 7,754,775. The hair dyeing compositions described in WO2015 / 112787 also have liquid crystal MLEs. The use of liquid crystal MLEs results in an opaque hair dyeing composition with a cream consistency.

[0018] In contrast, the MLE in the hair dyeing composition described in the present invention is not a liquid crystal MLE, but a gel MLE, which has a gel rather than a cream consistency. Compared with the cream formulations having liquid crystal MLEs, the hair dyeing formulations having gel MLEs are generally more transparent or translucent.

[0019] Gel MLEs generally require less fat than liquid crystal MLEs. The higher amounts of fat present in liquid crystal MLEs can have adverse effects, including less efficient hair dyeing compositions, since cream formulations do not allow the dye precursors to effectively penetrate the hair.

[0020] Gel MLEs allow better penetration of the dye into the hair and thus can achieve better coloring results and gray coverage. Accordingly, when compared to the most effective high-aqueous vehicles in commercial applications, the compositions provided herein allow a significant reduction in the dye concentration. The effect is more significant for compositions designed for shorter dwell times of 5 to 10 minutes.

[0021] Without wishing to be bound by a particular theory, it is believed that the ultra-high efficiency effect is due to improved delivery of the dye precursors from the gel MLE; however, this is negated when the composition contains higher and more typical levels of emulsified fat, even when an MLE is formed. In such cases, the increased percentage of material and the cream rheology of the vehicle impede the penetration of the dye into the hair and cannot be used for deposition onto the hair. Since the cosmetically acceptable emulsified fat is at such a low level in the formulation, it can be suspended by thickening the composition with a cosmetically acceptable water-soluble suspending polymer. To form a multi-layer gel emulsion, the total HLB of the composition is from about 4 to about 9, or from about 5 to 9. The presence of the gel MLE structure can be confirmed, for example, by observing the sample through a polarizing filter at a magnification level of 400 under an optical microscope. In particular, the presence of light bursts similar to a "Maltese cross" pattern will be visible upon such examination. For example, in Figure 1 and 3 corresponding to Compositions 100 and 104 (Table 1), light bursts are clearly present. If the cosmetically acceptable emulsified fat, the cosmetically acceptable nonionic surfactant, and the water-soluble polymer do not combine to form a gel MLE, then upon examination with a polarizing filter microscope, light bursts with a Maltese cross pattern will not be seen, as shown, for example, in Figure 2 and 4 corresponding to Compositions 101 and 105 (Table 1). Without applying a polarizing filter, the light bursts are not visible even when a gel MLE is formed.

[0022] According to the present invention, at least two cosmetically acceptable emulsifying fats are used to achieve an HLB value of from about 4 to about 9, or from about 5 to about 9. The cosmetically acceptable emulsifying fats used according to the present invention are materials that do not have a charge group at their head end. For example, materials such as fatty alcohols, ethoxylated and propoxylated fatty alcohols, fatty esters, and vegetable oils can be cosmetically acceptable emulsifying fats. Nonionic materials such as Montanov 68 (cetearyl alcohol and cetearyl glucoside) from Seppic Inc. can also be used as cosmetically acceptable emulsifying fats. Additionally, certain phosphate esters that produce a negative charge when neutralized at an alkaline pH can be cosmetically acceptable emulsifying fats. The phosphate esters according to the present invention can be Crodafos CES (cetearyl alcohol, dicetyl phosphate, and ceteth-10 phosphate) or Crodafos CS20A (cetearyl alcohol, dicetyl phosphate, and ceteth-20 phosphate) from Croda, Inc. In one embodiment, at least two cosmetically acceptable fats are a combination of at least two phosphate esters. In one embodiment, at least two cosmetically acceptable fats are a combination of at least a nonionic material and a phosphate ester. Cosmetically acceptable emulsifying fats that can be used according to the present invention further include: ethylene glycol distearate, sorbitan trioleate, propylene glycol isostearate, ethylene glycol stearate, sorbitan sesquioleate, glyceryl stearate, lecithin, sorbitan oleate, sorbitan monostearate, sorbitan stearate, sorbitan isostearate, steareth-2, oleth-2, glyceryl laurate, ceteth-2, PEG-30 dipolyhydroxystearate, glyceryl stearate, Prolipid 141, isononyl ethoxylate-3, cetyl alcohol, stearyl alcohol, behenyl alcohol, cetearyl alcohol, almond oil, lanolin, apricot kernel oil, borage seed oil, rapeseed oil, castor oil, jojoba oil, olive oil, shea butter, soybean oil, behenyl alcohol, lauryl alcohol, myristyl alcohol, palmitic acid, stearic acid, sucrose cocoate, PEG-4 dilaurate, methyl glucoside sesquistearate, C11-15 pareth-3, sorbitan palmitate, PEG-8 dioleate, sorbitan laurate, PEG-40 sorbitan tetraoleate, laureth-4, PEG-7 glyceryl cocoate, PEG-20 almond glycerides, PEG-25 hydrogenated castor oil, sorbitan laurate, cetearyl olivate, sorbitan olivate, ceteth-20, isononyl ethoxylate-6, behenyl glucoside, stearamide MEA, PEG-100 stearate, polysorbate 85, PEG-7 oleate, and combinations thereof.

