Sulfur-containing anti-dandruff compositions with enhanced efficacy and aesthetics

By optimizing the particle size and formulation methods of sulfur in shampoo, combining surfactant, stable polymer and suspended wax, the problems of excessive sulfur deposition and foul smell are solved, the stability and beauty effect of the product are improved, and the more Long-term anti-dandruff effect.

CN115151310BActive Publication Date: 2024-12-20PROCTER & GAMBLE CO
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Patent Information

Application Number
CN202080097513.2
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Priority Date
2020-02-27
Filing Date
2020-12-04
Publication Date
2024-12-20
Estimated Expiration
2040-12-04

AI Technical Summary

Technical Problem

The small particle size of sulfur in existing shampoos leads to excessive deposition on the scalp, affecting the use effect, and the sulfur reacts with the skin to produce a foul smell, and the physical instability of large-grained sulfur leads to sedimentation problems.

Method used

Personal care compositions using 10% to 25% surfactant, 0.1% to 10% sulfur (average particle size 5μm to 150μm), 0.05% to 10% stable polymer and 0.01% to 4% suspension wax , optimize the particle size and formulation methods of sulfur through simulation and modeling analysis to improve stability and beauty effects.

Benefits of technology

It achieves a longer effect of sulfur on the scalp, reduces foul odor, improves the physical stability and beauty effect of the product, and ensures more efficient anti-dandruff effect.

✦ Generated by Eureka AI based on patent content.

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Patent Text Reader

Abstract

The present invention relates to a personal care composition comprising: from about 10% to about 25% of one or more surfactants; from about 0.1% to 10% of sulfur; wherein the sulfur has an average particle size (D50) of from about 5 μm to about 150 μm; from about 0.05% to about 10% of one or more stabilizing polymers; and from about 0.01% to about 4% of a suspending wax.
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Description

Technical Field

[0001] The present invention relates to personal care compositions wherein it has surprisingly been discovered that the addition of larger particle sulfur provides powerful benefits while minimizing inherent sulfur malodor aesthetics. Background Art

[0002] It has been found that conventional wisdom in the anti-dandruff shampoo category is that achieving maximum efficacy benefit from deposited particulate anti-dandruff (AD) actives is a function of reducing particle size and maximizing deposition on the scalp. Quite surprising to conventional understanding, we have found that when working with sulfur, the opposite applies. The present invention has shown that due to the higher solubility of sulfur in sebum (many orders of magnitude when compared to common AD actives such as zinc pyrithione), reducing its surface area on the scalp via increasing particle size ensures that the active has a significantly longer resonance time on the scalp relative to smaller particles that dissolve more quickly and dilute below the minimum inhibitory concentration (MIC). Further analysis via simulation and modeling exercises showed that there is also a reduced return point where particle size becomes too large, thereby reducing solubility to the point where the desired efficacy dose is never reached. This understanding allows the present invention to use particles of a target size range to maximize the efficacy efficiency of our AD products at lower deposition amounts than we can achieve with smaller particles and increased deposition.

[0003] In addition to the AD efficacy benefits achieved by moving to larger particles, there is also a direct link to the consumer acceptability of the product through the reduction of malodors associated with sulfur-containing products. These malodors are formed when sulfur interacts with specific chemical moieties in the skin to produce strong and unpleasant compounds such as hydrogen sulfide and methyl mercaptan. By minimizing the amount of sulfur deposited on the skin while maintaining effective dosing through the use of sulfur with increased particle size, the expected tradeoff between clinical performance and cosmetic acceptance can be significantly alleviated.

[0004] As the particle size of sulfur actives has increased in desire, the new technological dilemma has presented itself in the form of compromised finished product shelf stability. Early formulation efforts utilizing larger particle sizes of sulfur, while effective, have proven to be physically unstable, resulting in significant in situ settling of the sulfur particles. Research to address this problem has shown that by using a complementary combination of stabilizing ingredients, products that are not only physically shelf stable, but also cosmetically acceptable and processable can be achieved on a large scale. Summary of the invention

[0005] The present invention relates to a personal care composition comprising: from about 10% to about 25% of one or more surfactants; from about 0.1% to 10% of sulfur; wherein the sulfur has an average particle size (D50) of from about 5 μm to about 150 μm; from about 0.05% to about 10% of one or more stabilizing polymers; and from about 0.01% to about 4% of a suspending wax. BRIEF DESCRIPTION OF THE DRAWINGS

[0006] Figure 1 A 2 micron (μm) sulfur particle size simulation using a dissolution and diffusion model.

[0007] Figure 2 A simulation of a 34 micron (μm) sulfur particle size using a dissolution and diffusion model.

[0008] Figure 3 A simulation of a sulfur particle size of 100 micrometers (μm) using a dissolution and diffusion model.

[0009] Figure 4 A sulfur particle size of 150 micrometers (μm) was simulated using a dissolution and diffusion model.

[0010] Figure 5 This is a photograph of sample A after it was left to stand for 16.434 hours after being homogenized at 40°C.

[0011] Figure 6 This is a photograph of sample C after it was left to stand for 16.102 hours after being homogenized at 40°C.

[0012] Figure 7 is a schematic diagram of this type of tunneling failure mode.

[0013] Figure 8 This is a photograph of sample D after it was left to stand for 110.5 days after being homogenized at 40°C.

[0014] Fig. 9 This is a photograph of sample B after it was left to stand for 110 days after being homogenized at 40°C.

[0015] Fig.10 is a schematic diagram in which 5% sulfur particles (SP) exert a net downward force and silicone droplets (SD) provide a smaller upward force. DETAILED DESCRIPTION

[0016] Unless otherwise indicated, all percentages and ratios used herein are by weight of the total composition. Unless otherwise indicated, all measurements are understood to be made under ambient conditions, wherein "ambient conditions" means conditions at about 25°C, at about one atmosphere of pressure, and at about 50% relative humidity. All numerical ranges are inclusive of narrower ranges; the upper and lower limits of the ranges described are combinable to form additional ranges not explicitly described.

[0017] The compositions of the present invention may comprise, consist essentially of, or consist of the essential components and optional ingredients described herein. As used herein, "consisting essentially of" means that the composition or component may include additional ingredients as long as the additional ingredients do not materially change the basic and novel characteristics of the claimed composition or method.

[0018] "Applying" or "applying" as used with reference to a composition means applying or spreading the composition of the present invention onto keratinous tissue such as hair.

[0019] "Dermatologically acceptable" means that the compositions or components described are suitable for use in contact with human skin tissue without undue toxicity, incompatibility, instability, allergic response, and the like.

[0020] A "safe and effective amount" refers to an amount of a compound or composition sufficient to significantly induce a positive beneficial effect.

[0021] While the specification concludes with claims which particularly point out and distinctly claim the invention, it is believed that the present invention will be better understood from the following description.

[0022] As used herein, the term "fluid" includes liquids and gels.

[0023] As used herein, the articles including "a" and "an" when used in a claim should be understood to mean one or more of what is claimed or described.

[0024] As used herein, "comprising" means that other steps and other ingredients which do not affect the end result can be added. The term encompasses the terms "consisting of" and "consisting essentially of."

[0025] As used herein, "mixture" is intended to include a simple combination of substances as well as any compounds that may result from their combination.

[0026] As used herein, "molecular weight" refers to weight average molecular weight, unless otherwise indicated.Molecular weight is measured using the industry standard method, gel permeation chromatography ("GPC").

[0027] Where content ranges are given, these should be understood to be the total amount of the ingredient in the composition, or where more than one material falls within an ingredient definition, the total amount of all ingredients in the composition that meet the definition.

[0028] For example, if a composition comprises 1% to 5% fatty alcohol, a composition comprising 2% stearyl alcohol and 1% cetyl alcohol and no other fatty alcohols would fall within the range.

[0029] The amount of each specific ingredient or mixtures thereof described below may comprise up to 100% (or 100%) of the total amount of ingredients in the hair care composition.

[0030] As used herein, "personal care composition" includes such liquid compositions as shampoos, shower gels, liquid hand cleansers, hair colorants, facial cleansers, and other surfactant-based compositions.

[0031] As used herein, the terms "including," "comprising," and "containing" are intended to be non-limiting, and are understood to mean "having," "having," and "comprising," respectively.

[0032] Unless otherwise specified, all percentages, parts and ratios are based upon the total weight of the compositions of the present invention. All such weights as they pertain to listed ingredients are based on the active level, and, therefore, do not include carriers or by-products that may be included in commercially available materials.

[0033] Unless otherwise indicated, all component or composition levels are in terms of the active portion of that component or composition and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such component or composition.

[0034] It should be understood that each maximum numerical limit given throughout this specification includes each lower numerical limit, as if such lower numerical limits were expressly written herein. Each minimum numerical limit given throughout this specification will include each higher numerical limit, as if such higher numerical limits were expressly written herein. Each numerical range given throughout this specification will include each narrower numerical range falling within such wider numerical range, as if such narrower numerical ranges were all expressly written herein.

[0035] sulfur

[0036] The personal care compositions of the present invention may contain sulfur. Sulfur suitable for use herein may be in any form of elemental sulfur. Sulfur exists primarily as rhombic crystals at room temperature. The two most common ways to obtain elemental sulfur are precipitation from hydrogen sulfide, one of which is from acid gas pollution via the Claus process, and underground deposits collected using superheated water (known as the Frasch process). Other forms of sulfur such as monoclinic crystalline sulfur, oligomeric or polymeric sulfur are the normal major forms of elemental sulfur that are present in certain higher temperature ranges. At room temperature, these forms are converted or reversed to rhombic sulfur. Sulfur in elemental form may be sulfur that has been physically mixed with a protective colloid such as gum arabic, clay, wax, oil, activated carbon, zeolite, silica, or a dispersant such as a surfactant, or has been subjected to a treatment step to change its particle size or other physical properties. Sulfur can be commercially available in a variety of forms such as pellets, puffs, pellets, colloids, micronized, sublimated, precipitated, and commercial powders.

[0037] The sulfur may have a particle size distribution in which 90% of the particles (D90) are between about 30 micrometers (μm) and about 250 micrometers (μm); the sulfur may have a particle size distribution in which the D90 is between about 30 micrometers (μm) and about 200 micrometers (μm); the sulfur may have a particle size distribution in which the D90 is between about 30 micrometers (μm) and about 150 micrometers (μm); the sulfur may have a particle size distribution in which the D90 is between about 30 micrometers (μm) and about 100 micrometers (μm).

[0038] The sulfur may have a particle size distribution in which 50% of the particles (D50) are between about 5 micrometers (μm) and about 150 micrometers (μm); the sulfur may have a particle size distribution in which the D50 is between about 10 micrometers (μm) and about 100 micrometers (μm); the sulfur may have a particle size distribution in which the D50 is between about 15 micrometers (μm) and about 75 micrometers (μm); the sulfur may have a particle size distribution in which the D50 is between about 20 micrometers (μm) and about 50 micrometers (μm).

[0039] The sulfur may have a particle size distribution in which 10% of the particles (D10) are between about 1 micrometer (μm) and about 25 micrometers (μm); the sulfur may have a particle size distribution in which the D10 is between 5 micrometers (μm) and about 25 micrometers (μm); the sulfur may have a particle size distribution in which the D10 is between about 10 micrometers (μm) and about 25 micrometers (μm); the sulfur may have a particle size distribution in which the D10 is between about 18 micrometers (μm) and about 25 micrometers (μm).

[0040] The sulfur may be present in a D(90) / D(10) ratio of about 3 to about 100; the sulfur may be present in a D(90) / D(10) ratio of about 3 to about 50; the sulfur may be present in a D(90) / D(10) ratio of about 3 to about 10; the sulfur may be present in a D(90) / D(10) ratio of about 3 to about 10.

[0041] Sulfur may be present in amounts of about 0.01% to 10%, about 0.1% to about 9%, about 0.25% to 8%, and about 0.5% to 6%.

[0042] Detergent surfactant

[0043] The hair care composition may contain greater than about 10% by weight of a surfactant system that provides cleaning performance to the composition, and may be greater than 12% by weight of a surfactant system that provides cleaning performance to the composition. The surfactant system comprises an anionic surfactant and / or a combination of anionic surfactants and / or a combination of anionic surfactants and a co-surfactant selected from the group consisting of amphoteric, zwitterionic, nonionic, and mixtures thereof. Various examples and descriptions of detersive surfactants are shown in U.S. Pat. No. 8,440,605; U.S. Patent Application Publication No. 2009 / 155383; and U.S. Patent Application Publication No. 2009 / 0221463, which are incorporated herein by reference in their entirety.

[0044] The hair care composition may contain from about 10 wt % to about 25 wt %, from about 10 wt % to about 18 wt %, from about 10 wt % to about 14 wt %, from about 10 wt % to about 12 wt %, from about 11 wt % to about 20 wt %, from about 12 wt % to about 20 wt %, and / or from about 12 wt % to about 18 wt % of one or more surfactants.

[0045] Suitable anionic surfactants for use in the composition are alkyl sulfates and alkyl ether sulfates. Other suitable anionic surfactants are water-soluble salts of organic sulfuric acid reaction products. Other suitable anionic surfactants are the reaction products of fatty acids esterified with isethionates and neutralized with sodium hydroxide. Other similar anionic surfactants are described in U.S. Pat. Nos. 2,486,921; 2,486,922; and 2,396,278, which are incorporated herein by reference in their entirety.

[0046] Exemplary anionic surfactants for use in the hair care composition include ammonium lauryl sulfate, ammonium laureth sulfate, ammonium C10-15 alkyl polyoxyethylene ether sulfate, C10-15 alkyl ammonium sulfate, C11-15 alkyl ammonium sulfate, decyl sulfate, ammonium decyl polyoxyethylene ether sulfate, undecyl sulfate, ammonium undecyl polyoxyethylene ether sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, sodium lauric acid monoglyceride sulfate, sodium lauryl sulfate, sodium laureth sulfate, sodium C10-15 alkyl polyoxyethylene ether sulfate, sodium C10-15 alkyl sulfate, C11-15 alkyl Sodium sulfate, sodium decyl sulfate, sodium decyl polyoxyethylene sulfate, sodium undecyl sulfate, sodium undecyl polyoxyethylene sulfate, potassium lauryl sulfate, potassium laureth sulfate, potassium C10-15 alkyl polyoxyethylene sulfate, potassium C10-15 alkyl sulfate, potassium C11-15 alkyl sulfate, potassium decyl sulfate, potassium decyl polyoxyethylene sulfate, potassium undecyl sulfate, potassium undecyl polyoxyethylene sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecylbenzene sulfonate, sodium dodecylbenzene sulfonate, sodium cocoyl isethionate, and combinations thereof. The anionic surfactant may be sodium lauryl sulfate or sodium laureth sulfate.

