Low surfactant aerosol anti-dandruff composition
A low surfactant shampoo composition with a propellant enhances anti-dandruff agent deposition on the scalp, addressing inefficiencies in existing shampoos by improving efficacy and gentleness, and maintaining hair feel and cleaning properties.
Patent Information
- Application Number
- JP2020570543
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2018-06-29
- Filing Date
- 2018-10-25
- Publication Date
- 2025-10-22
- Estimated Expiration
- 2038-10-25
AI Technical Summary
Existing anti-dandruff shampoos face challenges in efficiently depositing surfactant-soluble anti-dandruff agents on the scalp, leading to high rinsing losses and increased costs due to the expense of these agents, while consumers seek improved efficacy and gentler hair care products.
A low surfactant concentration shampoo composition delivered in foam form, enhanced with a propellant, improves deposition of surfactant-soluble anti-dandruff agents by reducing solubility and promoting precipitation on the scalp, maintaining effective cleaning and moisturizing properties.
The composition achieves higher deposition of anti-dandruff agents with reduced skin irritation and hair fiber stripping, providing superior efficacy and faster rinsing while maintaining hair feel and sebum removal.
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Abstract
Description
[Technical Field]
[0001] The present invention relates to an aerosol anti-dandruff composition having a low surfactant concentration that provides active deposition and improved hair feel while maintaining the effectiveness of the composition. [Background technology]
[0002] For many years, anti-dandruff shampoos have been widely used to treat dandruff and cleanse the hair and scalp, but there remains a need for improved anti-dandruff shampoos. Anti-dandruff shampoos are typically formulated with an anti-dandruff agent in combination with a surfactant and aqueous system intended to deposit the anti-dandruff agent on the scalp. The anti-dandruff agent can be an insoluble particulate, such as zinc pyrithione, and / or a surfactant-soluble substance, such as climbazole or piroctone olamine. A key aspect of anti-dandruff shampoos is their ability to adequately deposit the anti-dandruff agent on the scalp. This is particularly challenging with surfactant-soluble anti-dandruff agents, which can prove difficult to achieve on the scalp much more than 1-2% of the amount of agent present in the product while simultaneously rinsing out the remaining 98-99% of the soluble agent in the formulation. Because many anti-dandruff agents can be relatively expensive, rinsing out more than 97% of the soluble agent is a waste of money. Thus, there remains a need for shampoos that can more efficiently deposit soluble anti-dandruff agents. Also, as consumers continue to desire shampoos that provide superior anti-dandruff efficacy, there remains a need for shampoos that can deposit a higher percentage of the soluble agents present in anti-dandruff shampoos onto the scalp.
[0003] The present invention has surprisingly found that shampoos with a relatively low surfactant concentration delivered in foam form can deliver a greater amount of surfactant-soluble anti-dandruff agent onto the scalp.The low surfactant content of such shampoo compositions provides additional benefits.It is well known that low surfactant compositions provide gentler cleaning with less skin irritation and less hair fiber stripping.The compositions of the present invention rinse faster, yet still provide (a) good moisturizing feel and combability, and (b) high sebum removal ability.
[0004] Without being bound by theory, the observation that the improved adhesion of anti-dandruff foam active substance to scalp observed by the low surfactant shampoo composition delivered as aerosol may be related to the use of propellant in the composition.More specifically, the existence of propellant in shampoo composition may contribute to reducing the solubility of active substance in shampoo, since propellant may be partially or entirely present in surfactant micelle.As a result, the solubility of anti-dandruff decreases, or in other words, the saturation concentration of anti-dandruff active substance decreases, and as the propellant and aqueous carrier evaporate, the active substance tends to precipitate as a water-insoluble substance on scalp. Summary of the Invention [Means for solving the problem]
[0005] The present invention is directed to a foaming composition comprising from about 5% to about 13% total surfactants having one or more anionic surfactants, from 0.1% to about 2% surfactant-soluble anti-dandruff actives, and from about 3% to about 15% foaming agent, the foaming composition having a pH of from about 3.5 to 6.5. DETAILED DESCRIPTION OF THE INVENTION
[0006] While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed the present invention will be better understood from the following description.
[0007] As used herein, the term "fluid" includes liquids and gels.