[0023] The content of the cosmetically acceptable emulsifying fat of the composition can be from about 0.5% to about 4% by weight, and the increased dye efficiency rapidly drops outside this range. In one embodiment, the content of the cosmetically acceptable fat of the composition can be from about 0.5% to about 3% by weight, or from about 0.5% to about 2% by weight, or from about 0.5% to about 1.5% by weight, or from about 0.5% to about 1% by weight, or from about 1.0% to about 1.5% by weight.

[0024] Cosmetically acceptable nonionic surfactants (which are also co-emulsifiers and viscosity builders and can be used according to the present disclosure) include: cetearyl glucoside, decyl glucoside, coco glucoside, lauryl glucoside, caprylyl capryl glucoside, PEG-8 oleate, polyglyceryl-3 methylglucose distearate, oleth-10, polyoxyethylene 10 oleyl ether, ceteth-10, PEG-8 laurate, cocoamide MEA, polysorbate 60, isoleth-10, polysorbate 80, isosteareth-20, PEG-60 almond glycerides, PEG-20 methylglucose sesquistearate, cetearyl alcohol polyether-20, oleth-20, steareth-20, steareth-21, ceteth-20, C11-15 pareth-7, C11-15 pareth-9, C11-15 pareth-30, steareth-10, steareth-100, polysorbate-20 and any combination thereof. The content of the cosmetically acceptable nonionic surfactant of the composition can be from about 0.1% to about 2% by weight, or from about 0.25% to about 1% by weight, and any combination thereof.

[0025] To obtain sufficient viscosity and the desired rheological properties for easy application by the consumer and adhesion to the hair, at least two cosmetically acceptable emulsifying fats and cosmetically acceptable nonionic surfactants are suspended in at least one water-soluble suspending polymer. The water-soluble suspending polymer can provide sufficient viscosity to keep the oil phase suspended. Thus, the viscosity of the product can be from about 5000 cps to about 200,000 cps, or from about 10,000 cps to about 175,000 cps, or from about 20,000 cps to about 150,000 cps, or from about 40,000 to about 100,000 cps.

[0026] There is no particular limitation on the type of water-soluble suspension polymer that can be used, but it should be suitable for application to hair. The water-soluble suspension polymer can be selected from: nonionic, anionic, cationic or amphoteric polymers, saturated or unsaturated long-chain fatty acids, carboxymethyl cellulose, sodium alginate, crosslinked homopolymers or associative polymers of acrylic acid or acrylamidopropylsulfonic acid, carbomers (including but not limited to Carbopol Ultrez 10), hydroxyethyl cellulose, hydroxypropyl cellulose, guar gum, xanthan gum, scleroglucan gum, hydroxyethyl cellulose, hydroxypropyl cellulose, guar gum, scleroglucan gum in quaternized form, polyquaternium-10, polyquaternium-7, polyquaternium-11, guar gum hydroxypropyltrimethylammonium chloride, hydroxypropylmethyl cellulose, carboxymethylhydroxyethyl cellulose, carboxymethylhydroxypropyl guar gum, or any combination thereof.

[0027] The water-soluble suspension polymer is part of the gel MLE system. The content of the water-soluble suspension polymer in the composition can be from about 0.1% by weight to about 2% by weight, or from about 0.3% by weight to about 1.7% by weight, or about 0.5% by weight and 1.5% by weight and any combination thereof. As described above, the viscosity can be adjusted to a preferred range according to the desired application method.

[0028] One embodiment of the present invention is a composition for hair coloring comprising a multilayer gel emulsion, wherein the multilayer gel emulsion comprises: (a) a hair coloring formulation; (b) at least two cosmetically acceptable emulsifying fats; (c) a cosmetically acceptable nonionic surfactant; (d) a water-soluble suspension polymer; and (e) water.