[0047] The composition of the present invention may further comprise an anionic surfactant selected from the group consisting of:

[0048] a)R1 O(CH2CHR3O) y SO3M;

[0049] b) CH3(CH2) z CHR2 CH2 O(CH2 CHR3O) y SO3M; and

[0050] c) mixtures thereof,

[0051] Where R1 represents CH3(CH2) 10 , R2 represents H or a hydrocarbon group containing 1 to 4 carbon atoms such that the sum of the carbon atoms in z and R2 is 8, R3 is H or CH3, y is 0 to 7, when y is not zero (0), the average value of y is about 1, and M is a monovalent or divalent positively charged cation.

[0052] Suitable anionic alkyl sulfate and alkyl ether sulfate surfactants include, but are not limited to, those with branched alkyl chains synthesized from C8 to C18 branched alcohols that can be selected from Guerbet alcohols, alcohols derived from aldol condensation, oxo alcohols, FT oxo alcohols, and mixtures thereof. Non-limiting examples of 2-alkyl branched alcohols include oxo alcohols such as 2-methyl-1-undecanol, 2-ethyl-1-decanol, 2-propyl-1-nonanol, 2-butyl-1-octanol, 2-methyl-1-dodecanol, 2-ethyl-1-undecanol, 2-propyl-1-decanol, 2-butyl-1-nonanol, 2-pentyl-1-octanol, 2-pentyl-1-heptanol, and those sold under the following trade names: (Sasol), (Sasol), and (Shell); and Guerbet and aldol-derived alcohols such as 2-ethyl-1-hexanol, 2-propyl-1-butanol, 2-butyl-1-octanol, 2-butyl-1-decanol, 2-pentyl-1-nonanol, 2-hexyl-1-octanol, 2-hexyl-1-decanol and alcohols sold under the names (Sasol) or as alcohol ethoxylates and alkoxylates under the trade name LUTENSOL (BASF) and LUTENSOL Those sold by BASF.

[0053] Anionic alkyl sulfates and alkyl ether sulfates may also include those synthesized from C8 to C18 branched chain alcohols derived from butene or propylene, which are marketed under the trade name EXXAL TM (Exxon) and The compositions of the present invention may also include sodium tridecyl sulfate.

[0054] The compositions of the present invention may also include anionic alkyl and alkyl ether sulfosuccinates and / or dialkyl and dialkyl ether sulfosuccinates and mixtures thereof. The dialkyl and dialkyl ether sulfosuccinates may be C6-15 linear or branched dialkyl or dialkyl ether sulfosuccinates. The alkyl moieties may be symmetrical (i.e., identical alkyl moieties) or asymmetrical (i.e., different alkyl moieties). Non-limiting examples include: disodium lauryl sulfosuccinate, disodium lauryl polyoxyethylene ether sulfosuccinate, sodium ditridecyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium dihexyl sulfosuccinate, sodium dicyclohexyl sulfosuccinate, sodium diamyl sulfosuccinate, sodium diisobutyl sulfosuccinate, linear bis(tridecyl) sulfosuccinates and mixtures thereof.

[0055] Suitable surfactants that are substantially free of sulfates can include sodium, ammonium, or potassium salts of isethionates; sodium, ammonium, or potassium salts of sulfonates; sodium, ammonium, or potassium salts of ether sulfonates; sodium, ammonium, or potassium salts of sulfosuccinates; sodium, ammonium, or potassium salts of sulfoacetates; sodium, ammonium, or potassium salts of glycinates; sodium, ammonium, or potassium salts of sarcosinates; sodium, ammonium, or potassium salts of glutamate; sodium, ammonium, or potassium salts of alaninates; sodium, ammonium, or potassium salts of carboxylates; sodium, ammonium, or potassium salts of taurates; sodium, ammonium, or potassium salts of phosphates; and combinations thereof.

[0056] As used herein, "substantially free" of sulfate-based surfactants refers to from about 0% to about 3% by weight, alternatively from about 0% to about 2% by weight, alternatively from about 0% to about 1% by weight, alternatively from about 0% to about 0.5% by weight, alternatively from about 0% to about 0.25% by weight, alternatively from about 0% to about 0.1% by weight, alternatively from about 0% to about 0.05% by weight, alternatively from about 0% to about 0.01% by weight, alternatively from about 0% to about 0.001% by weight, and / or alternatively free of sulfate. As used herein, "free" refers to 0% by weight.

[0057] The hair care composition may include an auxiliary surfactant. The auxiliary surfactant may be selected from amphoteric surfactants, zwitterionic surfactants, nonionic surfactants, and mixtures thereof. The auxiliary surfactant may include, but is not limited to, lauroamidopropyl betaine, cocamidopropyl betaine, lauryl hydroxysultaine, sodium lauroamphoacetate, disodium cocoamphodiacetate, cocamide monoethanolamide, and mixtures thereof.

[0058] The hair care composition may also contain from about 0.25% to about 15%, from about 1% to about 14%, from about 2% to about 13% by weight of one or more amphoteric, zwitterionic, nonionic co-surfactants, or mixtures thereof.

[0059] Suitable amphoteric or zwitterionic surfactants for use in the hair care compositions herein include those known for use in shampoos or other hair care cleansing. Non-limiting examples of suitable zwitterionic or amphoteric surfactants are described in U.S. Pat. Nos. 5,104,646 and 5,106,609, which are incorporated herein by reference in their entirety.

[0060] Suitable amphoteric auxiliary surfactants for use in the composition include those described as derivatives of aliphatic secondary and tertiary amines, wherein the aliphatic group may be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms, and one aliphatic substituent contains an anionic group such as a carboxyl, sulfonate, sulfate, phosphate, or phosphonate. Suitable amphoteric surfactants include, but are not limited to, those selected from the group consisting of sodium cocoaminopropionate, sodium cocoaminodipropionate, sodium cocoamphoacetate, sodium cocoamphodiacetate, sodium cocoamphohydroxypropylsulfonate, sodium cocoamphopropionate, sodium corn amphopropionate, sodium lauraminopropionate, sodium lauroamphoacetate, sodium lauroamphodiacetate, sodium lauroamphohydroxypropylsulfonate, sodium lauroamphopropionate, sodium corn amphopropionate, sodium lauriminodipropionate, ammonium cocoaminopropionate, Ammonium Cocoamphopropionate, Ammonium Cocoamphoacetate, Ammonium Cocoamphodiacetate, Ammonium Cocoamphohydroxypropylsulfonate, Ammonium Cocoamphopropionate, Ammonium Cornamphopropionate, Ammonium Lauroylaminopropionate, Ammonium Lauroylamphoacetate, Ammonium Lauroylamphodiacetate, Ammonium Lauroylamphohydroxypropylsulfonate, Ammonium Lauroylamphopropionate, Ammonium Cornamphopropionate, Ammonium Lauriminodipropionate, Triethanolamine Cocoaminopropionate, Triethanolamine Cocoamphodiacetate, Triethanolamine Cocoamphohydroxypropylsulfonate Triethanolamine, triethanolamine cocoamphopropionate, triethanolamine corn amphopropionate, triethanolamine lauryl propionate, triethanolamine lauroamphoacetate, triethanolamine lauroamphohydroxypropyl sulfonate, triethanolamine lauroamphopropionate, triethanolamine corn amphopropionate, triethanolamine lauriminodipropionate, cocoamphodipropionic acid, disodium capryloamphodiacetate, disodium capryloamphodipropionate, disodium capryloamphodiacetate, disodium capryloamphodipropionate, disodium cocoamphocarboxyethyl hydroxypropyl sulfonate Sodium, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Dicarboxyethyl Cocopropylenediamine, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauriminodipropionate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleylamphodipropionate, PPG-2-Isodeceth-7 Carboxyamphodiacetate, Laurylaminopropionic acid, Lauroamphodipropionic acid, Laurylaminopropyl glycine, Lauryldiethylenediaminoglycine, and mixtures thereof.

[0061] The composition may include a zwitterionic co-surfactant, wherein the zwitterionic surfactant is a derivative of an aliphatic quaternary ammonium, phosphonium and sulfonium compound, wherein the aliphatic group may be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one of the aliphatic substituents contains an anionic group such as carboxyl, sulfonate, sulfate, phosphate or phosphonate. The zwitterionic surfactant may be selected from the group consisting of cocamidoethyl betaine, cocamidopropylamine oxide, cocamidopropyl betaine, cocamidopropyl dimethylaminohydroxypropyl hydrolyzed collagen, cocamidopropyl dimonium hydroxypropyl hydrolyzed collagen, cocamidopropyl hydroxysultaine, cocobetainamidoamphopropionate, cocobetaine, cocohydroxysultaine, coco / oleamidopropyl betaine, cocosultaine, lauramidopropyl betaine, lauryl betaine, lauryl hydroxysultaine, lauryl sultaine, and mixtures thereof.

[0062] Nonionic surfactants suitable for use in the present invention include those described in McCutcheon's "Detergents and Emulsifiers" North American Edition (1986, Allured Publishing Corp.) and McCutcheon's "Functional Materials" North American Edition (1992). Nonionic surfactants suitable for use in the personal care compositions of the present invention include, but are not limited to, polyoxyethylated alkylphenols, polyoxyethylated alcohols, polyoxyethylated polypropylene glycols, glycerol esters of alkanoic acids, polyglycerol esters of alkanoic acids, propylene glycol esters of alkanoic acids, sorbitol esters of alkanoic acids, polyoxyethylated sorbitol esters of alkanoic acids, polyoxyethylene glycol esters of alkanoic acids, polyoxyethylated alkanoic acids, alkanolamides, N-alkyl pyrrolidones, alkyl glycosides, alkyl polyglucosides, alkyl amine oxides, and polyoxyethylated siloxanes.

[0063] The auxiliary surfactant can be a nonionic surfactant, which is selected from the group consisting of cocamide, cocamide methyl MEA, cocamide DEA, cocamide MEA, cocamide MIPA, lauramide DEA, lauramide MEA, lauramide MIPA, myristicamide DEA, myristicamide MEA, PEG-20 cocamide MEA, PEG-2 cocamide, PEG-3 cocamide, PEG-4 cocamide, PEG-5 cocamide, PEG-6 cocamide, PEG-7 cocamide, PEG-3 lauramide, PEG-5 lauramide, PEG-3 oleamide, PPG-2 cocamide, PPG-2 hydroxyethyl cocamide, PPG-2 hydroxyethyl isostearamide and mixtures thereof.

[0064] Representative polyoxyethylated alcohols include those having alkyl chains in the C9-C16 range and having from about 1 to about 110 alkoxy groups, including but not limited to laureth-3, laureth-23, ceteth-10, steareth-10, steareth-100, beheneth-10, and those available under the trade name 91. twenty three, 25. 45. 135. 167, PC100, PC 200, PC 600, those commercially available from Shell Chemicals (Houston, Texas), and mixtures thereof.

[0065] Also commercially available is Polyoxyethylene fatty esters are commercially available from Uniqema (Wilmington, Delaware) under the trade names HYDROGEN(R) and include, but are not limited to: 30. 35. 52. 56. 58. 72. 76. 78. 93. 97. 98. 721, and mixtures thereof.

[0066] Suitable alkyl glycosides and alkyl polyglucosides can be represented by the formula (S)nOR, wherein S is a sugar moiety such as glucose, fructose, mannose, galactose, and the like; n is an integer from about 1 to about 1000, and R is a C8-C30 alkyl group. Examples of long chain alcohols from which the alkyl group can be derived include decyl alcohol, lauryl alcohol, tetradecanol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and the like. Examples of these surfactants include alkyl polyglucosides, wherein S is a glucose moiety, R is a C8-20 alkyl group, and n is an integer from about 1 to about 9. Commercially available examples of these surfactants include those sold under the trade names 325 CS, 600CS and Decyl polyglucoside and lauryl polyglucoside are available from Cognis (Ambler, Pa.) as 625CS. Also useful herein are sucrose ester surfactants such as sucrose cocoate and sucrose laurate, and those sold under the trade name Triton TM BG-10 and Triton TM CG-110 is an alkyl polyglucoside available from The Dow Chemical Company (Houston, Tx).

[0067] Other nonionic surfactants suitable for use in the present invention are glyceryl esters and polyglyceryl esters, including, but not limited to, glyceryl monoesters, glyceryl monoesters of C12-22 saturated, unsaturated and branched fatty acids such as glyceryl oleate, glyceryl monostearate, glyceryl monopalmitate, glyceryl monobehenate, and mixtures thereof, and polyglyceryl esters of C12-22 saturated, unsaturated and branched fatty acids such as polyglyceryl-4 isostearate, polyglyceryl-3 oleate, polyglyceryl-2-sesquioleate, diisostearate triglyceride, monooleate diglyceryl, monooleate tetraglyceryl, and mixtures thereof.

[0068] Also useful as nonionic surfactants herein are sorbitan esters. Sorbitan esters of C12-22 saturated, unsaturated and branched fatty acids can be used herein. These sorbitan esters generally include mixtures of monoesters, diesters, triesters, and the like. Representative examples of suitable sorbitan esters include sorbitan monolaurate ( 20) Sorbitan monopalmitate ( 40) Sorbitan monostearate ( 60), Sorbitan tristearate ( 65), Sorbitan monooleate ( 80), Sorbitan trioleate ( 85), and sorbitan isostearate.

[0069] Also suitable for use herein are alkoxylated derivatives of sorbitan esters, including but not limited to polyoxyethylene (20) sorbitan monolaurate ( 20), polyoxyethylene (20) sorbitan monopalmitate ( 40), polyoxyethylene (20) sorbitan monostearate ( 60), polyoxyethylene (20) sorbitan monooleate ( 80), Polyoxyethylene (4) sorbitan monolaurate ( 21) Polyoxyethylene (4) sorbitan monostearate ( 61), Polyoxyethylene (5) sorbitan monooleate ( 81), and mixtures thereof.

[0070] Also suitable for use herein are alkylphenol ethoxylates, including but not limited to nonylphenol ethoxylates (available as Tergitol TM NP-4, NP-6, NP-7, NP-8, NP-9, NP-10, NP-11, NP-12, NP-13, NP-15, NP-30, NP-40, NP-50, NP-55, NP-70) and octylphenol ethoxylate (Triton purchased from The Dow Chemical Company (Houston, TX) TM X-15, X-35, X-45, X-114, X-100, X-102, X-165, X-305, X-405,

[0071] Also suitable for use herein are tertiary alkyl amine oxides including lauryl amine oxide and cocoamine oxide.

[0072] Non-limiting examples of other anionic, zwitterionic, amphoteric and nonionic additional surfactants suitable for use in the hair care compositions are described in McCutcheon's Emulsifiers and Detergents, 1989 Annual, published by MC Publishing Co., and in U.S. Pat. Nos. 3,929,678; 2,658,072; 2,438,091; 2,528,378, the entireties of which are incorporated herein by reference.