[0008] As used herein, articles such as "a" and "an," when used in a claim, are understood to mean one or more of what is claimed or described.
[0009] As used herein, "comprising" means that other steps and other ingredients that do not affect the end result can be added. This term encompasses the terms "consisting of" and "consisting essentially of."
[0010] As used herein, "mixture" is meant to include the simple combination of materials and any compounds that can result from such a combination.
[0011] As used herein, "molecular weight" or "molecular weight" refers to weight average molecular weight, unless otherwise specified. Molecular weight is measured using gel permeation chromatography ("GPC"), an industry standard method.
[0012] As used herein, "personal care compositions" include products such as shampoos, shower gels, liquid hand washes, hair dyes, facial cleansers, and other surfactant-based liquid compositions.
[0013] As used herein, the terms "include," "includes," and "including" are meant to be open-ended and are understood to mean "comprise," "comprises," and "comprising," respectively.
[0014] All percentages, parts and ratios are based on the total weight of the compositions of the present invention unless otherwise specified. All such weights, as they pertain to listed ingredients, are based on the active ingredient level and, therefore, do not include carriers or by-products that may be included in commercially available materials.
[0015] Unless otherwise stated, all ingredient or composition concentrations are in terms of the active portion of that ingredient or composition and are exclusive of impurities, such as residual solvents or by-products, that may be present in commercial sources of such ingredient or composition.
[0016] It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification includes every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification includes every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
[0017] Detergent surfactants The hair care composition may comprise greater than about 20% by weight of a surfactant system that provides the composition with cleansing performance. The surfactant system comprises an anionic surfactant and / or a combination of an anionic surfactant and a co-surfactant selected from the group consisting of amphoteric, zwitterionic, nonionic, and mixtures thereof. Various examples and descriptions of cleansing surfactants are described in U.S. Patent No. 8,440,605, U.S. Patent Application Publication Nos. 2009 / 155383, and 2009 / 0221463, which are incorporated herein by reference in their entireties.
[0018] The hair care composition may comprise from about 18% to about 36%, from about 20% to about 32%, and / or from about 22% to about 28% by weight of one or more anionic surfactants.
[0019] The composition of the present invention also comprises a) RO(CHCHR0) y SO3M, b) CH3(CH2) z CHR2CH2O(CH2CHR3O) y SO3M, and c) mixtures thereof; In the formula, R1 is CH3(CH2) 10 wherein 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, and when y is not zero (0), the average value of y is about 1; and M is a monovalent or divalent positively charged cation.
[0020] Suitable anionic surfactants for use in the present composition are alkyl and alkyl ether sulfates.Other suitable anionic surfactants are water-soluble salts of organic sulfuric acid reaction products.Still other suitable anionic surfactants are reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide.Other similar anionic surfactants are described in U.S. Patent Nos. 2,486,921, 2,486,922, and 2,396,278, which are incorporated herein by reference in their entirety.
[0021] Exemplary anionic surfactants for use in the hair care compositions include ammonium lauryl sulfate, ammonium laureth 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, lauryl monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth 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 tridecylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium cocoyl isethionate, undecyl sulfate, and combinations thereof. The anionic surfactant may be sodium lauryl sulfate or sodium laureth sulfate.
[0022] Suitable anionic alkyl sulfate and alkyl ether sulfate surfactants include, but are not limited to, those having branched alkyl chains synthesized from C8 to C18 2-alkyl branched alcohols, which may be selected from the group consisting of Guerbet alcohols, aldol alcohols, oxo alcohols, and mixtures thereof. Non-limiting examples of 2-alkyl branched alcohols include 2-methyl-1-undecanol, 2-ethyl-1-decanol, 2-methyl-1-dodecanol, 2-butyl-1-octanol, 2-butyl-1-nonanol, 2-ethyl-1-undecanol, 2-propyl-1-nonanol, 2-pentyl-1-octanol, 2-pentyl-1-heptanol, and Guerbet alcohols such as those sold under the trademark ISOFOL® (Sasol), and oxo alcohols such as those sold under the trademarks LIAL® (Sasol), ISALCHEM® (Sasol), NEODOL® (Shell).