[0029] One embodiment of the present invention is a composition for hair coloring comprising a multilayer gel emulsion, wherein the multilayer gel emulsion comprises: (a) a hair coloring formulation; (b) at least two cosmetically acceptable emulsifying fats in an amount from about 0.50% by weight to about 4% by weight; (c) a cosmetically acceptable nonionic surfactant in an amount from about 0.1% by weight to about 2.0% by weight; (d) a water-soluble suspension polymer; and (e) at least 80% by weight of water, or from about 80% by weight to about 95% by weight of water, or from about 83% by weight to about 95% by weight of water, or from about 85% by weight to about 95% by weight of water, or from about 86% by weight to about 95% by weight of water, or from about 92% by weight to about 95% by weight of water.

[0030] The pH of the composition should be within the range that allows color development, preferably from about 5 to about 12.

[0031] The multi-layer gel emulsion in the composition for hair dyeing contains a hair dyeing formulation (which can be a developer such as hydrogen peroxide, persulfate, percarbonate, or any other developer used in traditional two-component hair dyeing systems or kits), or a hair dyeing composition. The hair dyeing composition referred to herein is an aqueous composition containing an oxidative dye, a non-oxidative dye, or any combination thereof.

[0032] Oxidative (or oxidation) dyes are a class of compounds used in traditional two-component permanent hair dyeing systems, where the oxidative dyes undergo oxidation when mixed with an oxidizing agent such as hydrogen peroxide. These two-component kits typically contain an alkaline composition of the oxidative hair dye in a liquid, gel, or cream vehicle, and a developer composition using an oxidizing agent (usually hydrogen peroxide). The two compositions are mixed immediately before application to the hair. The alkaline pH of the resulting mixture causes the hair to swell dry, allowing the dye precursors to penetrate into the cortex of the hair. These dye precursors are then oxidized and combined to form larger molecules. These larger molecules contain a significant level of conjugated double bonds, thus producing a coloring product visible from the outside of the hair. After an appropriate developing time for the composition to remain on the hair, the mixture is rinsed off the hair. Then the color of the hair is permanently changed. Depending on the pH of the mixture and the concentration of the developer, these systems can have the ability to both brighten the natural pigment of the hair and deposit color, or only have the ability to deposit color.

[0033] Oxidative dye precursors are mainly aromatic compounds and generally have low molecular weights. Oxidative dyes form the basis of hair dyes and are usually divided into two groups: primary intermediates and couplers. Thus, primary intermediates form the basis of permanent hair dyeing products.

[0034] In certain embodiments, the primary intermediate is selected from para-substituted benzene derivatives such as p-phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine sulfate, p-aminophenol, 2,4,5,6-tetraaminopyrimidine, p-toluenediamine, 2-chloro-p-phenylenediamine, N-phenyl-p-phenylenediamine, p-methylaminophenol, 1-amino-4-(2-methoxyethyl)-aminobenzene, 2-(hydroxymethyl)-p-phenylenediamine, 3-methyl-p-aminophenol, 2-(2-hydroxyethyl)-p-phenylenediamine, 4,4'-diaminodiphenylamine, 1,3-dimethyl-2,5-diaminobenzene, 2-isopropyl-p-phenylenediamine, N-(β-hydroxypropyl)-p-phenylenediamine, 2-methyl-p-aminophenol, N-2-methoxyethyl-p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 3-methyl-p-aminophenol, 2-propyl-p-phenylenediamine, 2-(2'-hydroxyethylaminomethyl)-p-aminophenol, 2-(methoxymethyl)-p-aminophenol, 2-methyl-4-dimethylaminoaniline, 5-aminosalicylic acid, 2,3-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, N,N-dipropyl-p-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, 4-N,N-bis(2-hydroxyethyl)-amino-2-methylaniline, 4-N,N-bis(2-hydroxyethyl)-amino-2-chloroaniline, 2-(2-hydroxyethyl)-p-phenylenediamine, 2-fluoro-p-phenylenediamine, N-(2-hydroxypropyl)-p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N,N-dimethyl-2-methyl-p-phenylenediamine, N-ethyl-N-(2-hydroxyethyl)-p-phenylenediamine, N-(2,3-dihydroxypropyl)-p-phenylenediamine, N-(4'-aminophenyl)-p-phenylenediamine, 2-(2-hydroxyethoxy)-p-phenylenediamine, 2-(acetylaminoethoxy)-p-phenylenediamine, 2-methyl-1-N-(2-hydroxyethyl)-p-phenylenediamine, 4-methyl-o-phenylenediamine, their salts and any combination thereof.