[0073] Suitable surfactant combinations include an average weight percent of alkyl branching of from about 0.5% to about 30%, or from about 1% to about 25%, or from about 2% to about 20%. The surfactant combination may have a cumulative average weight percent of C8 to C12 alkyl chain lengths of from about 7.5% to about 25%, or from about 10% to about 22.5%, or from about 10% to about 20%. The surfactant combination may have an average C8-C12 / C13-C18 alkyl chain ratio of from about 3 to about 200, or from about 25 to about 175.5, or from about 50 to about 150, or from about 75 to about 125.

[0074] Cationic polymers

[0075] The hair care composition further comprises a cationic polymer. These cationic polymers may include at least one of the following: (a) a cationic guar polymer, (b) a cationic non-guar galactomannan polymer, (c) a cationic tapioca polymer, (d) a cationic copolymer of an acrylamide monomer and a cationic monomer, and / or (e) a synthetic non-crosslinked cationic polymer that may or may not form a lyotropic liquid crystal after being combined with a detersive surfactant, (f) a cationic cellulose polymer. In addition, the cationic polymer may be a mixture of cationic polymers.

[0076] The hair care compositions may comprise cationic guar polymers which are cationically substituted galactomannan (guar) gum derivatives. The guar gum used to prepare these guar gum derivatives is generally obtained in the form of naturally occurring material from the seeds of the guar gum plant. The guar gum molecule itself is a linear mannan branched at regular intervals with monogalactose units on alternating mannose units. The mannose units are linked to each other via β (1-4) glycosidic linkages. Galactose branching occurs via α (1-6) bonds. Cationic derivatives of guar gum are obtained by reaction between the hydroxyl groups of the polygalactomannan with a reactive quaternary ammonium compound. The degree of substitution of the cationic groups onto the guar gum structure should be sufficient to provide the desired cationic charge density as described above.

[0077] Cationic polymers may include, but are not limited to, cationic guar polymers having a weight average molecular weight of less than 2,200,000 g / mol, or about 150,000 to about 2,200,000 g / mol, or about 200,000 to about 2,200,000 g / mol, or about 300,000 to about 1,200,000 g / mol, or about 750,000 to about 1,000,000 g / mol. Cationic guar polymers may have a charge density of about 0.2 meq / g to about 2.2 meq / g, or about 0.3 meq / g to about 2.0 meq / g, or about 0.4 meq / g to about 1.8 meq / g; or about 0.5 meq / g to about 1.8 meq / g.

[0078] The cationic guar polymer may have a weight average molecular weight of less than about 1,500,000 g / mol and a charge density of about 0.1 meq / g to about 2.5 meq / g. The cationic guar polymer can have a weight average molecular weight of less than 900,000 g / mol, or from about 150,000 g / mol to about 800,000 g / mol, or from about 200,000 g / mol to about 700,000 g / mol, or from about 300,000 g / mol to about 700,000 g / mol, or from about 400,000 g / mol to about 600,000 g / mol, or from about 150,000 g / mol to about 800,000 g / mol, or from about 200,000 g / mol to about 700,000 g / mol, or from about 300,000 g / mol to about 700,000 g / mol, or from about 400,000 g / mol to about 600,000 g / mol. The cationic guar polymer may have a charge density of about 0.2 meq / g to about 2.2 meq / g, or about 0.3 meq / g to about 2.0 meq / g, or about 0.4 meq / g to about 1.8 meq / g; or about 0.5 meq / g to about 1.5 meq / g.

[0079] Cationic guar gum polymers can be formed from quaternary ammonium compounds. The quaternary ammonium compounds used to form cationic guar gum polymers can conform to Formula 1:

[0080]

[0081] Where R 3 , R 4 and R 5 is a methyl or ethyl group; R 6 is an alkylene oxide group having the general formula 2:

[0082]

[0083] or R 6 is a halohydrin group having the general formula 3:

[0084]

[0085] Where R 7 is a C1 to C3 alkylene group; X is chlorine or bromine, and Z is an anion such as Cl-, Br-, I- or HSO4-.

[0086] Cationic guar gum polymers may conform to the general formula 4:

[0087]

[0088] Where R 8 is guar gum; and wherein R4 , R 5 , R 6 and R 7 As defined above; and wherein Z is halogen. The cationic guar polymer may conform to Formula 5:

[0089]

[0090] Suitable cationic guar gum polymers include cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride. The cationic guar gum polymer may be guar hydroxypropyltrimonium chloride. Specific examples of guar hydroxypropyltrimonium chloride include those commercially available from Solvay series, such as those commercially available from Solvay C-500. C-500 has a charge density of 0.8 meq / g and a molecular weight of 500,000 g / mol. Other suitable guar hydroxypropyltrimonium chlorides are: having a charge density of about 1.3 meq / g and a molecular weight of about 500,000 g / mol and sold under the trade name Optima is available from Solvay as guar hydroxypropyltrimonium chloride. Other suitable guar hydroxypropyltrimonium chlorides are: having a charge density of about 0.7 meq / g and a molecular weight of about 1,500,000 g / mol and sold under the trade name Guar hydroxypropyltrimonium chloride is available from Solvay at Excel. Other suitable guar hydroxypropyltrimonium chlorides are: guar hydroxypropyltrimonium chloride having a charge density of about 1.1 meq / g and a molecular weight of about 500,000 g / mol and available from ASI, guar hydroxypropyltrimonium chloride having a charge density of about 1.5 meq / g and a molecular weight of about 500,000 g / mol and available from ASI.

[0091] Other suitable guar hydroxypropyltrimonium chlorides are: Hi-Care 1000, which has a charge density of about 0.7 meq / g and a molecular weight of about 600,000 g / mol, and is available from Solvay; N-Hance 3269 and N-Hance 3270, which have a charge density of about 0.7 meq / g and a molecular weight of about 425,000 g / mol, and are available from ASI; N-Hance 3196, which has a charge density of about 0.8 meq / g and a molecular weight of about 1,100,000 g / mol, and is available from ASI. AquaCat CG518 has a charge density of about 0.9 meq / g and a molecular weight of about 50,000 g / mol, and is available from ASI. BF-13, which is a borate (boron) free guar gum having a charge density of about 1 meq / g and a molecular weight of about 800,000, and BF-17, which is a borate (boron) free guar gum having a charge density of about 1.5 meq / g and a molecular weight of about 800,000, were both purchased from ASI.

[0092] The hair care composition of the present invention may comprise a galactomannan polymer derivative having a mannose to galactose ratio of greater than 2:1 on a monomer to monomer basis, the galactomannan polymer derivative being selected from the group consisting of a cationic galactomannan polymer derivative and an amphoteric galactomannan polymer derivative having a net positive charge. As used herein, the term "cationic galactomannan" refers to a galactomannan polymer to which a cationic group has been added. The term "amphoteric galactomannan" refers to a galactomannan polymer to which a cationic group and an anionic group have been added so that the polymer has a net positive charge.

[0093] Galactomannan polymers are present in the endosperm of leguminous seeds. Galactomannan polymers are composed of a combination of mannose monomers and galactose monomers. Galactomannan molecules are linear mannans branched with single-segment galactose units on specific mannose units at regular intervals. The mannose units are linked to each other via β (1-4) glycosidic linkages. Galactose branching occurs via α (1-6) bonds. The ratio of mannose monomers to galactose monomers varies depending on the variety of the plant and is also affected by climate. On a monomer-to-monomer basis, the non-guar galactomannan polymer derivatives of the present invention have a mannose to galactose ratio greater than 2:1. Suitable mannose to galactose ratios may be greater than about 3:1, and mannose to galactose ratios may be greater than about 4:1. Analysis of mannose to galactose ratios is well known in the art and is typically based on measurements of galactose content.

[0094] The gums used to prepare the non-guar galactomannan polymer derivatives are generally obtained in the form of naturally occurring materials, such as seeds or bean-shaped fruits from plants. Examples of various non-guar galactomannan polymers include, but are not limited to, tara gum (3 parts mannose / 1 part galactose), locust bean gum or carob gum (4 parts mannose / 1 part galactose), and cassia gum (5 parts mannose / 1 part galactose).

[0095] The non-guar galactomannan polymer derivatives may have an M.Wt. of about 1,000 to about 10,000,000, and / or about 5,000 to about 3,000,000.

[0096] The hair care compositions of the present invention may also include a galactomannan polymer derivative having a cationic charge density of from about 0.5 meq / g to about 7 meq / g. The galactomannan polymer derivative may have a cationic charge density of from about 1 meq / g to about 5 meq / g. The degree of substitution of the cationic groups on the galactomannan structure should be sufficient to provide the desired cationic charge density.

[0097] The galactomannan polymer derivative may be a cationic derivative of a non-guar galactomannan polymer obtained by reaction between the hydroxyl groups of the polygalactomannan polymer and a reactive quaternary ammonium compound. Suitable quaternary ammonium compounds for forming cationic galactomannan polymer derivatives include those conforming to Formulas 1 to 5 as defined above.

[0098] The cationic non-guar galactomannan polymer derivative formed by the above reagents is represented by Formula 6:

[0099]

[0100] Wherein R is gum. The cationic galactomannan derivative may be gum hydroxypropyltrimethylammonium chloride, which may be more specifically represented by general formula 7:

[0101]

[0102] Alternatively, the galactomannan polymer derivative may be an amphoteric galactomannan polymer derivative having a net positive charge, and when the cationic galactomannan polymer derivative further comprises an anionic group, an amphoteric galactomannan polymer derivative is obtained.

[0103] The cationic non-guar galactomannans may have a mannose to galactose ratio of greater than about 4:1, a molecular weight of about 1,000 g / mol to about 10,000,000 g / mol, and / or about 50,000 g / mol to about 1,000,000 g / mol, and / or about 100,000 g / mol to about 900,000 g / mol, and / or about 150,000 g / mol to about 400,000 g / mol, and a cationic charge density of about 1 meq / g to about 5 meq / g, and / or 2 meq / g to about 4 meq / g, and may be derived from the cinnamon plant.

[0104] The hair care composition may include a water-soluble cationically modified starch polymer. As used herein, the term "cationically modified starch" refers to a starch to which cationic groups are added before the starch is degraded to have a smaller molecular weight, or to which cationic groups are added after the starch is modified to obtain a desired molecular weight. The definition of the term "cationically modified starch" also includes amphoteric modified starches. The term "amphoteric modified starch" refers to a starch hydrolyzate to which cationic groups and anionic groups are added.

[0105] The cationically modified starch polymers disclosed herein have a bound nitrogen percentage of about 0.5% to about 4%.

[0106] Cationic modified starch polymers for use in the hair care compositions can have a molecular weight of from about 850,000 g / mol to about 1,500,000 g / mol and / or from about 900,000 g / mol to about 1,500,000 g / mol.

[0107] The hair care composition may include a cationic modified starch polymer having a charge density of from about 0.2 meq / g to about 5 meq / g, and / or from about 0.2 meq / g to about 2 meq / g. Chemical modifications to obtain such charge density include, but are not limited to, the addition of amino and / or ammonium groups to the starch molecule. Non-limiting examples of these ammonium groups may include substituents such as hydroxypropyltrimethylammonium chloride, trimethylhydroxypropylammonium chloride, dimethylstearylhydroxypropylammonium chloride, and dimethyldodecylhydroxypropylammonium chloride. See Solarek, DB, Cationic Starches in Modified Starches: Properties and Uses (Wurzburg, OB, ed., CRC Press, Inc., Boca Raton, Fla. 1986, pp. 113-125). The cationic groups may be added to the starch before it is degraded to have a smaller molecular weight, or the cationic groups may be added thereto after such modification.

[0108] The cationically modified starch polymers typically have a degree of substitution of cationic groups of from about 0.2 to about 2.5. As used herein, the "degree of substitution" of a cationically modified starch polymer is an average measure of the number of hydroxyl groups on each anhydroglucose unit derived from a substituent. Since each anhydroglucose unit has three hydroxyl groups that can be substituted, the maximum possible degree of substitution is 3. On a molar average, the degree of substitution is expressed as the number of moles of substituents per mole of anhydroglucose unit. The degree of substitution can be determined using proton nuclear magnetic resonance spectroscopy (".sup.1H NMR") methods well known in the art. Suitable .sup.1H NMR techniques include those described in "Observation on NMR Spectra of Starches in Dimethyl Sulfoxide, Iodine-Complexing, and Solvating in Water-Dimethyl Sulfoxide", Qin-Ji Peng and Arthur S. Perlin, Carbohydrate Research, 160 (1987), 57-72; and "An Approach to the Structural Analysis of Oligosaccharides by NMR Spectroscopy", J. Howard Bradbury and J. Grant Collins, Carbohydrate Research, 71, (1979), 15-25.

[0109] The source of starch before chemical modification can be selected from a variety of sources, such as tubers, beans, cereals and grains. Non-limiting examples of starch from such sources can include corn starch, wheat starch, rice starch, waxy corn starch, oat starch, cassava starch, waxy barley starch, waxy rice starch, gluten rice starch, gluten rice starch, amylopectin, potato starch, tapioca starch, oat starch, sago starch, gluten, or mixtures thereof.

[0110] The cationically modified starch polymer may be selected from degraded cationic corn starch, cationic tapioca, cationic potato starch, and mixtures thereof. Alternatively, the cationically modified starch polymer is cationic corn starch and cationic tapioca.

[0111] Before degradation to have a smaller molecular weight or after modification to have a smaller molecular weight, the starch may include one or more additional modifications. For example, these modifications may include cross-linking, stabilization reactions, phosphorylation and hydrolysis. Stability reactions may include alkylation and esterification.

[0112] The cationic modified starch polymer can be incorporated into the composition in the form of hydrolyzed starch (e.g., acid, enzyme or alkaline degradation), oxidized starch (e.g., peroxide, peracid, hypochlorite, alkali or any other oxidizing agent), physically / mechanically degraded starch (e.g., via thermomechanical energy input to processing equipment), or a combination thereof.

[0113] The best form of starch is one that dissolves readily in water and forms a substantially clear (about 80 percent transmittance at 600 nm) solution in water. The transparency of the composition is determined by ultraviolet / visible (UV / VIS) spectrophotometry using a Gretag Macbeth Colorimeter Color i 5 according to the relevant instructions to measure the absorption or transmission of UV / VIS light by the sample. It has been shown that a wavelength of light of 600 nm is sufficient to characterize the transparency of a cosmetic composition.

[0114] Suitable cationically modified starches for use in hair care compositions are available from known starch suppliers. Also suitable for use in hair care compositions are nonionically modified starches which can be further derivatized to form cationically modified starches as known in the art. Other suitable modified starch materials can be quaternized to produce cationically modified starch polymers suitable for use in hair care compositions as known in the art.

[0115] Starch degradation process: A starch slurry can be prepared by mixing granular starch in water. The temperature is raised to about 35°C. An aqueous potassium permanganate solution of about 50 ppm concentration based on starch is then added. The pH is raised to about 11.5 with sodium hydroxide, and the slurry is stirred thoroughly to prevent starch sedimentation. A solution of about 30% hydrogen peroxide diluted in water is then added to a level of about 1% peroxide based on starch. The pH is then restored to about 11.5 by adding additional sodium hydroxide. The reaction is completed over a period of about 1 to about 20 hours. The mixture is then neutralized with dilute hydrochloric acid. The degraded starch is recovered by filtration followed by washing and drying.