[0023] The hair care composition may also contain a co-surfactant. The co-surfactant may be selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, nonionic surfactants, and mixtures thereof. The co-surfactant may include, but is not limited to, lauramidopropyl betaine, cocoamidopropyl betaine, lauryl hydroxysultaine, sodium lauroamphoacetate, cocomonoethanolamide, and mixtures thereof.
[0024] The hair care composition may further comprise from about 1% to about 5%, from about 2% to about 4%, from about 2.5% to about 3% by weight of one or more amphoteric / zwitterionic, nonionic co-surfactants or mixtures thereof.
[0025] Suitable amphoteric or zwitterionic surfactants for use in the hair care compositions herein include those known for use in shampoos or other hair care cleansers. Non-limiting examples of suitable zwitterionic or amphoteric surfactants are described in U.S. Patent Nos. 5,104,646 and 5,106,609, which are incorporated herein by reference in their entireties.
[0026] Amphoteric co-surfactants suitable for use in the compositions include surfactants described as derivatives of aliphatic secondary and tertiary amines, where the aliphatic radicals can be straight or branched, and where one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group such as carboxy, sulfonate, sulfate, phosphate, or phosphonate. Suitable amphoteric surfactants include sodium cocaminopropionate, sodium cocaminodipropionate, sodium cocoamphoacetate, sodium cocoamphohydroxypropylsulfonate, sodium cocoamphopropionate, sodium cornamphopropionate, sodium lauraminopropionate, sodium lauroamphoacetate, sodium lauroamphohydroxypropylsulfonate, sodium lauroamphopropionate, sodium cornamphopropionate, sodium lauriminodipropionate, ammonium cocaminopropionate, ammonium cocaminodipropionate, ammonium cocoamphoacetate, ammonium cocoamphohydroxypropylsulfonate, ammonium cocoamphopropionate, ammonium cornamphopropionate, ammonium lauraminopropionate, ammonium lauroamphoacetate, ammonium lauroamphohydroxypropylsulfonate Ammonium lauroamphopropionate, ammonium cornamphopropionate, ammonium lauriminodipropionate, triethanolamine cocaminopropionate, triethanolamine cocaminodipropionate, triethanolamine cocoamphoacetate, triethanolamine cocoamphohydroxypropylsulfonate, triethanolamine cocoamphopropionate, triethanolamine cornamphopropionate, triethanolamine lauraminopropionate, triethanolamine lauroamphoacetate, triethanolamine lauroamphohydroxypropylsulfonate, triethanolamine lauroamphopropionate, triethanolamine cornamphopropionate, triethanolamine lauriminodipropionate, cocoamphodipropionic acid, disodium caproamphodiacetate, disodium caproamphodipropionate, disodium capryloamphodiacetateDisodium capryloamphodipriopionate, disodium cocoamphocarboxyethyl hydroxypropyl sulfonate, disodium cocoamphodiacetate, disodium cocoamphodipropionate, disodium dicarboxyethyl cocopropylenediamine, disodium laureth-5 carboxyamphodiacetate, disodium lauriminodipropionate, disodium lauroamphodiacetate, disodium lauroamphodipropionate, disodium oleoamphodipropionate, disodium PPG-2-isodecethyl-7 carboxyamphodiacetate, lauraminopropionic acid, lauroamphodipropionic acid, laurylaminopropylglycine, lauryldiethylenediaminoglycine, and mixtures thereof.
[0027] The amphoteric co-surfactant may be a surfactant according to the following structure:
[0028] [ka] wherein R12 is a C-linked monovalent substituent selected from the group consisting of substituted alkyls containing 9 to 15 carbon atoms, unsubstituted alkyls containing 9 to 15 carbon atoms, linear alkyls containing 9 to 15 carbon atoms, branched alkyls containing 9 to 15 carbon atoms, and unsaturated alkyls containing 9 to 15 carbon atoms; R13, R14, and R15 are each independently selected from the group consisting of C-linked divalent linear alkyls containing 1 to 3 carbon atoms and C-linked divalent branched alkyls containing 1 to 3 carbon atoms; and M+ is a monovalent counterion selected from the group consisting of sodium, ammonium, and protonated triethanolamine. The amphoteric surfactant may be selected from the group consisting of sodium cocoamphoacetate, sodium cocoamphodiacetate, sodium lauroamphoacetate, sodium lauroamphodiacetate, ammonium lauroamphoacetate, ammonium cocoamphoacetate, triethanolamine lauroamphoacetate, triethanolamine cocoamphoacetate, and mixtures thereof.