[0035] The hair dyeing composition may further comprise at least one dye coupler. The dye coupler is used to develop tones and obtain a wider color spectrum imparted by the hair dyeing composition. The dye coupler may be selected from meta-substituted benzene derivatives: resorcinol, 4-chlororesorcinol, 2-methylresorcinol, metol, 1-naphthol, 1,5-naphthalenediol, 2,7-naphthalenediol, 2,4-diaminophenol, hydroxybenzomorpholine, 1-hydroxy-3-dimethylaminobenzene, 4-amino-2-hydroxytoluene, 2-methyl-5-hydroxyethylaminophenol, 1-methoxy-2,5-diaminobenzene, phenylmethylpyrazolone, 2,4-diaminophenoxyethanol HCl, 4-ethoxy-m-phenylenediamine, 1-hydroxy-3-amino-4,6-dichlorobenzene, 1-hydroxy-2,5-diamino-4-methoxybenzene, 4-amino-m-cresol, 6-amino-m-cresol, 2-amino-4-hydroxyethylaminophenyl methyl ether, 5-amino-6-chloro-o-cresol, 6-amino-o-cresol, 4,6-bis(2-hydroxyethoxy)-m-phenylenediamine, 5-amino-4-chloro-o-cresol, 2-ethylamino-p-cresol, 2-amino-5-acetamidophenol, 2-methyl-1-naphthol, 1-acetoxy-2-methylnaphthalene, 1-hydroxy-6-aminonaphthalene-3-sulfonic acid, thymol, 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene, 2-chlororesorcinol, N,N-bis(hydroxyethyl)-2,4-diaminophenetole, 4,6-bis(hydroxyethyl)-m-phenylenediamine, N,N-bis(hydroxyethyl)-m-phenylenediamine, 2,6-diaminotoluene, 6-hydroxybenzomorpholine, 2-hydroxy-4-hydroxyethylaminotoluene, 4,6-dichloro-metol, 2-methyl-metol, 2-chloro-6-methyl-metol, 2-hydroxyethoxy-5-aminophenol, 2-chloro-5-trifluoroethylaminophenol, 4-chloro-6-methyl-metol, N-hydroxyethyl-4-methoxy-2-methyl-metol, 5-amino-4-methoxy-2-methylphenol, 2-dimethylamino-5-aminopyridine, 6-methoxy-8-aminoquinoline, 2,6-dihydroxy-4-methylpyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 5-chloro-2,3-dihydroxypyridine, 4-hydroxyindole, 5,6-dihydroxyindole, 7-hydroxyindole, 5-hydroxyindole, 2,3-dihydroxynaphthalene, 5-methyl-o-aminophenol, 6-methyl-o-aminophenol, 2-amino-5-acetamidophenol, 1,7-dihydroxynaphthalene, 1-hydroxy-6-aminonaphthalene-3-sulfonic acid, 2,3-dihydroxy-1,4-naphthoquinone, 3,4-methylenedioxy-1((β-hydroxyethyl)amino)benzene, 3,4-methylenedioxyphenol, 1-methoxy-2-amino-4-((β-hydroxyethyl)amino)benzene, 1-naphthol-4-sulfonic acid, m-phenylenediamine, 2,6-diaminotoluene, N,N-bis(hydroxyethyl)-2,4-diaminophenetole, bis(2,4-diaminophenoxy)-1,3-propane, 1-hydroxyethyl-2,4-diaminobenzene, aminoethoxy-2,4-diaminobenzene, 2,4-diaminophenoxyacetic acid, 2,4-diamino-5-methylphenetole, 2,4-diamino-5-hydroxyethoxytoluene, 2,4-dimethoxy-1,3-diaminobenzene, 2,6-bis(hydroxyethylamino)-toluene, 2-hydroxy-4-carbamoylmethylaminotoluene, 2-chloro-6-methyl-m-aminophenol, 2-hydroxyethoxy-5-aminophenol, N-cyclopentyl-3-aminophenol, N-hydroxyethyl-4-methoxy-2-methyl-m-aminophenol, 5-amino-4-methoxy-2-methylphenol, 6-methoxy-8-aminoquinoline, 5-hydroxy-1,4-benzodioxane, 3,4-methylenedioxyphenol, 4-hydroxyethylamino-1,2-methylenedioxybenzene, 2,6-dihydroxy-3,4-dimethylpyridine, and any combination thereof.,

[0036] Auto-oxidation (air oxidation) dyes are a subclass of oxidation dyes in which the dye undergoes auto-oxidation in the presence of air without the need to mix with a separate developer / oxidizing agent to develop color in the hair. After the air oxidation dye and the primary intermediate are applied to the hair in combination, they rapidly oxidize upon exposure to atmospheric oxygen to form a coupling product to impart color to the hair. The most effective air oxidation products are those that use transition metal salts to catalyze the air oxidation reaction. These compositions are capable of achieving gray coverage similar to formulations mixed with hydrogen peroxide.