[0116] The hair care composition may comprise a cationic copolymer of an acrylamide monomer and a cationic monomer, wherein the copolymer has a charge density of from about 1.0 meq / g to about 3.0 meq / g. The cationic copolymer may be a synthetic cationic copolymer of an acrylamide monomer and a cationic monomer.

[0117] Cationic copolymers may contain:

[0118] (i) an acrylamide monomer having the following formula AM:

[0119]

[0120] Where R 9H or C 1-4 alkyl; and R 10 and R 11 Independently selected from H, C 1-4 Alkyl, CH2OCH3, CH2OCH2CH(CH3)2 and phenyl, or together with C 3-6 Cycloalkyl; and

[0121] (ii) a cationic monomer conforming to formula CM:

[0122]

[0123] wherein k=1, each of v, v' and v" is independently an integer from 1 to 6, w is zero or an integer from 1 to 10, and X - It is an anion.

[0124] The cationic monomer may conform to the formula CM, and wherein k=1, v=3, and w=0, z=1, and X - Cl - , to form the following structure:

[0125]

[0126] The above structure may be referred to as a diquaternary ammonium salt. Alternatively, the cationic monomer may conform to the formula CM, and wherein v and v" are each 3, v' = 1, w = 1, y = 1, and X - Cl - , such as:

[0127]

[0128] The above structure can be called a triquaternary ammonium salt.

[0129] Suitable acrylamide monomers include, but are not limited to, acrylamide or methacrylamide.

[0130] The cationic copolymer (b) may be AM:TRIQUAT, which is a copolymer of acrylamide and N-[2-[[[dimethyl[3-[(2-methyl-1-oxo-2-propenyl)amino]propyl]ammonio]acetyl]amino]ethyl]2-hydroxy-N,N,N',N',N'-pentamethyl-1,3-propanediammonium trichloride. AM:TRIQUAT is also known as polyquaternium-76 (PQ76). AM:TRIQUAT may have a charge density of 1.6 meq / g and a molecular weight of 1,100,000 g / mol.

[0131] The cationic copolymer may have an acrylamide monomer and a cationic monomer, wherein the cationic monomer is selected from: dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, di-tert-butylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide; ethyleneimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine; trimethylammonium ethyl chloride (meth)acrylate, trimethylammonium ethyl methylsulfate (meth)acrylate, dimethylbenzylammonium ethyl chloride (meth)acrylate, 4-benzoylbenzyldimethylammonium ethyl chloride acrylate, trimethylammonium chloride ethyl (meth)acrylamide, trimethylammonium chloride propyl (meth)acrylamide, vinylbenzyltrimethylammonium chloride, diallyldimethylammonium chloride, and mixtures thereof.

[0132] The cationic copolymer may contain a cationic monomer selected from the group consisting of: cationic monomers including trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl methyl (meth)acrylate sulfate, dimethylbenzylammonium ethyl (meth)acrylate chloride, 4-benzoylbenzyldimethylammonium ethyl chloride acrylate, trimethylammonium chloride ethyl (meth)acrylamide, trimethylammonium chloride propyl (meth)acrylamide, vinylbenzyltrimethylammonium chloride, and mixtures thereof.

[0133] The cationic copolymer may be water soluble. The cationic copolymer is formed from (1) a copolymer of (meth)acrylamide and a cationic monomer based on (meth)acrylamide and / or a hydrolytically stable cationic monomer, (2) a terpolymer of (meth)acrylamide, a cationic (meth)acrylate-based monomer, and a (meth)acrylamide-based monomer, and / or a hydrolytically stable cationic monomer. The cationic (meth)acrylate-based monomer may be a cationized ester of (meth)acrylic acid containing a quaternized N atom. The cationized ester of (meth)acrylic acid containing a quaternized N atom may be a quaternized dialkylaminoalkyl (meth)acrylate having C1 to C3 in the alkyl and alkylene groups. Suitable cationized esters of (meth)acrylic acid containing quaternized N atoms may be selected from: ammonium salts of dimethylaminomethyl (meth)acrylate quaternized with methyl chloride, ammonium salts of dimethylaminoethyl (meth)acrylate, ammonium salts of dimethylaminopropyl (meth)acrylate, ammonium salts of diethylaminomethyl (meth)acrylate, ammonium salts of diethylaminoethyl (meth)acrylate; and ammonium salts of diethylaminopropyl (meth)acrylate. The cationized ester of (meth)acrylic acid containing quaternized N atoms may be dimethylaminoethyl acrylate (ADAME-Quat) quaternized with alkyl halides, or with methyl chloride, or benzyl chloride, or dimethyl sulfate. When based on (meth)acrylamide, the cationic monomer may be a quaternized dialkylaminoalkyl (meth)acrylamide having C1 to C3 in the alkyl and alkylene groups, or dimethylaminopropyl acrylamide quaternized with alkyl halides, or methyl chloride, or benzyl chloride, or dimethyl sulfate.

[0134] Suitable cationic (meth)acrylamide-based monomers include quaternized dialkylaminoalkyl (meth)acrylamides having C1 to C3 in the alkyl and alkylene groups. The cationic (meth)acrylamide-based monomer may be dimethylaminopropylacrylamide, quaternized with an alkyl halide (especially methyl chloride) or benzyl chloride or dimethyl sulfate.

[0135] The cationic monomer may be a hydrolytically stable cationic monomer. In addition to dialkylaminoalkyl (meth) acrylamide, the hydrolytically stable cationic monomer may also be all monomers that can be considered stable by the OECD hydrolysis test. The cationic monomer may be hydrolytically stable, and the hydrolytically stable cationic monomer may be selected from: diallyldimethylammonium chloride and water-soluble cationic styrene derivatives.

[0136] The cationic copolymer may be a terpolymer of acrylamide, 2-dimethylammoniumethyl (meth)acrylate quaternized with methyl chloride (ADAME-Q), and 3-dimethylammoniumpropyl (meth)acrylamide (DIMAPA-Q) quaternized with methyl chloride. The cationic copolymer may be formed from acrylamide and acrylamidopropyltrimethylammonium chloride, wherein the acrylamidopropyltrimethylammonium chloride has a charge density of about 1.0 meq / g to about 3.0 meq / g.

[0137] The cationic copolymer may have a charge density of about 1.1 meq / g to about 2.5 meq / g, or about 1.1 meq / g to about 2.3 meq / g, or about 1.2 meq / g to about 2.2 meq / g, or about 1.2 meq / g to about 2.1 meq / g, or about 1.3 meq / g to about 2.0 meq / g, or about 1.3 meq / g to about 1.9 meq / g.

[0138] The cationic copolymer can have a molecular weight of about 100,000 g / mol to about 1,500,000 g / mol, or about 300,000 g / mol to about 1,500,000 g / mol, or about 500,000 g / mol to about 1,500,000 g / mol, or about 700,000 g / mol to about 1,000,000 g / mol, or about 900,000 g / mol to about 1,200,000 g / mol.

[0139] The cationic copolymer may be trimethylammoniumpropylmethacrylamide chloride-N-acrylamide copolymer, also referred to as AM:MAPTAC. AM:MAPTAC may have a charge density of about 1.3 meq / g and a molecular weight of about 1,100,000 g / mol. The cationic copolymer may be AM:ATPAC. AM:ATPAC may have a charge density of about 1.8 meq / g and a molecular weight of about 1,100,000 g / mol.

[0140] (a) Cationic synthetic polymers

[0141] The hair care composition may comprise a cationic synthetic polymer which may be formed from

[0142] i) one or more cationic monomer units, and optionally

[0143] ii) one or more negatively charged monomer units, and / or

[0144] iii) nonionic monomers,

[0145] The subsequent charge of the copolymer is positive. The ratios of the three types of monomers are given as "m", "p" and "q", where "m" is the number of cationic monomers, "p" is the number of monomers with a negative charge, and "q" is the number of nonionic monomers.

[0146] The cationic polymer may be a water-soluble or water-dispersible non-crosslinked and synthetic cationic polymer having the following structure:

[0147]

[0148] Wherein A can be one or more of the following cationic moieties:

[0149]

[0150] Wherein @ = amide, alkylamide, ester, ether, alkyl, or alkylaryl;

[0151] Wherein Y = C1-C22 alkyl, alkoxy, alkylidene, alkyl, or aryloxy;

[0152] Wherein ψ=C1-C22 alkyl, alkoxy, alkylaryl, or alkylaryloxy;.

[0153] Wherein Z=C1-C22 alkyl, alkoxy, aryl, or aryloxy;

[0154] Wherein R1=H, C1-C4 straight chain or branched alkyl;

[0155] Where s = 0 or 1, n = 0 or ≥ 1;

[0156] wherein T and R7 = C1-C22 alkyl; and

[0157] wherein X-=halogen, hydroxide, alkanolate, sulfate or alkylsulfate.

[0158] The negatively charged monomer is defined as follows: R2'=H, C1-C4 straight or branched chain alkyl, and R3 is:

[0159]

[0160] Where D=O, N, or S;

[0161] Where Q = NH2 or O;

[0162] Where u = 1 to 6;

[0163] wherein t = 0 to 1; and

[0164] Wherein J = an oxidized functional group containing the following elements P, S, C.

[0165] The nonionic monomer is defined as follows: R2″=H, C1-C4 straight chain or branched alkyl, R6=straight chain or branched alkyl, alkylaryl, aryloxy, alkoxy, alkylaryloxy, and β is defined as

[0166] and

[0167] wherein G′ and G″ are independently O, S or NH, and L=0 or 1.

[0168] Examples of cationic monomers include aminoalkyl (meth)acrylates, (meth)aminoalkyl (meth)acrylamides; monomers containing at least one secondary, tertiary or quaternary ammonium functional group, or a heterocyclic group containing a nitrogen atom, vinylamine or ethyleneimine; diallyldialkylammonium salts; mixtures thereof, their salts and macromonomers derived therefrom.

[0169] Additional examples of cationic monomers include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, di-tert-butylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, ethyleneimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine, trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methylsulfate, dimethylbenzylammonium ethyl (meth)acrylate chloride, 4-benzoylbenzyldimethylammonium ethyl chloride acrylate, trimethylammonium chloride ethyl (meth)acrylamide, trimethylammonium chloride propyl (meth)acrylamide, vinylbenzyltrimethylammonium chloride, and diallyldimethylammonium chloride.

[0170] Suitable cationic monomers include those comprising the formula -NR3 + Those of quaternary ammonium groups, wherein R is the same or different, represents a hydrogen atom, an alkyl group containing 1 to 10 carbon atoms, or a benzyl group, optionally with a hydroxyl group, and includes an anion (counter ion). Examples of anions are halides (such as chloride, bromide), sulfate, hydrogen sulfate, alkyl sulfate (e.g., containing 1 to 6 carbon atoms), phosphate, citrate, formate and acetate.

[0171] Suitable cationic monomers include trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methylsulfate, dimethylbenzylammonium ethyl (meth)acrylate chloride, 4-benzoylbenzyldimethylammonium ethyl chloride acrylate, trimethylammonium chloride ethyl (meth)acrylamide, trimethylammonium chloride propyl (meth)acrylamide, vinylbenzyltrimethylammonium chloride.

[0172] Additional suitable cationic monomers include trimethylammonium chloride propyl (meth)acrylamide.

[0173] Examples of monomers having a negative charge include α-ethylenically unsaturated monomers containing a phosphate or phosphonate group, α-ethylenically unsaturated monocarboxylic acids, monoalkyl esters of α-ethylenically unsaturated dicarboxylic acids, monoalkyl amides of α-ethylenically unsaturated dicarboxylic acids, α-ethylenically unsaturated compounds containing a sulfonic acid group, and salts of α-ethylenically unsaturated compounds containing a sulfonic acid group.

[0174] Suitable monomers having a negative charge include acrylic acid, methacrylic acid, vinyl sulfonic acid, salts of vinyl sulfonic acid, vinylbenzenesulfonic acid, salts of vinylbenzenesulfonic acid, α-acrylamidomethylpropanesulfonic acid, salts of α-acrylamidomethylpropanesulfonic acid, 2-sulfoethyl methacrylate, salts of 2-sulfoethyl methacrylate, acrylamido-2-methylpropanesulfonic acid (AMPS), salts of acrylamido-2-methylpropanesulfonic acid, and styrene sulfonate (SS).

[0175] Examples of nonionic monomers include vinyl acetate, amides of α-ethylenically unsaturated carboxylic acids, esters of α-ethylenically unsaturated monocarboxylic acids with hydrogenated or fluorinated alcohols, polyethylene oxide (meth)acrylates (i.e., polyethoxylated (meth)acrylic acids), monoalkyl esters of α-ethylenically unsaturated dicarboxylic acids, monoalkyl amides of α-ethylenically unsaturated dicarboxylic acids, vinyl nitriles, vinylamine amides, vinyl alcohol, vinyl pyrrolidone, and vinyl aromatic compounds.

[0176] Suitable nonionic monomers include styrene, acrylamide, methacrylamide, acrylonitrile, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, 2-ethyl-hexyl acrylate, 2-ethyl-hexyl methacrylate, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.

[0177] The anionic counterion (X-) associated with the synthetic cationic polymer can be any known counterion, so long as the polymer remains soluble or dispersible in water, in the hair care composition, or in a coacervate phase in the hair care composition, and so long as the counterion is physically and chemically compatible with the essential components of the hair care composition, or does not otherwise unduly impair product performance, stability, or aesthetics. Non-limiting examples of such counterions include halides (e.g., chloride, fluoride, bromide, iodide), sulfate, and methylsulfate.

[0178] The cationic polymers described herein can help provide a replacement hydrophobic F-layer to damaged hair, especially chemically treated hair. The extremely thin F-layer helps seal in moisture and prevent further damage while providing natural weather resistance. Chemical treatments damage the hair cuticle and strip its protective F-layer. As the F-layer is stripped, the hair becomes increasingly hydrophilic. It has been found that when lyotropic liquid crystals are applied to chemically treated hair, the hair becomes more hydrophobic and more natural in both appearance and feel. Without being bound by any theory, it is believed that the lyotropic liquid crystal complex forms a hydrophobic layer or film that covers the hair fiber and protects the hair, just as the natural F-layer protects the hair. The hydrophobic layer restores the hair to a generally untreated, healthier state. The lyotropic liquid crystals are formed by mixing the synthetic cationic polymers described herein with the anionic detersive surfactant component of the aforementioned hair care composition. The synthetic cationic polymers have a relatively high charge density. It should be noted that some synthetic polymers with relatively high cationic charge density do not form lyotropic liquid crystals, which is mainly due to their abnormal linear charge density. Such synthetic cationic polymers are described in WO 94 / 06403 to Reich et al. The synthetic polymers described herein can be formulated into stable hair care compositions that provide improved conditioning properties for damaged hair.