[0029] The composition may also include zwitterionic co-surfactants, which are derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, where the aliphatic radicals may be straight or branched chain, and one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group such as carboxy, 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, cocamidopropyldimonium hydroxypropyl hydrolyzed collagen, cocamidopropyl hydroxysultaine, cocobetaine amide amphopropionate, coco-betaine, coco-hydroxysultaine, coco / oleamidopropyl betaine, coco-sultaine, lauramidopropyl betaine, lauryl betaine, lauryl hydroxysultaine, lauryl sultaine, and mixtures thereof. A preferred zwitterionic surfactant is lauryl hydroxysultaine. The zwitterionic surfactant may be selected from the group consisting of lauryl hydroxysultaine, cocamidopropyl hydroxysultaine, coco-betaine, coco-hydroxysultaine, coco-sultaine, lauryl betaine, lauryl sultaine, and mixtures thereof.
[0030] The co-surfactant may be a zwitterionic surfactant selected from the group consisting of lauryl hydroxysultaine, cocamidopropyl hydroxysultaine, coco-betaine, coco-hydroxysultaine, coco-sultaine, lauryl betaine, lauryl sultaine, and mixtures thereof.
[0031] The co-surfactant may be a nonionic surfactant selected from the group consisting of cocamide, cocamide methyl MEA, cocamide DEA, cocamide MEA, cocamide MIPA, lauramide DEA, lauramide MEA, lauramide MIPA, myristamide DEA, myristamide 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, and mixtures thereof.
[0032] 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 U.S. Pat. Nos. 3,929,678, 2,658,072, 2,438,091, and 2,528,378, which are incorporated herein by reference in their entireties.
[0033] Non-sulfate surfactants Suitable surfactants that are substantially sulfate-free can include isethionates, sulfonates, sulfosuccinates, sulfoacetates, acylglucosides, acylglycinates, acylsarcosinares, acylglutamates, acylalaninates, alkylglucosides, alkylpolyglucosides, acylglucosides, glucamides, glucosecarboxylates, amphoacetates, taurates, other acylamino acids, betaines, sultaines, and / or phosphate esters. Suitable surfactants that are substantially sulfate-free can contain carboxylic acids.
[0034] Viscosity reducer The hair care composition may comprise from about 1% to about 5%, alternatively from about 2% to about 4%, alternatively from about 1% to about 3%, by weight of the hair care composition, of one or more viscosity reducing agents.
[0035] The viscosity reducing agent may be selected from the group consisting of: ethanol, dipropylene glycol, sodium xylene sulfonate, alkoxylated silicone / ethoxylated silicone / propoxylated silicone / polyoxyethylene silicone / polyoxypropylene silicone / polyethylene glycol silicone / PEG-8 silicone / PEG-9 silicone / PEG-n silicone / silicone ether (n can be another integer), non-limiting examples of which include PEG8-Dimethicone A208) MW 855, PEG8 Dimethicone D208 MW 2706, Silsurf, and combinations thereof.
[0036] The hair care compositions described herein may have a liquidus viscosity (composition prior to addition of propellant) of about 8 centipoise to about 25,000 centipoise, alternatively about 9 centipoise to about 15,000 centipoise, alternatively about 10 centipoise to about 11,000 centipoise, or about 100 centipoise to about 3,000 centipoise. Furthermore, the viscosity measured at 25°C may be less than 3,000 centipoise. Viscosity values for concentrated hair compositions can be measured at 25°C at a shear rate of 2 reciprocal seconds using a TA Instruments AR-G2 rheometer equipped with a concentric cylinder attachment. In the present invention, the hair care compositions may have a viscosity range that facilitates dispensing from a packaging structure.
[0037] Water-miscible solvents The composition can include water-miscible glycols and other diols, non-limiting examples of which include dipropylene glycol, tripropylene glycol, diethylene glycol, ethylene glycol, propylene glycol, 1,3-propanediol, 2,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1-propene, 1,3,3,3 tetrafluoro-(1E), and 2-methyl-2,4-pentanediol.