[0037] In one embodiment, the air oxidation precursors are selected from: 1,2,4-benzenetriol, 2,4,5-trihydroxytoluene, pyrogallol, 2,5-dihydroxyanisole, 3,4-diaminophenol, 3,4-diaminoanisole, 5,6-dihydroxyindole and its derivatives, 5,6-dihydroxyindoline and its derivatives, 2-hydroxy-p-phenylenediamine, N-methyl-2-hydroxy-p-phenylenediamine, N,N-dimethyl-2-hydroxy-p-phenylenediamine, 2-methoxy-p-phenylenediamine, 2,4-diaminophenol, 2,4-diaminoanisole, 3,4-dihydroxyanisole, 4-amino-2-hydroxyphenol, 2-methoxy-4-aminophenol, 2-hydroxy-4-aminomethoxybenzene, 2-amino-4-hydroxyphenol, 2-amino-4-methoxyphenol, 2-amino-4-hydroxymethoxybenzene, 2-amino-p-phenylenediamine, 2,4-dihydroxyaniline, 3-methoxy-4-aminophenol, and similar compounds having N-substituted alkyl groups such as: methyl, ethyl, propyl, methanol, ethanol, isopropanol, and any combination thereof.

[0038] Non-oxidative dyes are dyes (coloring molecules) that can be directly applied to hair to obtain semi-permanent color. Non-limiting examples of non-oxidative dyes include: Acid Yellow 1, Disperse Red 17, Basic Brown 17, Acid Black 1, 4-nitro-o-phenylenediamine, picramic acid, HC Red 13, N,N'-bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine, HC Red 7, HC Blue 2, HC Yellow 4, HC Yellow 2, HC Orange 1, HC Red 1, HC Red 3, 4-amino-3-nitrophenol, 2-hydroxyethylamino-5-nitroanisole, 3-nitro-p-hydroxyethylaminophenol, 3-methylamino-4-nitrophenoxyethanol, 2-nitro-5-glycerylmethylaniline, HC Violet 1, HC Orange 2, HC Yellow 9, 4-nitrophenylaminoethylurea, HC Red 10, HC Red 11, 2-hydroxyethyl picramic acid, HC Blue 12, hydroxyethyl-2-nitro-p-toluidine, HC Blue 11, HC Yellow 7, HC Yellow 10, 4-amino-2-nitrophenyl-amine-2'-carboxylic acid, 2-chloro-6-ethylamino-4-nitrophenol, HC Violet 2, 2-amino-6-chloro-4-nitrophenol, HC Yellow 13, 2,6-diamino-3-((pyridin-3-yl)azo)pyridine, Basic Orange 69, N-(2-nitro-4-aminophenyl)-allylamine, Basic Violet 2, Basic Red 51, Basic Yellow 87, Basic Orange 31, HC Blue 16, Basic Red 76, Basic Brown 16, Basic Yellow 57, Acid Orange 7, Acid Red 33, Acid Yellow 23, Acid Blue 9, Acid Red 92, Acid Yellow 3, Basic Blue 99, Acid Violet 43, Disperse Violet 1, Acid Blue 62, Disperse Black 9, hydroxyanthraquinone aminopropyl methylmorpholinium methyl sulfate, lawsone, henna, hc Blue 14, curry re, Acid Red 18, Acid Red 52, Acid Green 25 and Disperse Blue 377.

[0039] In certain embodiments, the composition for hair dyeing further comprises at least one reagent known for use in hair dyeing compositions. One or more of these reagents can be added to enhance the formation of the gel MLE or to improve other beneficial properties such as rheology, softening or conditioning effects. The reagents can include: conditioners, alkalizing agents, humectants, catalysts, cationic surfactants, polymers or any combination thereof.

[0040] Any suitable conditioner can be used. In certain embodiments, the conditioner is selected from: quaternized gums, quaternized polymers, quaternary ammonium salts, synthetic oils, vegetable oils, natural or synthetic waxes, silicones, fatty amines, cationic and amino-functional polysiloxanes, quaternized proteins, quaternized polysaccharides, polyamines, polyaminoamides, cationic celluloses, quaternary polymers of vinyl pyrrolidone and vinyl imidazole, polyalkyleneimines and any combination thereof. The conditioner content of the composition can be from about 0.1 wt% to about 2 wt% to maintain the high water integrity of the composition.

[0041] The alkalizing agent can be organic or inorganic. In certain embodiments, the alkalizing agent is selected from: ethanolamine, triethanolamine, aminomethylpropanol, ammonium hydroxide, carbonates, bicarbonates, isopropanolamine, propan-1,3-diamine, oxyethylated and oxypropylated hydroxyalkylamines, and ethylenediamine, polyamines, sodium hydroxide, potassium hydroxide, alkali silicate, alkali metasilicate, and any combination thereof. The alkalizing agent content of the composition can be from about 0.01 wt% to about 10 wt%, or from about 0.1 wt% to about 7 wt%, or from about 0.5 wt% to about 5 wt%, and any combination thereof.