[0179] The cationic synthetic polymers that can form lyotropic liquid crystals have a cationic charge density of about 2 meq / gm to about 7 meq / gm, and / or about 3 meq / gm to about 7 meq / gm, and / or about 4 meq / gm to about 7 meq / gm. The cationic charge density can be about 6.2 meq / gm. The polymer also has an M.Wt. of about 1,000 to about 5,000,000, and / or about 10,000 to about 1,500,000, and / or about 100,000 to about 1,500,000.

[0180] In the present invention, cationic synthetic polymers that provide enhanced conditioning and benefit agent deposition without forming lyotropic liquid crystals may have a cationic charge density of from about 0.7 meq / gm to about 7 meq / gm, and / or from about 0.8 meq / gm to about 5 meq / gm, and / or from about 1.0 meq / gm to about 3 meq / gm. The polymer may also have an M.Wt. of from about 1,000 to about 1,500,000, from about 10,000 to about 1,500,000, and from about 100,000 to about 1,500,000.

[0181] Suitable cationic cellulose polymers are salts obtained by reacting hydroxyethylcellulose with trimethylammonium substituted epoxides, which are known in the industry (CTFA) as polyquaternium-10, and are available from Dow / Amerchol Corp. (Edison, NJ, USA) as their Polymer LR, JR and KG polymer series. Non-limiting examples include: JR-30M, KG-30M, JP, LR-400 and mixtures thereof. Other suitable types of cationic cellulose include polymeric quaternary ammonium salts obtained by reacting hydroxyethylcellulose with lauryl dimethyl ammonium substituted epoxides, which are known in the industry (CTFA) as polyquaternium-24. These materials are available from Dow / Amerchol Corp. under the trade name Polymer LM-200. Other suitable types of cationic cellulose include polymeric quaternary ammonium salts obtained by reacting hydroxyethylcellulose with lauryl dimethyl ammonium substituted epoxides and trimethyl ammonium substituted epoxides, which are known in the industry (CTFA) as polyquaternium-67. These materials are available from Dow / Amerchol Corp. under the trade designations SoftCAT Polymer SL-5, SoftCAT Polymer SL-30, Polymer SL-60, Polymer SL-100, Polymer SK-L, Polymer SK-M, Polymer SK-MH, and Polymer SK-H.

[0182] Concentrations of the cationic polymer range from about 0.025% to about 5%, from about 0.1% to about 3%, and / or from about 0.2% to about 1% by weight of the hair care composition.

[0183] Stabilized polymer

[0184] The personal care composition may include a stabilizing polymer to increase the viscosity or yield stress of the composition. Suitable stabilizing polymers may be used. The hair care composition may include from about 0.05% to 10% and 0.1% to about 9% stabilizing, from about 0.4% to about 8% stabilizing polymers, from about 0.7% to about 5% stabilizing modified polymers, and from about 1% to about 2.5% stabilizing polymers. Stabilizing polymer modifiers may be polyacrylates, polyacrylamide thickeners. Stabilizing polymers may be anionic stabilizing polymers.

[0185] The hair personal care composition may comprise a stabilizing polymer based on homopolymers of acrylic acid, methacrylic acid or other related derivatives, non-limiting examples of which include polyacrylates, polymethacrylates, polyethyl acrylates and polyacrylamides.

[0186] The stabilizing polymer may be an alkali swellable and hydrophobically modified alkali swellable acrylic copolymer or methacrylate copolymer, non-limiting examples of which include acrylic acid / acrylonitrile copolymer, acrylates / stearyl polyoxyethylene ethoxylate-20 itaconate copolymer, acrylates / cetyl polyoxyethylene ethoxylate-20 itaconate copolymer, acrylates / aminoacrylate / C10-30 alkyl PEG-20 itaconate copolymer, acrylates / aminoacrylate copolymer, acrylates / stearyl polyoxyethylene ethoxylate-20 methacrylate copolymer, acrylic acid Acrylates / Beheneth-25 Methacrylate Copolymer, Acrylates / Steareth-20 Methacrylate Crosspolymer, Acrylates / Beheneth-25 Methacrylate / HEMA Crosspolymer, Acrylates / Vinyl Neodecanoate Crosspolymer, Acrylates / Vinyl Isodecanoate Crosspolymer, Acrylates / Ceteth-25 Acrylate Copolymer, Acrylic Acid / Acrylamidomethylpropane Sulfonic Acid Copolymer, and Acrylates / C10-C30 Alkyl Acrylate Crosspolymer.

[0187] The stabilizing polymer may be a soluble cross-linked acrylic polymer, non-limiting examples of which include carbomers.

[0188] The stabilizing polymer may be an associative polymer thickener, non-limiting examples of which include: hydrophobically modified alkali swellable emulsions, non-limiting examples of which include hydrophobically modified polyacrylates; hydrophobically modified polyacrylic acids and hydrophobically modified polyacrylamides; hydrophobically modified polyethers, wherein these materials may have a hydrophobe selected from cetyl, stearyl, oleyl, and combinations thereof.

[0189] Stabilizing polymers can be used in combination with polyvinyl pyrrolidone, cross-linked polyvinyl pyrrolidone and derivatives. Stabilizing polymers can be combined with polyvinyl alcohol and derivatives. Stabilizing polymers can be combined with polyethylene imine and derivatives.

[0190] Stabilizing polymers may be combined with alginic acid based materials, non-limiting examples of which include sodium alginate and propylene glycol alginate.

[0191] Stabilizing polymers may be used in combination with polyurethane polymers, non-limiting examples of which include: hydrophobically modified alkoxylated urethane polymers, non-limiting examples of which include PEG-150 / decyl alcohol / SMDI copolymer, PEG-150 / stearyl alcohol / SMDI copolymer, polyurethane-39.

[0192] The stabilizing polymer may be combined with an associative polymer thickener, non-limiting examples of which include: hydrophobically modified cellulose derivatives; and hydrophilic moieties having 10-300, 30-200, and 40-150 repeating units of ethylene oxide repeating groups. Non-limiting examples of this type include PEG-120-methyl glucose dioleate, PEG-(40 or 60) sorbitan tetraoleate, PEG-150 pentaerythritol tetrastearate, PEG-55 propylene glycol oleate, PEG-150 distearate.

[0193] Stabilizing polymers can be combined with cellulose and derivatives including cellulose gums, non-limiting examples of which include microcrystalline cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, ethyl cellulose; nitrocellulose; cellulose sulfate; cellulose powder; hydrophobically modified cellulose.

[0194] Stabilizing polymers may be combined with guar gum and guar gum derivatives, non-limiting examples of which include hydroxypropyl guar and hydroxypropyl guar hydroxypropyltrimonium chloride.

[0195] Stabilizing polymers can be combined with: polyethylene oxide; polypropylene oxide; and POE-PPO copolymers.

[0196] The stabilizing polymer may be combined with a polyalkylene glycol characterized by the following general formula:

[0197]

[0198] Wherein R is hydrogen, methyl, or a mixture thereof, preferably hydrogen, and n is an integer having an average number of 2,000-180,000, or 7,000-90,000, or 7,000-45,000. Non-limiting examples of this type include PEG-7M, PEG-14M, PEG-23M, PEG-25M, PEG-45M, PEG-90M, or PEG-100M.

[0199] The stabilizing polymer may be combined with silica, non-limiting examples of which include fumed silica, precipitated silica, and silicone surface-treated silica.

[0200] The stabilizing polymer may be combined with a water-swellable clay, non-limiting examples of which include laponite, bentonite, montmorillonite, smectite, and hectorite.

[0201] Stabilizing polymers may be combined with gums, non-limiting examples of which include xanthan gum, guar gum, hydroxypropyl guar gum, gum arabic, gum tragacanth, galactan, carob gum, karaya gum, and locust bean gum.

[0202] Stabilizing polymers can be combined with dibenzylidene sorbitol, karaggenan, pectin, agar, quince seeds (quinces), starch (from rice, corn, potato, wheat, etc.), starch derivatives (e.g., carboxymethyl starch, methylhydroxypropyl starch), algae extracts, dextran, succinoglucan, and pulleran.

[0203] Non-limiting examples of stabilizing polymers include acrylamide / ammonium acrylate copolymer (and) polyisobutylene (and) polysorbate 20; acrylamide / sodium acryloyldimethyl taurate copolymer / isohexadecane / polysorbate 80, ammonium acryloyldimethyl taurate / VP copolymer, sodium acrylate / sodium acryloyldimethyl taurate copolymer, acrylates copolymer, acrylates crosspolymer-4, acrylates crosspolymer-3, acrylates / beheneth-25 methacrylate copolymer, acrylates / C10-C30 alkyl acrylate crosspolymer, acrylates / stearyl polyoxyethylene ethoxylate-20 itaconate copolymer, poly Ammonium acrylate / isohexadecane / PEG-40 castor oil; Carbomer, sodium carbomer, cross-linked polyvinyl pyrrolidone (PVP), polyacrylamide / C13-14 isoparaffin / laureth-7, polyacrylate 13 / polyisobutylene / polysorbate 20, polyacrylate crosspolymer-6, polyamide-3, polyquaternium-37 (and) hydrogenated polydecene (and) trideceth-6, acrylamide / sodium acryloyldimethyl taurate / acrylic acid copolymer, sodium acrylate / acryloyldimethyl taurate / dimethylacrylamide, crosspolymer (and) isohexadecane (and) polysorbate 60, sodium polyacrylate. Exemplary commercially available stabilizing polymers include: ACULYN TM 28. ACULYN TM 88. ACULYN TM 33. ACULYN TM 22. ACULYN TM Excel, Aqua SF-1, ETD 2020, Ultrez 20, Ultrez 21, Ultrez 10, Ultrez 30, 1342, Aqua SF-2 polymer, Sepigel TM 305.Simulgel TM 600、SepimaxZen、 SMART 1000, TTA, SC-Plus, PLUS, AVC, Stabylen 30, and their combinations.

[0204] Suspension wax

[0205] Suspension waxes include suitable stabilizers to increase yield stress and viscosity. Such materials may include monoesters and / or diesters of alkylene glycols having the formula:

[0206]

[0207] Wherein R1 is a straight or branched C12-C22 alkyl group;

[0208] R is a linear or branched C2-C4 alkylene group;

[0209] P is selected from H, C1-C4 alkyl or -COR2, R2 is C4-C22 alkyl, or may be C12-C22 alkyl; and

[0210] n=1-3.

[0211] In the present invention, the long-chain fatty ester may have the general structure described above, wherein R1 is a linear or branched C16-C22 alkyl group, R is -CH2-CH2-, and P is selected from H or -COR2, wherein R2 is a C4-C22 alkyl group, or may be a C12-C22 alkyl group.

[0212] Typical examples are monoesters and / or diesters of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol or tetraethylene glycol with fatty acids containing from about 6 to about 22, from about 12 to about 18 carbon atoms, such as caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid, erucic acid, and mixtures thereof.

[0213] In the present invention, ethylene glycol monostearate (EGMS) and / or ethylene glycol distearate (EGDS) and / or polyethylene glycol monostearate (PGMS) and / or polyethylene glycol distearate (PGDS) may be the suspending wax used in the composition. There are several commercial sources of these materials. For example, Available from Stepan, Empilan Available from Albright & Wilson.

[0214] Traditionally, glyceride compounds can be used as structurants in personal care compositions. For example, R is trihydroxystearin, a commercial hydrogenated castor oil produced by Elementis Specialties of New Jersey and sold as a stabilizer and structurant for personal care compositions. Glycerides suitable for use in the personal care compositions described herein may be selected from any crystallizable glycerides that can allow for the formation of coacervates in a personal care composition comprising a suitable surfactant and a cationic polymer. For example, a suitable glyceride is hydrogenated castor oil, such as trihydroxystearin or dihydroxystearin.

[0215] The example of additional crystallizable glyceride can include the triglyceride of substantially pure 12-hydroxystearic acid. 12-hydroxystearic acid is the triglyceride of 12-hydroxy-9-cis-octadecenoic acid of pure form fully hydrogenated. It is appreciated that many other glycerides are possible. For example, the variation of hydrogenation process and the natural variation of castor oil can make it possible to produce other suitable glycerides from castor oil.

[0216] Suitable glycerides can also be formed by a mixture of one or more glycerides. For example, a glyceride mixture containing castor oil of about 80% or more by weight of the mixture may be suitable. Other suitable mixtures may include a mixture of only triglycerides, a mixture of diglycerides and triglycerides, a mixture of triglycerides and diglycerides and a limited amount of glycerol monoesters (e.g., less than about 20% by weight of the mixture); or any mixture thereof, which contains a corresponding acid hydrolyzate of any glyceride of about 20% or less by weight of the mixture. A mixture of about 80% or more by weight may be chemically identical to the glyceride of fully hydrogenated ricinoleic acid (i.e., the glyceride of 12-hydroxystearic acid). Hydrogenated castor oil may be modified so that in a given triglyceride, two 12-hydroxystearic acid moieties and one stearic acid moiety will be present. Alternatively, partial hydrogenation may be used. However, poly (alkoxylated) castor oil is not suitable because it has an inappropriate melting point.

[0217] Castor oil includes glycerides, especially triglycerides, containing C10 to C22 alkyl or alkenyl moieties doped with hydroxyl groups. The hydrogenation of castor oil produces hydrogenated castor oil by converting double bonds, which are present in the starting oil as castor oil-based moieties. These moieties are converted into castor oil-based moieties, which are saturated hydroxyalkyl moieties, such as hydroxystearyl. The hydrogenated castor oil (HCO) herein may be selected from: trihydroxystearin; dihydroxystearin; and mixtures thereof. HCO may be processed in any suitable starting form, including but not limited to those selected from solids, melts, and mixtures thereof. Available HCO may have the following characteristics: a melting point of about 40°C to about 100°C, alternatively about 65°C to about 95°C; and / or an iodine value range of about 0 to about 5, alternatively about 0 to about 4, and alternatively about 0 to about 2.6. The melting point of HCO may be measured using DSC: differential scanning calorimetry.

[0218] Suitable HCOs include those that are commercially available. Non-limiting examples of commercially available HCOs suitable for use include: (supplied by Elementis), which is supplied as a powder with small particles (99% by weight less than 44 microns).

[0219] The present invention is not intended to involve only the use of hydrogenated castor oil. Any other suitable crystallizable glycerides can be used. In one example, the structurant is a substantially pure triglyceride of 12-hydroxystearic acid. This molecule represents a triglyceride of 12-hydroxy-9-cis-octadecenoic acid that is fully hydrogenated in pure form. In essence, the composition of castor oil can vary slightly. Likewise, the hydrogenation procedure can vary. Any other suitable equivalent material can be used, such as a mixture of triglycerides, wherein at least about 80% by weight is from castor oil. Exemplary equivalent materials mainly include or consist of triglycerides; or mainly include or consist of a mixture of diglycerides and triglycerides; or mainly include or consist of a mixture of triglycerides with diglycerides and a limited amount (e.g., less than about 20% by weight of the weight of the glyceride mixture) of monoglycerides; or mainly include or consist of any of the aforementioned glycerides: it has a limited amount (e.g., less than about 20% by weight) of the corresponding acid hydrolyzate of any of the glycerides.