[0038] Soluble Anti-Dandruff Agents The anti-dandruff agent may be one or a mixture selected from the group consisting of azoles such as climbazole, ketoconazole, itraconazole, econazole, and elubiol; hydroxypyridones such as octopirox (piroctone olamine), hydroxylpyridone, N-hydroxy-6-octyloxypyridin-2(1H)one, hexamidine diisethionate, ciclopirox, rilopirox, and MEA-hydroxyoctyloxypyridinone; kerolytic agents such as salicylic acid and other hydroxy acids; strobilurins such as azoxystrobin, and metal chelators such as 1,10-phenanthroline.
[0039] In the present invention, the azole antibacterial agent may be an imidazole selected from the group consisting of benzimidazole, benzothiazole, bifonazole, butaconazole nitrate, climbazole, clotrimazole, cloconazole, eberconazole, econazole, elubiol, fenticonazole, fluconazole, flutimazole, isoconazole, ketoconazole, lanoconazole, metronidazole, miconazole, neticonazole, omoconazole, oxiconazole nitrate, sertaconazole, sulconazole nitrate, tioconazole, thiazole, and mixtures thereof; alternatively, the azole antibacterial agent may be a triazole selected from the group consisting of terconazole, itraconazole, and mixtures thereof. The azole antibacterial agent may be ketoconazole.
[0040] The soluble anti-dandruff agent may be present in an amount of about 0.01% to 10%, about 0.1% to about 2%, and about 0.6% to about 1%, and about 0.5% to about 0.8%. The soluble anti-dandruff agent may be surfactant soluble and thus may be a surfactant soluble anti-dandruff agent.
[0041] cationic polymer The hair care composition further comprises a cationic polymer. These cationic polymers may include at least one of: (a) cationic guar polymers, (b) cationic non-guar galactomannan polymers, (c) cationic tapioca polymers, (d) cationic copolymers of acrylamide monomers and cationic monomers, and / or (e) synthetic non-crosslinked cationic polymers that may or may not form lyotropic liquid crystals when combined with a detersive surfactant; and (f) cationic cellulose polymers. Additionally, the cationic polymer may be a mixture of cationic polymers.
[0042] The hair care composition may contain cationic guar polymers, which are cationically substituted galactomannan (guar) gum derivatives. The guar gum used to prepare these guar gum derivatives is typically obtained as a naturally occurring material from the seeds of the guar plant. The guar molecule itself is a regularly branched linear mannan in which single-membered galactose units alternate with mannose units. The mannose units are linked to each other by β(1-4) glycosidic bonds. The galactose branches arise from α(1-6) linkages. The cationic derivatives of guar gum are obtained by the reaction between the hydroxyl groups of the polygalactomannan and reactive quaternary ammonium compounds. The degree of substitution of cationic groups on the guar structure must be sufficient to provide the required cationic charge density described above.
[0043] Cationic polymers include, but are not limited to, cationic guar polymers that may have a molecular weight of less than 1,000,000 g / mol, or from about 10,000 to about 1,000,000 g / mol, or from about 25,000 to about 1,000,000 g / mol, or from about 50,000 to about 1,000,000 g / mol, or from about 100,000 to about 1,000,000 g / mol. The cationic guar polymers may have a charge density of from about 0.2 to about 2.2 meq / g, or from about 0.3 to about 2.0 meq / g, or from about 0.4 to about 1.8 meq / g, or from about 0.5 meq / g to about 1.7 meq / g.
[0044] The cationic guar polymer may have a weight average molecular weight of less than about 1,000,000 g / mol and a charge density of from about 0.1 meq / g to about 2.5 meq / g. The cationic guar polymer may have a weight average molecular weight of less than 950,000 g / mol, or from about 10,000 to about 900,000 g / mol, or from about 25,000 to about 900,000 g / mol, or from about 50,000 to about 900,000 g / mol, or from about 100,000 to about 900,000 g / mol, or from about 150,000 to about 800,000 g / mol. The cationic guar polymer can have a charge density of from about 0.2 to about 2.2 meq / g, or from about 0.3 to about 2.0 meq / g, or from about 0.4 to about 1.8 meq / g, or from about 0.5 meq / g to about 1.5 meq / g.