[0042] Any humectant for use on hair can be added to the compositions disclosed herein. For example, humectants can include humectants, occlusives, and emollients. Humectants can be selected from the group consisting of: polydimethylsiloxane, petrolatum, paraffin wax, lanolin, natural oils, mineral oils, glycerin, sorbitol, sodium hyaluronate, hyaluronic acid, urea, propylene glycol, alpha-hydroxy acids, sugars, propylene glycol, ceramides, 1,2,6-hexanetriol, butylene glycol, dipropylene glycol, hexylene glycol, panthenol, phytantriol, inositol, hexylene glycol, hydrolyzed silk protein, hydrolyzed keratin, erythritol, octylene glycol, squalene, cocoa butter, shea butter, lecithin, and beeswax. The humectant content of the composition can be from about 0.01 wt% to about 2 wt%, or from about 0.1 wt% to about 1.7 wt%, and any combination thereof.

[0043] The catalyst can be used with air oxidation dyes. The catalyst can be a water-soluble salt of a transition metal such as copper, cobalt, zinc, silver, nickel, and / or iron. In another embodiment, the catalyst is a metal, metal salt, and / or metal complex, wherein the metal is selected from: manganese, copper, cobalt, zinc, silver, nickel, chromium, vanadium, molybdenum, osmium, ruthenium, rhodium, palladium, platinum, cadmium, iron, and any combination thereof. The salts can be selected from: sulfates, chlorides, nitrates, carbonates, phosphates, fumarates, citrates, and / or tartrates. In one embodiment, the catalyst is a manganese salt. The catalyst content can be from about 0.01 wt% to about 1.0 wt%, or from about 0.05 wt% to about 0.5 wt%, or from about 0.1 wt% to about 0.4 wt%, and any combination thereof.

[0044] Cationic surfactants can be used in the compositions according to the present disclosure. These cationic surfactants can be selected from the group consisting of: behenyl trimethyl ammonium chloride, behenyl trimethyl ammonium methyl sulfate, benzalkonium chloride, cetrimonium chloride, cinnamidopropyl trimethyl ammonium chloride, cocoyl trimethyl ammonium chloride, dicetyldimethyl ammonium chloride, dicocoyl dimethyl ammonium chloride, dihydrogenated tallow dimethyl ammonium chloride, hydrogenated palm trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, quaternium-15, quaternium-18, bentonite quaternium-18, quaternium-22, stearalkonium chloride, tallow trimethyl ammonium chloride, tricetyl dimethyl ammonium chloride, myristyl methyl ammonium bromide, cetyl trimethyl ammonium bromide, olealkonium chloride, isostearamidopropyl ethyldimethyl ammonium ethyl sulfate, and PEG-9, and any combination thereof. The content of the cationic surfactant in the composition can be from about 0.1% by weight to about 2% by weight.

[0045] Any other ingredients known in the art for formulating hair dyeing compositions can also be added to the compositions according to the present invention, including but not limited to at least one opacifier such as ethylene glycol stearate, stearamide AMP, at least one preservative such as a parabens preservative, at least one fragrance, at least one chelating agent, at least one antioxidant and / or at least one hair growth active ingredient.

[0046] Chelating agents can be added to increase the stability of the product by reducing the presence of metal ions, which otherwise, if present, may cause damage to the hair or undesirably color the hair. The chelating agents can be selected from: EDTA, sodium salts of EDTA, HEDTA, etidronic acid, citric acid, aminopolycarboxylic acids, 2,3-dihydroxybenzoic acid, dimercaptosuccinic acid, iminodiacetic acid, gluconic acid, trisodium citrate, and any combination thereof. The content of the chelating agent in the composition can be from about 0.01% by weight to about 1% by weight.

[0047] For stability reasons, the antioxidant content in the composition can be adjusted to delay the onset of coloring, or to minimize potential staining of the skin, or simply added in small amounts to increase the absorption of the dye on the hair. When used, the antioxidant content can be from about 0.02% to about 1% by weight of the composition. Further increasing the antioxidant content can lead to poor color deposition in the hair. Any antioxidant or reducing agent or a combination thereof can be used, including but not limited to sodium sulfite, bisulfite, thioglycolate, erythorbic acid, etidronic acid, ascorbic acid, thiosulfate, ascorbic acid compounds, cysteine, sodium dithionite, thiourea, thiolactic acid, glyceryl monothiolgycolate, thioglycerol, 2,5-dihydroxybenzoic acid, zinc formosulfoxylate, and any combination thereof.