[0220] The stabilizing premix comprises from about 4% to about 30%, by weight of the personal care composition, of a 100% active stabilizer. In the present invention, the stabilizing premix may comprise from about 15% to about 25% of a stabilizer.

[0221] Suspended wax may be present in the present invention at about 0.01% to about 4%; suspended wax may be present in the present invention at about 0.1% to about 3%; suspended wax may be present in the present invention at about 0.5% to about 2%; suspended wax may be present in the present invention at about 0.3% to about 1.5%.

[0222] Water miscible solvents

[0223] The carrier of the hair care composition can include water and aqueous solutions of lower alkyl alcohols, polyols, ketones having 3 to 4 carbon atoms, C1-C6 esters of C1-C6 alcohols, sulfoxides, amides, carbonates, ethoxylated and propoxylated C1-C10 alcohols, lactones, pyrrolidones, and mixtures thereof. Non-limiting lower alkyl alcohols are monohydric alcohols having 1 to 6 carbons, such as ethanol and isopropanol. Non-limiting examples of polyols useful herein include propylene glycol, dipropylene glycol, butylene glycol, hexylene glycol, glycerol, propylene glycol, and mixtures thereof.

[0224] In the present invention, the hair care composition may contain a hydrotrope / viscosity modifier which is an alkali metal or ammonium salt of a lower alkylbenzene sulfonate, such as sodium xylene sulfonate, sodium cumene sulfonate or sodium toluene sulfonate.

[0225] In the present invention, the hair care composition may include silicone / PEG-8 silicone / PEG-9 silicone / PEG-n silicone / silicone ether (n may be another integer), non-limiting examples of which include PEG8-dimethicone A208) MW855, PEG 8 dimethicone D208 MW2706.

[0226] Scalp Health Supplement

[0227] In the present invention, in addition to the antifungal / anti-dandruff effects provided by sulfur, one or more scalp health agents may be added to provide scalp benefits. This group of materials is varied and provides a wide range of benefits, including moisturizing, barrier improvement, antifungal, antimicrobial and antioxidant agents, anti-itch agents and sensory agents, and additional anti-dandruff agents such as polyvalent metal salts of pyrithione, non-limiting examples include zinc pyrithione (ZPT) and copper pyrithione or selenium sulfide. Such scalp health agents include, but are not limited to: vitamins E and F, salicylic acid, niacinamide, caffeine, panthenol, zinc oxide, zinc carbonate, basic zinc carbonate, glycols, glycolic acid, PCA, PEG, erythritol, glycerin, triclosan, lactate, hyaluronate, allantoin and other ureas, betaine, sorbitol, glutamate, xylitol, menthol, menthyl lactate, isocyclic ketones, benzyl alcohol, compounds containing the following structure:

[0228]

[0229] R1 is selected from H, alkyl, aminoalkyl, alkoxy;

[0230] Q=H2, O, -OR1, -N(R1)2, -OPO(OR1) x 、-PO(OR1)x 、-P(OR1) x , where x = 1-2;

[0231] V=NR1、O、-OPO(OR1) x 、-PO(OR1) x 、-P(OR1) x , where x = 1-2;

[0232] W=H2、O;

[0233] For n=0, X, Y=are independently selected from H, aryl, naphthyl;

[0234] For n ≥ 1, X, Y = aliphatic CH2 or aromatic CH, and Z is selected from aliphatic CH2, aromatic CH or a heteroatom;

[0235] A = lower alkoxy, lower alkylthio, aryl, substituted aryl or condensed aryl; and

[0236] Stereochemistry can be varied at the positions marked *.

[0237] and natural extracts / oils including peppermint, spearmint, argan, jojoba and aloe vera.

[0238] The composition may also include one or more of the following scalp health agents, including coal tar, charcoal, compound benzoic acid ointment, castellani's paint, aluminum chloride, gentian violet, hydroxymethyl octopirox (piroctone olamine), ciclopirox olamine, undecylenic acid and its metal salts, azoxystrobin and other strobulins, potassium permanganate, sodium thiosulfate, propylene glycol, bitter orange oil, urea preparations, griseofulvin, 8-hydroxyquinoline clioquinol, thiodibutazole, thiocarbamates, haloprogin, polyene, hydroxypyridone, morpholine, benzylamine, allylamine (such as terbinafine), tea tree oil, clove leaf oil, coriander, palmarosa, berberine, thyme red, cinnamon oil, cinnamaldehyde, citronellal acid, hinokitiol, shale oil, Sensiva SC-50, Elestab HP-100, azelaic acid, lytic enzymes, iodopropynyl butylcarbamate (IPBC), isothiazolinones such as octylisothiazolinone, and azoles, itraconazole, ketoconazole, benzimidazole, benzothiazole, bifonazole, butaconazole nitrate, climbazole, clotrimazole, cloconazole, eberconazole, econazole, evoconazole, fenticonazole, fluconazole, flutrimazole, isoconazole, ketoconazole, lannoconazole, metronidazole, miconazole, neticonazole, omoconazole, oxiconazole nitrate, sertaconazole, sulconazole nitrate, tioconazole, thiazole, terconazole, and mixtures thereof.

[0239] Optional Ingredients

[0240] In the present invention, the hair care composition may also include one or more optional ingredients, including benefit agents. Suitable benefit agents include, but are not limited to, conditioning agents, cationic polymer silicone emulsions, anti-dandruff agents, gel networks, chelating agents, and natural oils such as sunflower oil or castor oil. In addition, suitable optional ingredients include, but are not limited to, fragrances, fragrance microcapsules, colorants, particles, antimicrobial agents, foam inhibitors, antistatic agents, rheology modifiers and thickeners, suspending materials and structurants, pH adjusters and buffers, preservatives, pearlescent agents, solvents, diluents, antioxidants, vitamins, and combinations thereof. In the present invention, fragrances may be present in an amount of about 0.5% to about 7%.

[0241] One or more stabilizers may be included. For example, one or more of ethylene glycol distearate, citric acid, citrate salts, preservatives such as kathon, sodium chloride, sodium benzoate, and ethylenediaminetetraacetic acid ("EDTA") may be included to improve the longevity of the personal care composition.

[0242] Such optional ingredients should be physically and chemically compatible with the components of the composition and should not otherwise unduly impair product stability, aesthetics or performance. The CTFA Cosmetic Ingredient Handbook, Tenth Edition (published by the Cosmetic, Toiletry and Fragrance Association, Inc., Washington) (2004) (hereinafter "CTFA") describes a wide variety of non-limiting materials that can be added to the compositions herein.

[0243] Conditioning Agents

[0244] The conditioning agent of the hair care composition can be a silicone conditioning agent. The silicone conditioning agent can include volatile silicones, non-volatile silicones, or combinations thereof. The concentration of the silicone conditioning agent is typically in the range of about 0.01% to about 10%, about 0.1% to about 8%, about 0.1% to about 5%, and / or about 0.2% to about 3% by weight of the composition. Non-limiting examples of suitable silicone conditioning agents and optional suspending agents for silicones are described in U.S. Reissue Patent 34,584, U.S. Pat. No. 5,104,646, and U.S. Pat. No. 5,106,609, which are incorporated herein by reference.

[0245] The silicone conditioning agent used in the present compositions can have a viscosity of about 20 to about 2,000,000 centistokes ("csk"), about 1,000 to about 1,800,000 csk, about 10,000 to about 1,500,000 csk, and / or about 20,000 to about 1,500,000 csk as measured at 25C.

[0246] The dispersed silicone conditioning agent particles typically have a volume average particle size in the range of about 0.01 microns to about 60 microns. For small particles applied to the hair, the volume average particle size is typically in the range of about 0.01 microns to about 4 microns, about 0.01 microns to about 2 microns, about 0.01 microns to about 0.5 microns.

[0247] Additional information on silicones, including chapters discussing silicone fluids, silicone gums, and silicone resins, and silicone manufacturing, can be found in Encyclopedia of Polymer Science and Engineering, Vol. 15, 2nd Edition, pp. 204-308, John Wiley & Sons, Inc. (1989), which is incorporated herein by reference.

[0248] Silicone emulsions suitable for use in the present invention may include, but are not limited to, insoluble polysiloxane emulsions prepared according to the descriptions provided in U.S. Pat. No. 6,316,541 or U.S. Pat. No. 4,476,282 or U.S. Patent Application Publication No. 2007 / 0276087. Thus, suitable insoluble polysiloxanes include polysiloxanes, such as α,ω-hydroxyl-terminated polysiloxanes or α,ω-alkoxy-terminated polysiloxanes, having an internal phase viscosity of about 5 csk to about 500,000 csk. For example, the insoluble polysiloxane may have an internal phase viscosity of less than 400,000 csk, preferably less than 200,000 csk, more preferably about 10,000 csk to about 180,000 csk. The insoluble polysiloxane may have an average particle size in the range of about 10 nm to about 10 microns. The average particle size may range from about 15 nm to about 5 microns, from about 20 nm to about 1 micron, or from about 25 nm to about 500 nm.

[0249] The average molecular weight of the insoluble polysiloxane, the viscosity of the internal phase of the insoluble polysiloxane, the viscosity of the silicone emulsion, and the size of the particles containing the insoluble polysiloxane are determined by methods commonly used by those skilled in the art, such as the method disclosed in Smith, AL, The Analytical Chemistry of Silicones, John Wiley & Sons, Inc.: New York, 1991. For example, the viscosity of the silicone emulsion can be measured at 30° C. using a Brookfield viscometer and spindle 6 at 2.5 rpm. The silicone emulsion may also include additional emulsifiers as well as anionic surfactants.

[0250] Other types of silicones suitable for use in the compositions of the present invention include, but are not limited to: i) silicone fluids, including but not limited to silicone oils, which are flowable materials having a viscosity of less than about 1,000,000 csk as measured at 25°C; ii) aminosilicones comprising at least one primary, secondary or tertiary amine; iii) cationic silicones comprising at least one quaternary ammonium functional group; iv) silicone gums; which include materials having a viscosity greater than or equal to 1,000,000 csk as measured at 25°C; v) silicone resins comprising highly crosslinked polymerized siloxane systems; vi) high refractive index silicones having a refractive index of at least 1.46, and vii) mixtures thereof.

[0251] The conditioning agent of the hair care composition of the present invention may also include at least one organic conditioning material such as an oil or wax, alone or in combination with other conditioning agents such as the above-mentioned silicones. The organic material may be non-polymeric, oligomeric or polymeric. It may be in the form of an oil or wax and may be added as a pure formulation or in a pre-emulsified form. Some non-limiting examples of organic conditioning materials include, but are not limited to: i) hydrocarbon oils; ii) polyolefins; iii) fatty esters; iv) fluorinated conditioning compounds; v) fatty alcohols; vi) alkyl glucosides and alkyl glucoside derivatives; vii) quaternary ammonium compounds; viii) polyethylene glycols and polypropylene glycols having a molecular weight of up to about 2,000,000, including those having the CTFA designations PEG-200, PEG-400, PEG-600, PEG-1000, PEG-2M, PEG-7M, PEG-14M, PEG-45M, and mixtures thereof.

[0252] Gel Network

[0253] In the present invention, a gel network may be present. The gel network component of the present invention comprises at least one fatty amphiphile. As used herein, "aliphatic amphiphile" refers to a compound having a hydrophobic tail group and a hydrophilic head group, wherein the hydrophobic tail group is defined as C 12 -C 70 Length alkyl, alkenyl (containing up to 3 double bonds), alkyl aromatic or branched alkyl group, the hydrophilic head group renders the compound insoluble in water, wherein the compound also has a net neutrality at the pH of the shampoo composition.

[0254] The shampoo compositions of the present invention comprise the fatty amphiphile as part of a preformed dispersed gel network phase in an amount from about 0.05% to about 14%, preferably from about 0.5% to about 10%, and more preferably from about 1% to about 8%, by weight of the shampoo composition.

[0255] According to the present invention, suitable fatty amphiphiles or suitable mixtures of two or more fatty amphiphiles have a melting point of at least about 27°C. As used herein, melting point can be determined by, for example, US Pharmacopeia, USP-NF General Chapter <741> The melting point of a mixture of two or more materials is determined by mixing the two or more materials at a temperature above their respective melting points and then cooling the mixture. If the resulting composite material is a homogeneous solid below about 27°C, the mixture has a melting point suitable for use in the present invention. A mixture of two or more fatty amphiphiles is also suitable for use in the present invention, provided that the composite melting point of the mixture is at least about 27°C, wherein the mixture contains at least one fatty amphiphile having an individual melting point less than about 27°C.

[0256] Suitable fatty amphiphiles of the present invention include fatty alcohols, alkoxylated fatty alcohols, fatty phenols, alkoxylated fatty phenols, fatty amides, alkoxylated fatty amides, fatty amines, fatty alkylamidoalkylamines, fatty alkoxylated amines, fatty carbamates, fatty amine oxides, fatty acids, alkoxylated fatty acids, fatty diesters, fatty sorbitan esters, fatty sugar esters, methyl glucoside esters, fatty glycol esters, mono-, di- and triglycerides, polyglycerol fatty esters, alkyl glyceryl ethers, propylene glycol fatty acid esters, cholesterol, ceramides, fatty silicone waxes, fatty glucamides and phospholipids, and mixtures thereof.

[0257] In the present invention, shampoo compositions may include fatty alcohol gel networks. These gel networks are formed by mixing fatty alcohols with surfactants in a ratio of about 1:1 to about 40:1, about 2:1 to about 20:1, and / or about 3:1 to about 10:1. The formation of the gel network involves heating a dispersion of fatty alcohols in water with the surfactant to a temperature above the melting point of the fatty alcohols. During the mixing process, the fatty alcohols melt, thereby allowing the surfactants to separate into fatty alcohol droplets. The surfactants carry water with them into the fatty alcohols. This turns the isotropic fatty alcohol drops into liquid crystal phase drops. When the mixture is cooled to below the chain melting temperature, the liquid crystal phase transitions to a solid crystalline gel network. The gel networks provide stabilization benefits to cosmetic creams and hair conditioners. In addition, they also deliver the conditioning feel benefits of hair conditioners.

[0258] The fatty alcohol may be included in the fatty alcohol gel network at a content of about 0.05 wt % to about 14 wt %. For example, the fatty alcohol content may be in the range of about 1 wt % to about 10 wt %, and / or about 6 wt % to about 8 wt %.

[0259] Fatty alcohols useful herein include those having from about 10 to about 40 carbon atoms, from about 12 to about 22 carbon atoms, from about 16 to about 22 carbon atoms, or from about 16 to about 18 carbon atoms. These fatty alcohols may be straight chain alcohols or branched chain alcohols, and may be saturated or unsaturated. Non-limiting examples of fatty alcohols include cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof. A mixture of cetyl alcohol and stearyl alcohol in a ratio of about 20:80 to about 80:20 is suitable.

[0260] Gel Network Preparation: Water is charged to a container and heated to about 74°C. Cetyl alcohol, stearyl alcohol, and SLES surfactant are added to the heated water. After incorporation, the resulting mixture is passed through a heat exchanger where the mixture is cooled to about 35°C. Upon cooling, the fatty alcohol and surfactant crystallize to form a crystalline gel network. Table 1 provides the components of an exemplary gel network composition and their corresponding amounts.

[0261] Table 1 Gel network components

[0262]

[0263]

[0264] In the present invention, there may be present a personal care composition wherein the composition does not comprise a gel network.

[0265] Emulsifier

[0266] A variety of anionic and nonionic emulsifiers can be used in the hair care compositions of the present invention. Anionic and nonionic emulsifiers can be monomeric or polymeric in nature. For example, examples of monomers include, but are not limited to, alkyl ethoxylates, alkyl sulfates, soaps, and fatty acid esters, and their derivatives. By way of illustration and not limitation, examples of polymers include polyacrylates, polyethylene glycols, and block copolymers, and their derivatives. Naturally occurring emulsifiers such as lanolin, lecithin, and lignin, and their derivatives, are also non-limiting examples of useful emulsifiers.

[0267] Chelating agents

[0268] The personal care composition may also include a chelating agent. Suitable chelating agents include those listed in Critical Stability Constants Vol. 1 of AE Martell & RM Smith (Plenum Press, New York & London (1974)) and Metal Complexes in Aqueous Solution of AE Martell & RD Hancock (Plenum Press, New York & London (1996)), both of which are incorporated herein by reference. When chelating agents are involved, the term "their salts and derivatives" refers to salts and derivatives having the same functional structure (e.g., the same chemical backbone) as the chelating agent to which they are involved and having similar or better chelating properties. The term includes alkali metal salts, alkaline earth metal salts, ammonium salts, substituted ammonium (i.e., monoethanolamine, diethanolamine, triethanolammonium) salts, esters, and mixtures thereof, especially all sodium salts, potassium salts, or ammonium salts of chelating agents having an acidic portion. The term "derivative" also includes "chelating surfactant" compounds such as those exemplified in U.S. Pat. No. 5,284,972, and macromolecules containing one or more chelating groups having the same functional structure as the parent chelating agent such as the polymer EDDS (ethylenediamine disuccinic acid) disclosed in U.S. Pat. No. 5,747,440.

[0269] Chelating agents may be incorporated into the compositions herein in an amount ranging from 0.001% to 10.0%, preferably from 0.01% to 2.0% by weight of the total composition.

[0270] Non-limiting classes of chelating agents include carboxylic acids, aminocarboxylic acids including amino acids, phosphoric acids, phosphonic acids, polyphosphonic acids, polyethyleneimines, polyfunctionally substituted aromatic compounds, their derivatives and salts.

[0271] Non-limiting chelating agents include the following and their salts. Ethylenediaminetetraacetic acid (EDTA), ethylenediaminetriacetic acid, ethylenediamine-N,N'-disuccinic acid (EDDS), ethylenediamine-N,N'-diglutaric acid (EDDG), salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid, histidine, diethylenetriaminepentaacetate (DTPA), N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, ethanol diglycine, propylenediaminetetraacetate (PDTA), methylglycine diacetic acid (MODAA), diethylenetriaminepentaacetic acid, methylglycine diacetic acid (MGDA), N-acyl-N,N',N' -ethylenediaminetriacetic acid, nitrilotriacetic acid, ethylenediamine diglutaric acid (EDGA), 2-hydroxypropylenediamine disuccinic acid (HPDS), glycinamide-N,N'-disuccinic acid (GADS), 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS), N-2-hydroxyethyl-N,N-diacetic acid, glycerol iminodiacetic acid, iminodiacetic acid-N-2-hydroxypropyl sulfonic acid, aspartic acid N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid, alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid N-monoacetic acid, iminodisuccinic acid, diamine-N,N'-dicarboxylic acid, mono Amide-N,N'-dicarboxylic acid, diaminoalkyl di(sulfosuccinic acid) (DDS), ethylenediamine-N-N'-bis(o-hydroxyphenylacetic acid), N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, ethylenediamine tetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, pyridine dicarboxylic acid, ethylenedicysteine ​​(EDC), ethylenediamine-N,N'-bis(2-hydroxyphenylacetic acid) (EDDHA), glutamic acid diacetic acid (GLDA), hexaadenylic acid aminocarboxylate (HBED), polyethyleneimine, 1-hydroxydiphosphonate, aminotri(methylenephosphonic acid) (ATMP), Nitrilotrimethylenephosphonate (NTP), ethylenediaminetetramethylenephosphonate, diethylenetriaminepentamethylenephosphonate (DTPMP), ethane-1-hydroxydiphosphonate (HEDP), 2-phosphonobutane-1,2,4-tricarboxylic acid, polyphosphoric acid, sodium tripolyphosphate, tetrasodium diphosphate, hexametaphosphoric acid, sodium metaphosphate, phosphonic acid and its derivatives, aminoalkylene-poly(alkylenephosphonic acid), aminotri(1-ethylphosphonic acid), ethylenediaminetetra(1-ethylphosphonic acid), aminotri(1-propylphosphonic acid), aminotri(isopropylphosphonic acid), ethylenediaminetetra(methylenephosphonic acid) (EDTMP), 1,2-dihydroxy-3,5-disulfonylbenzene.

[0272] Aqueous carrier

[0273] The personal care composition may be in the form of a pourable liquid (under ambient conditions). Such compositions will therefore typically comprise a carrier present at a level of from about 40% to about 85%, alternatively from about 45% to about 80%, or alternatively from about 50% to about 75%, by weight of the hair care composition. The carrier may comprise water, or a miscible mixture of water and an organic solvent, and in one aspect, may comprise water with minimal or insignificant concentrations of organic solvents, except for those otherwise incidentally incorporated into the composition as minor ingredients of other essential or optional components.

[0274] The carriers useful in the personal care compositions of the present invention may include water and aqueous solutions of lower alkyl alcohols and polyols. The lower alkyl alcohols useful herein are monohydric alcohols having 1 to 6 carbons, in one aspect, ethanol and isopropanol. Exemplary polyols useful herein include propylene glycol, hexylene glycol, glycerol, and propane diol.

[0275] Product form

[0276] The personal care compositions of the present invention may be in the form of typical hair care formulations. They may be in the form of solutions, dispersions, emulsions, powders, talcs, encapsulations, spheres, sponges, solid dosage forms, foams, and other delivery mechanisms. The compositions of the present invention may be hair tonics, leave-in hair products such as treatments, and styling products, rinse-off hair products such as shampoos and personal cleansing products, and treatment products; and any other form that may be applied to the hair.

[0277] Application device

[0278] In the present invention, the hair care composition can be dispensed from an applicator for direct dispensing to the scalp area. Dispensing directly onto the scalp via a targeted delivery applicator enables deposition of undiluted cleansing agent directly where the cleaning need is highest. This also minimizes the risk of eye contact with the cleaning solution.

[0279] The applicator is attached or attachable to a bottle containing a clean hair care composition. The applicator may consist of a base that houses or extends to a single or multiple tines. The tines have openings that may be located at the tip, the base, or any point between the tip and the base. These openings allow the product to be dispensed directly from the bottle onto the hair and / or scalp.

[0280] Alternatively, the applicator may also consist of brush-like bristles attached to or extending from a base. In this case, the product will be dispensed from the base, and the bristles will allow product dispensing via a combing or brushing motion.

[0281] Applicator and tine design and materials may also be optimized to achieve scalp massage. In this case, it may be advantageous to have the tine or bristle geometry at the tip be more rounded, similar to a roller ball applicator for eye cream. Materials that are smoother and softer may also be beneficial; for example, metallic or metallic-like finishes, "rubbery materials".

[0282] method

[0283] Viscosity measurement

[0284] A cone-plate Brookfield RS rheometer with cone C75-1 can be used at 2 s -1 Shampoo viscosity was measured at a constant shear rate of 500 Å at 27° C. at 3 minutes for 2.5 mL of sample.

[0285] Measurement of sulfur deposition

[0286] In vivo deposition of sulfur on the scalp can be determined by ethanol extraction of the agent after the scalp has been treated with a sulfur-containing cleaning composition and rinsed off. The concentration of the agent in the ethanol extraction solvent is measured by HPLC. Quantification is performed by reference to a standard curve. The concentration detected by HPLC is converted to the amount collected in grams by multiplying the concentration by the volume.

[0287] The mass per reagent volume concentration was then converted to mass per deposited area by multiplying the measured HPLC concentration by the volume of extraction solvent divided by the extracted scalp area.

[0288] Measurement of sulfur particle size distribution

[0289] The sulfur particle size distribution was measured using a Horiba LA-950 laser scattering particle size analyzer with LA-950 for Windows software version 8.10. The sulfur material was stirred continuously in a 1% SDS solution until uniformly dispersed. While stirring continuously, the dispersed sulfur was transferred to a Horiba instrument 0.1% SDS dispersant with circulation (speed: 3), stirring (speed: 1) and ultrasonic treatment (power: 1) turned on. The dispersed sulfur sample was added until the transmittance percentage was about 90%. Refractive index values ​​of 2.245-0.10i (sulfur) and 1.333 (dispersant) were used to report D10, D50 and D90 values ​​based on volume.

[0290] Odor Assessment Methods

[0291] In order to evaluate the effectiveness of additives in eliminating malodors of sulfur-containing shampoos, small sections (hair clusters) of uniform human hair with plastic tape and adhesive fixed on one end were washed and dried to simulate the shampooing and hair styling process. At various points during and after this process, individuals trained in fragrance evaluation were assigned a sulfur malodor intensity value of 0 (no malodor) to 9 (extremely high malodor) at each time point during foaming, after rinsing, and after blow-drying, and then the scores were totaled for an overall cumulative range score of 0 to 27. Formulations that produced no or slight malodor (0-1) scores at all points of hair cluster treatment were considered to be effective in eliminating sulfur malodor. All shampoo formulations were pre-screened via self-washing on the forearm or head, and subsequent evaluations of pass / fail perceived sulfur malodor in potential effective examples were more formally evaluated.

[0292] Yield stress tables and yield stress determination methods

[0293] To perform these measurements, the present invention used a TA DHR3 rheometer equipped with cone and plate geometry.

[0294] A solvent trap was added to avoid sample evaporation during the measurement. This used a cone and plate geometry, ran up to 40 °C and lasted approximately 30 minutes.

[0295] Test 1 - Flow curve at 25°C: At a fixed temperature of 25°C, a steady-state flow curve in strain control mode starting at 100 1 / s and decreasing to 0.011 / s was performed. The choice of controlling the shear rate and starting at high shear was made in order to measure the dynamic yield stress. This measurement scheme minimizes the effects of sample thixotropy, which can induce variability in the yield stress measurement based on the sample shear history. The total duration of this test is ~8 minutes.

[0296] Test 2 - Temperature ramp: Temperature ramp starting from 25°C up to 40°C at a fixed shear rate of 2s-1. The choice of 2s-1 shear rate was made because it captures the low shear plateau value of the worm-like micelle microstructure present in the transparent phase. The total duration of this test is ~8 minutes.

[0297] Test 3 - Flow curve at 40°C: At a fixed temperature of 40°C, a steady-state flow curve in strain control mode starting at 100 1 / s and decreasing to 0.011 / s was performed. The total duration of this step was ~8 minutes.

[0298] The total duration of the complete procedure including sample loading was approximately 30 minutes.

[0299] The data were analyzed fitting the data to a three component model [3 component model articles referenced below] in combination with a power law model described by the following expression:

[0300]

[0301] In expressions:

[0302] σ: To maintain the target shear rate Required shear stress

[0303] σ y : is the yield stress

[0304] Critical shear rate

[0305] K PL : consistency parameter describing the viscosity of the continuous phase

[0306] n PL : is the power law exponent describing the shear thinning behavior of the continuous phase

[0307] The data obtained from Test 1, the room temperature data, and the Test 40 C data were fit via a standard nonlinear regression algorithm to estimate the best set of model parameters that fit the data.

[0308] In the following Table 2 we report the obtained yield stress parameters for the different samples presented:

[0309] Table 2

[0310]

[0311]

[0312] Caggioni, Marco, Veronique Trappe, and Patrick T. Spicer. “Variations of the Herschel-Bulkley exponent reflecting contributions of the viscous continuous phase to the shear rate-dependent stress of soft glassy materials.” Journal of Rheology 64.2 (2020): 413-422. (incorporated herein by reference).

[0313] result

[0314] In vivo fungal efficacy testing

[0315] Subjects from all test groups will have a baseline scalp swab for measuring scalp Malassezia. Subjects will take one or more test products and will use the test products as directed throughout the week. Testing ends in Week 2, where panelists are swabbed and samples collected. Malassezia is quantified from scalp surface swabs via qPCR. Changes in the amount of Malassezia across time will be reported as a % reduction in fungi from baseline at the Week 2 time point.

[0316] Example Composition

[0317]

[0318]

[0319] *Example 6 was run in two studies as a common control between them

[0320]

[0321] A dissolution and diffusion model was used to help maintain sulfur solubility in sebum over a 24 hour period. For the fungus that causes dandruff (Malassezia), the model predicts that sulfur concentration will rise to the minimum inhibitory concentration (for sulfur, the MIC is known to be in the range of 10-50 ppm). Over a 24 hour period, the model factors in sulfur dissolution that change sebum thickness and sebum production rate, as well as the loss term for sulfur migration into the scalp / stratum corneum. Figures (1-4) show the simulation output for sulfur particles with an average sulfur particle size of 2, 34, 100 and 150 microns, respectively, where each figure is a compilation of curves representing the initial sebum thickness and the change in production rate. The gray box in each figure represents a series of sulfur concentrations including the recognized MIC (log10(MIC) range is 1-1.7). It was observed from the simulation that as the particle size increased, the approximate number of times the sulfur concentration was above the MIC expanded until the particle size was about 150 microns, where the dissolution of sulfur in sebum became the rate limiting step, and the concentration of sulfur never exceeded the MIC required for the dandruff benefit.

[0322]

[0323] Understanding the need for increased stability requirements

[0324] Since the sulfur particles have a higher density than the suspending fluid, in order to maintain product homogeneity, it is necessary to add an elastic microstructure to the fluid. This microstructure must be strong enough to prevent particle settling during shelf life, and weak enough under stress to allow the fluid to flow during dispensing, and also spread with relative ease during application and foaming.