[0048] Another embodiment of the present disclosure is a method for preparing a composition for hair dyeing comprising a multi-layer gel emulsion. The method comprises the steps of: a) heating a formulation comprising water to obtain heated water in which a dye, an antioxidant, and a chelating agent are dissolved, b) dispersing a water-soluble suspension polymer in the aqueous phase, c) mixing a cosmetically acceptable emulsifying fat in the hot water / polymer phase, d) simultaneously cooling and homogenizing the mixed and heated formulation to obtain a hair dyeing composition in the form of a multi-layer gel emulsion.

[0049] Homogenization as used herein is a method of breaking an oil and water system using a high-speed high-shear device to prepare a fine emulsion. While the use of a homogenizer in the heating step of the present invention is optional, homogenization should be used during the cooling step to ensure the successful formation of the MLE according to the present invention. It has been found that the MLE is not formed in the absence of homogenization introduced during the cooling step. Any homogenizer capable of performing the above process can be used, i.e., a device for achieving high speed and high shear. For example, one such homogenizer is the Olsa MAXILAB.

[0050] In the cooling step, the mixed and heated formulation is cooled from a temperature far above the melting point of the cosmetically acceptable emulsifying fat to a temperature below the melting point of each of these.

[0051] The terms used in connection with this embodiment have the same meaning as the terms with respect to the above embodiment.

[0052] Examples

[0053] Specific embodiments of the present invention will now be illustrated with reference to the following examples. It should be understood that these examples are merely disclosed for the purpose of illustrating the present invention and should not limit the scope of the present invention in any way.

[0054] Example 1

[0055] High-water-content hair dyeing compositions with and without cosmetically acceptable emulsified fats. A hair dyeing composition of a two-component hair dyeing system containing a low level of fat (and gel MLE) is prepared using the ingredients listed in Table 1.

[0056] Table 1

[0057]

[0058] The above hair dyeing composition was mixed with a commercially available cream developer at a ratio of 1:1 and applied to 90% gray hair (from humans in IHIP) for 5 minutes, 10 minutes, and 20 minutes respectively. The resulting color of the sample was measured using a Hunterlab Ultra Scan colorimeter (L a b color scale). The L value ranges from 0 to 100, which represents the color intensity, where L = 100 is white and L = 0 is black. There are no numerical limitations for the "a" and "b" values. +a is red and -a is green, +b is yellow and -b is blue. A Δ"L" of 0.5 or greater is visible to the human eye. It was found that including a small amount of cosmetically acceptable emulsified fat (which produces gel MLE) in an already effective hair dyeing system would significantly enhance color delivery, with a change in color depth (L value) of up to 7.7 units (Table 2). This improved efficiency is most evident at short dwell times (e.g., 5 - 10 minutes), but is also visible at a 20-minute dwell time.

[0059] Table 2. L a b values of the colored samples after coloring for 5 minutes using various formulations

[0060]

[0061]

[0062] Example 2

[0063] High-water-content hair dyeing compositions with and without cosmetically acceptable emulsified fats. A hair dyeing composition of a single-component hair dyeing system containing a low level of fat (and gel MLE) with an air oxidation dye (e.g., not mixed with a developer) is prepared using the ingredients listed in Table 3.

[0064] Table 3

[0065]

[0066] The above compositions were separately dyed on 90% grey hair (human from IHIP) for 10 and 20 minutes. The resulting color of the samples was recorded using a Hunterlab Ultra Scan colorimeter. It was found that inclusion of a small amount of emulsified fat (which gives gel MLE) in an already effective hair dyeing system significantly promoted color delivery, with a change in color depth (L value) of up to 4.5 units. This improved efficiency was most evident at short dwell times (e.g., 5 - 10 minutes), but was also visible at a 20 - minute dwell time (Table 4).

[0067] Table 4. L a b values of the colored samples after 10 minutes of coloring using a single - component formulation

[0068] 10-minute staining "L” "a” "b” ΔL Light brown with fat, No. 106 28.7 5.0 11.9 Light brown without fat, No. 107 33.2 4.8 13.0 4.5 Black with fat, No. 110 19.8 1.3 2.2 Black without fat, No. 111 21.9 2.3 4.8 2.1

[0069] While the invention has been described above with reference to specific embodiments of the invention, it will be apparent that many changes, modifications, and variations can be made without departing from the concepts disclosed herein. Accordingly, it is intended to embrace all such changes, modifications, and variations that fall within the spirit and broad scope of the appended claims.