[0325] To achieve this goal, colloidal-scale particles (ethylene glycol distearate platelets, trihydroxystearin, etc.) or polymer thickeners such as acrylate copolymers are often added separately to transform the fluid into a yield stress fluid. Yield stress fluids have a permanent elastic microstructure at rest that prevents particles from settling, but may flow when a stress exceeding the yield stress is applied.

[0326] Failure Mode 1 - Tunneling :

[0327] The first necessary condition for product stability is to have a yield stress that is higher than the stress exerted by each individual particle in and around the microstructure. The minimum yield stress can be found using the following formula:

[0328]

[0329] See Beris, AN, Tsamopoulos, JA, Armstrong, RC, and Brown, RA, 1985. Creeping motion of a sphere through a Bingham plastic. Journal of Fluid Mechanics, 158, pp. 219-244 (incorporated herein by reference).

[0330] Based on available models, one skilled in the art can estimate the minimum yield stress (σ) required to suspend sulfur particles. y ), the sulfur particle has a radius r P =50μm and density mismatch suspension fluid Δρ=1000Kg / m 3 :

[0331]

[0332] Where g is the acceleration due to gravity. If the yield stress is insufficient, the particles will settle (or emulsify). When this condition is met, one would expect the particles to be trapped in the elastic microstructure.

[0333] Tunneling failure mode: occurs when the structure does not exist (sample A) ( Figure 5 ) or does not provide sufficient yield stress (Sample C) ( Figure 6 ). Sulfur particles, which are denser than the continuous phase, are present in sample A (without structure) ( Figure 5 ) and sample C (weak structure) settled to the bottom ( Figure 6 ). The silicone droplets are emulsified to the top. Figure 7 Schematic diagram of such tunneling failure mode, including 5% sulfur particles (SP) and silicone droplets (SD).

[0334] Stable: The distribution of suspended particles remains constant over time. No visible settling, emulsification or compression, such as sample D ( Figure 8 ) as shown in the figure.

[0335] Sample D (40°C) Figure 8 ) The colloidal gel provides sufficient yield stress to prevent sedimentation and emulsification of the sulfur and silicone particles. The acrylate copolymer increases the low shear viscosity of the surfactant solution, thereby avoiding the compression failure mode observed in Sample B ( Fig. 9 ).

[0336] Failure Mode 2 - Compression :

[0337] However, a sufficiently high yield stress is not sufficient to ensure homogeneity of the product throughout its intended shelf life. Even if each individual particle is successfully captured, the total stress exerted by the particles can induce deformation and compression of the elastic microstructure, where the suspended particles and colloidal network remain intact but the diluted surfactant is expressed and presents as a separate phase on top of the product.

[0338] The structurant microstructure is a porous network filled by the continuous phase of the product, like a sponge. Under the weight of the particles, the structure gets "squeezed" and a transparent layer appears. To avoid this problem, the inventors have seen two options: increase the strength of the structure so that it cannot deform, and / or increase the viscosity of the fluid to slow down the compression and delay failure later than the desired shelf life of the product.

[0339] Compression failure mode: Compression of the colloidal gel network describes the instability induced by the accumulated stress (which is attributed to the particles trapped in the colloidal gel network). In the present invention, the network yield stress is sufficient to successfully stop the particle sedimentation. However, the total stress exerted by the particles trapped on the structurant network induces its slow compression, resulting in the appearance of a transparent layer on the top or bottom of the sample.

[0340] Fig.10 Schematic diagram in which 5% sulfur particles (SP) exert a net downward force. Silicone droplets (SD) provide a smaller net upward force. Fig.10 The grid in represents the compression of the colloidal gel network towards the bottom, resulting in the appearance of a transparent layer (no network, no silicone, and no sulfur) on the top of the sample.

[0341] Microstructure design

[0342] Microstructure design formula

[0343]

[0344]

[0345]

[0346] With the goal of preventing both tunneling and compression failure modes, the inventors have explored different stabilization methods:

[0347]

[0348] * The sample was placed in a clear glass jar at high temperature (40°C) and the changes over time were observed.

[0349] **Acrylate copolymers form swollen microgel particles when dissolved in a surfactant solution. These domains construct the product by forming space-filling colloidal glasses that can provide a yield stress to the fluid. In this case, an undetectable yield stress was measured by rheological characterization. Time lapse monitoring confirmed the absence of a yield stress, thereby detecting sulfur particle sedimentation similar to (although slower than) that observed in the control sample. However, the effect of the material on the formulation structure can be seen in the increase in the viscosity of the transparent phase with a value greater than 10 Pa·s for shear rates below 0.001 1 / s at 25°C and 40°C. This is important information because the shear rate associated with the sedimentation process is about 0.001 1 / s or less. While not providing a yield stress, the presence of the acrylate copolymer effectively increases the low shear transparent phase viscosity that controls the sedimentation and compression rates.

[0350] ***Based on previous observations, the present invention further combines two structurants: trihydroxystearin (to address tunneling failures) and acrylate copolymer (to slow down colloidal gel network compression by increasing viscosity at relevant shear rates for sedimentation). In this particular formulation, the yield stress is sufficient to suspend the sulfur particles, and the high viscosity at low shear provided by the acrylate copolymer slows down compression at high temperatures by a factor >100x, providing stability.

[0351] It should be noted that the strategy of combining yield stress and high low shear viscosity does not specifically require the combination of trihydroxystearin and acrylate copolymers. Different combinations of suspending waxes and stabilizing polymers should also work.

[0352] Preparation of shampoo compositions

[0353] The personal care composition is prepared by adding the remainder of the surfactant, anti-dandruff agent, fragrance, viscosity modifier, cationic polymer and water with sufficient stirring to ensure a uniform mixture. The mixture may be heated to 50-75°C to accelerate the dissolution of the soluble agents and then cooled. The product pH may be adjusted as needed to provide a shampoo composition of the present invention suitable for application to human hair and scalp, and may vary from about pH 4 to 9, or from about pH 4.5 to 6.5, or from about pH 5 to 6, based on the selection of specific detersive surfactants and / or other components.

[0354] Non-limiting Examples

[0355] The personal care compositions exemplified in the following examples can be prepared by conventional formulation and mixing methods. Unless otherwise specified, all exemplified amounts are listed as weight percentages based on active material, and except for minor materials such as diluents, preservatives, color solutions, hypothetical ingredients, botanicals, etc. Unless otherwise specified, all percentages are based on weight.

[0356]

[0357]

[0358] *Examples 13 and 14 show significant settling of sulfur particles over time when placed in a stability chamber at 40°C, indicating shelf stability failure in less than 12 weeks. Examples 7-12 show no significant settling of particles for greater than 12 weeks at 40C.

[0359]

[0360] The dimensions and values ​​disclosed herein are not to be understood as being strictly limited to the exact numerical values ​​cited. Instead, unless otherwise indicated, each such dimension is intended to represent the stated value and a functionally equivalent range around that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

[0361] Unless expressly excluded or otherwise limited, each document cited herein, including any cross-referenced or related patent or patent application and any patent application or patent to which this application claims priority or the benefit of, is hereby incorporated by reference in its entirety. The citation of any document is not an admission that it is prior art to any of the present invention disclosed or claimed herein, or an admission that it, by itself or in combination with any one or more of the references, proposes, suggests, or discloses any such invention. In addition, to the extent that any meaning or definition of a term in this invention conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this invention shall govern.

[0362] Although specific embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications may be made without departing from the spirit and scope of the present invention. Therefore, it is intended that all such changes and modifications within the scope of the present invention be covered in the appended claims.

Claims

1. A personal care composition comprising: (a) 10% to 25% of one or more surfactants; (b) 0.5 to 5% sulphur; (c) wherein the sulfur has an average particle size D50 of 34 μm to 150 μm; (d) 0.4% to 10% of one or more stabilizing polymers, wherein the one or more stabilizing polymers are selected from acrylamide / ammonium acrylate copolymer and polyisobutylene and polysorbate 20; acrylamide / sodium acryloyldimethyl taurate copolymer / isohexadecane / polysorbate 80, ammonium acryloyldimethyl taurate / VP copolymer, sodium acrylate / sodium acryloyldimethyl taurate copolymer, acrylates crosspolymer-4, acrylates crosspolymer-3, acrylates / beheneth-25 methacrylate copolymer, acrylates / C10-C30 alkyl acrylate crosspolymer, acrylates / stearyl eth-20 itaconic acid Ester copolymer, ammonium polyacrylate / isohexadecane / PEG-40 castor oil; carbomer, sodium carbomer, cross-linked polyvinyl pyrrolidone, polyacrylamide / C13-14 isoparaffin / laureth-7, polyacrylate 13 / polyisobutene / polysorbate 20, polyacrylate crosspolymer-6, polyamide-3, polyquaternium-37 and hydrogenated polydecene and trideceth-6, acrylamide / sodium acryloyldimethyltaurate / acrylic acid copolymer, sodium acrylate / acryloyldimethyltaurate / dimethylacrylamide, crosspolymer and isohexadecane and polysorbate 60, sodium polyacrylate, and mixtures thereof; and (e) 0.1% to 4% of a suspending wax, wherein the suspending wax is selected from the group consisting of trihydroxystearin, dihydroxystearin, and mixtures thereof.

2. A personal care composition comprising: (a) 10% to 25% of one or more surfactants; (b) 0.5 to 5% sulphur; (c) wherein the sulfur has an average particle size D50 of 34 μm to 150 μm; (d) 0.4% to 10% of one or more stabilizing polymers, wherein the one or more stabilizing polymers are selected from acrylate copolymers; and (e) 0.1% to 4% of a suspending wax, wherein the suspending wax is selected from the group consisting of trihydroxystearin, dihydroxystearin, and mixtures thereof.

3. A personal care composition according to claim 1 or 2, wherein the one or more surfactants are from 10% to 18%.

4. The personal care composition of claim 1 or 2, wherein the one or more surfactants are from 10% to 14%.

5. The personal care composition according to claim 1 or 2, wherein the sulfur has an average particle size D50 of 34 μm to 100 μm.

6. The personal care composition of claim 1 or 2, wherein the sulfur has an average particle size D50 of 34 μm to 75 μm.

7. The personal care composition of claim 1 or 2, wherein the sulfur has an average particle size D50 of 34 μm to 50 μm.

8. The personal care composition of claim 1 or 2, wherein the composition comprises from 0.4% to 8% of one or more stabilizing polymers.

9. The personal care composition of claim 1 or 2, wherein the composition comprises from 0.7% to 5% of one or more stabilizing polymers.

10. The personal care composition of claim 1 or 2, wherein the composition comprises from 0.1% to 3% of a suspended wax.

11. The personal care composition of claim 1 or 2, wherein the sulfur has an average particle size D90 of 30 micrometers (µm) to 250 micrometers (µm).

12. The personal care composition of claim 1 or 2, wherein the sulfur has an average particle size D90 of 30 micrometers (µm) to 100 micrometers (µm).

13. The personal care composition of claim 1 or 2, wherein the sulfur has an average particle size D10 of 1 micrometer (µm) to 25 micrometers (µm).

14. The personal care composition of claim 1 or 2, wherein the sulfur has an average particle size D10 of 18 micrometers (µm) to 25 micrometers (µm).

15. The personal care composition of claim 1 or 2, wherein the sulfur has an average particle size D90 / average particle size D10 ratio of 3 to 100.

16. The personal care composition of claim 1 or 2, wherein the sulfur has an average particle size D90 / average particle size D10 ratio of 3 to 50.

17. The personal care composition of claim 1 or 2, wherein the sulfur has an average particle size D90 / average particle size D10 ratio of 3 to 10.

18. The personal care composition of claim 1 or 2, wherein the sulfur has an average particle size D90 / average particle size D10 ratio of 3 to 4.

19. The personal care composition of claim 1 or 2, wherein the surfactant is an anionic surfactant or a combination of anionic surfactants.

20. The personal care composition according to claim 1 or 2, wherein the surfactant is an anionic surfactant selected from the group consisting of anionic alkyl sulfates and alkyl ether sulfates having a linear or branched alkyl chain and mixtures thereof.

21. The personal care composition of claim 1 or 2, wherein the surfactant is an anionic surfactant selected from the group consisting of: a) R1O(CH2CHR3O) y SO3M; b) CH3(CH2) z CHR2CH2O(CH2CHR3O) y SO3M; and c) mixtures thereof, Where R1 represents CH3(CH2) 10 , R2 represents H or a hydrocarbon group containing 1 to 4 carbon atoms, such that the sum of the carbon atoms in z and R2 is 8, R3 is H or CH3, y is 0 to 7, when y is not zero (0), the average value of y is 1, and M is a monovalent or divalent positively charged cation.

22. The personal care composition of claim 1 or 2, wherein the surfactant is one or more of the following sulfate-free surfactants: sodium, ammonium, or potassium salts of isethionates; sodium, ammonium, or potassium salts of sulfonates; sodium, ammonium, or potassium salts of ether sulfonates; sodium, ammonium, or potassium salts of sulfosuccinates; sodium, ammonium, or potassium salts of sulfoacetates; sodium, ammonium, or potassium salts of glycinates; sodium, ammonium, or potassium salts of sarcosinates; sodium, ammonium, or potassium salts of glutamates; sodium, ammonium, or potassium salts of alaninates; sodium, ammonium, or potassium salts of carboxylates; sodium, ammonium, or potassium salts of taurates; sodium, ammonium, or potassium salts of phosphates; and combinations thereof.

23. The personal care composition of claim 1 or 2, further comprising from 0.25% to 15% of one or more amphoteric co-surfactants, nonionic co-surfactants, or zwitterionic co-surfactants.

24. The personal care composition of claim 1 or 2, wherein the pH of the composition is from 4 to 9.

25. The personal care composition of claim 1 or 2, wherein the composition has a pH of 4.5 to 6.

5.

26. The personal care composition of claim 1 or 2, wherein the pH of the composition is from 5 to 6.

27. The personal care composition of claim 1 or 2, wherein the pH of the composition is from 4 to 5.

28. The personal care composition of claim 1 or 2, wherein the composition further comprises a cationic polymer.

29. The personal care composition of claim 1 or 2, wherein the composition further comprises a gel network.

30. The personal care composition of claim 1 or 2, wherein the composition further comprises a conditioning agent.

31. The personal care composition of claim 30, wherein the conditioning agent is a silicone.

32. The personal care composition of claim 1 or 2, further comprising one or more scalp health agents.

33. A personal care composition according to claim 32, wherein the scalp health agent is selected from zinc pyrithione, salicylic acid, piroctone olamine, azoxystrobin, climbazole, niacinamide, menthol and / or methyl lactate, and mixtures thereof.

34. The personal care composition of claim 32, wherein the scalp health agent is zinc pyrithione.

35. The personal care composition of claim 32, wherein the scalp health agent is salicylic acid.

36. The personal care composition of claim 32, wherein the scalp health agent is menthol and / or menthyl lactate.

37. The personal care composition of claim 1 or 2, further comprising 0.5% to 7% fragrance.

Citation Information

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