Claims

1. A method for preparing a composition for hair dyeing comprising a multi-layer gel emulsion, wherein the multi-layer gel emulsion comprises: (a) a hair dye formulation; (b) at least two cosmetically acceptable emulsifying fats; (c) a cosmetically acceptable non-ionic surfactant; (d) a water-soluble suspension polymer; and (e) water, wherein the content of the cosmetically acceptable emulsifying fat in the composition is from 0.5% to 4.0% by weight, wherein the content of the cosmetically acceptable non-ionic surfactant is from 0.1% to 2% by weight, and wherein the water content of the composition is at least 80% by weight, the method comprising: Heat a formulation containing water to obtain heated water; In the formulation obtained during heating, mix the water-soluble suspension polymer and the at least two cosmetically acceptable emulsifying fats; Simultaneously cool and homogenize the mixed and heated formulation to obtain a multi-layer gel emulsion.

2. The method according to claim 1, wherein the at least two cosmetically acceptable emulsifying fats are selected from: ethylene glycol distearate, sorbitan trioleate, propylene glycol isostearate, ethylene glycol stearate, sorbitan sesquioleate, glyceryl stearate, lecithin, sorbitan oleate, sorbitan monostearate, sorbitan stearate, sorbitan isostearate, steareth-2, oleth-2, glyceryl laurate, ceteth-2, PEG-30 dipolyhydroxystearate, Prolipid 141, isononyl ethoxylate-3, cetyl alcohol, stearyl alcohol, behenyl alcohol, cetearyl alcohol, almond oil, lanolin, apricot kernel oil, borage seed oil, rapeseed oil, castor oil, jojoba oil, olive oil, shea butter, soybean oil, lauryl alcohol, myristyl alcohol, palmitic acid, stearic acid, sucrose cocoate, PEG-4 dilaurate, methyl glucoside sesquistearate, C11-15 pareth-3, sorbitan palmitate, PEG-8 dioleate, sorbitan laurate, PEG-40 sorbitan tetraoleate, lauryl ethoxylate-4, PEG-7 glyceryl cocoate, PEG-20 almond glyceride, PEG-25 hydrogenated castor oil, sorbitan laurate, cetearyl olivate, sorbitan olivate, cetearyl ethoxylate-20, isononyl ethoxylate-6, behenyl glucoside, stearamide MEA, PEG-100 stearate, polysorbate 85, PEG-7 and combinations thereof.

3. The method according to claim 1, wherein the at least two cosmetically acceptable emulsifying fats are phosphate esters and non-ionic materials.

4. The method according to any one of claims 1 - 3, wherein the cosmetically acceptable nonionic surfactant is selected from: cetearyl glucoside, decyl glucoside, coco glucoside, lauryl glucoside, octyldodecyl glucoside, PEG - 8 oleate, polyglyceryl - 3 methylglucose distearate, oleth - 10, polyoxyethylene 10 oleyl ether, ceteth - 10, PEG - 8 laurate, cocoamide MEA, polysorbate 60, isoocteth - 10, polysorbate 80, isosteareth - 20, PEG - 60 almond glycerides, PEG - 20 methyl glucose sesquistearate, cetearyl ethoxylate - 20, oleth - 20, steareth - 20, steareth - 21, ceteth - 20, C11 - 15 pareth - 7, C11 - 15 pareth - 9, C11 - 15 pareth - 30, steareth - 10, steareth - 100, polysorbate - 20 and any combination thereof.

5. The method according to any one of claims 1 - 3, wherein the water - soluble suspension polymer is a nonionic, anionic, cationic or amphoteric polymer, a saturated or unsaturated long - chain fatty acid, carboxymethyl cellulose, sodium alginate, a cross - linked homopolymer or associative polymer of acrylic acid or acrylamidopropylsulfonic acid, carbomer, hydroxyethyl cellulose, hydroxypropyl cellulose, guar gum, xanthan gum, scleroglucan, the quaternized form of hydroxyethyl cellulose, hydroxypropyl cellulose, guar gum, scleroglucan, polyquaternium - 10, polyquaternium - 7, polyquaternium - 11, guar hydroxypropyltrimonium chloride, hydroxypropyl methyl cellulose, carboxymethyl hydroxyethyl cellulose, carboxymethyl hydroxypropyl guar gum, or any combination thereof.

6. The method according to any one of claims 1 - 3, wherein the water - soluble suspension polymer is carbomer or xanthan gum.

7. The method according to any one of claims 1 - 3, wherein the mixing further comprises mixing in at least one reagent selected from: conditioning agents, alkalizing agents, antioxidants, humectants, catalysts and any combination thereof.

8. The method according to any one of claims 1 - 3, wherein the mixing further comprises mixing in an oxidative dye.

9. The method according to any one of claims 1 - 3, wherein the mixing further comprises mixing in a non - oxidative dye.

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