[0045] The hair care composition may comprise from about 0.05% to less than about 1%, from about 0.05% to about 0.9%, from about 0.1% to about 0.8%, or from about 0.2% to about 0.7% by weight of the total weight of the composition of cationic polymer (a).
[0046] The cationic guar polymer can be formed from a quaternary ammonium compound. The quaternary ammonium compound for forming the cationic guar polymer can conform to the general formula 1:
[0047] [ka] In the formula, R3 , R 4 , and R 5 is a methyl or ethyl group, and R 6 is an epoxyalkyl group of general formula 2,
[0048] [ka] Or R 6 is a halohydrin group of general formula 3,
[0049] [ka] In the formula, R 7 is a C1-C3 alkylene, X is chlorine or bromine, and Z is an anion such as Cl-, Br-, I-, or HSO4-.
[0050] In one embodiment, the cationic guar polymer conforms to general formula 4:
[0051] [ka] In the formula, R 8 is guar gum, R 4 , R 5 , R 6 , and R 7 is as defined above and Z is a halogen. In one embodiment, the cationic guar polymer conforms to formula 5.
[0052] [ka]
[0053] Suitable cationic guar polymers include cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride.In one embodiment, the cationic guar polymer is guar hydroxypropyltrimonium chloride.Specific examples of guar hydroxypropyltrimonium chloride include the Jaguar® series available from Rhone-Poulenc Incorporated, such as Jaguar® C-500 available from Rhodia.Jaguar® 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 guar hydroxypropyltrimonium chloride having a charge density of about 1.1 meq / g and a molecular weight of about 500,000 g / mole, available from ASI, and guar hydroxypropyltrimonium chloride having a charge density of about 1.5 meq / g and a molecular weight of about 500,000 g / mole, available from ASI. Other suitable guar hydroxypropyltrimonium chlorides are Hi-Care 1000, having a charge density of about 0.7 meq / g and a molecular weight of about 600,000 g / mole, available from Rhodia; N-Hance 3269 and N-Hance 3270, having a charge density of about 0.7 meq / g and a molecular weight of about 425,000 g / mole, available from ASI; AquaCat CG518, having a charge density of about 0.9 meq / g and a molecular weight of about 50,000 g / mole, available from ASI; BF-13, a borate-free guar having a charge density of about 1.1 meq / g and a molecular weight of about 800,000; and BF-17, a borate-free guar having a charge density of about 1.7 meq / g and a molecular weight of about 800,000 (all available from ASI).
[0054] The hair care composition may contain 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 is selected from the group consisting of cationic galactomannan polymer derivatives and amphoteric galactomannan polymer derivatives having a net positive charge. As used herein, the term "cationic galactomannan" refers to a galactomannan polymer to which cationic groups have been added. The term "amphoteric galactomannan" refers to a galactomannan polymer to which cationic and anionic groups have been added such that the polymer has a net positive charge.
[0055] Galactomannan polymers are present in the endosperm of legume seeds. Galactomannan polymers are composed of a combination of mannose and galactose monomers. Galactomannan molecules are linear mannans with single-membered galactose units branching at regular intervals on specific mannose units. The mannose units are linked to each other by β(1-4) glycosidic bonds. Galactose branches occur via α(1-6) linkages. The ratio of mannose to galactose monomers varies depending on the plant species and is also influenced by climate. Non-guar galactomannan polymer derivatives may have a mannose to galactose ratio of greater than 2:1 on a monomer-to-monomer basis. Suitable mannose to galactose ratios may be greater than about 3:1, and may be greater than about 4:1. Analysis of the mannose to galactose ratio is well known in the art and is typically based on measuring galactose content.
[0056] Gums used in the preparation of non-guar galactomannan polymer derivatives are typically obtained as natural materials such as plant seeds or beans. Examples of various non-guar galactomannan polymers include, but are not limited to, tara gum (3 parts mannose / 1 part galactose), locust bean or carob (4 parts mannose / 1 part galactose), and cassia gum (5 parts mannose / 1 part galactose).
[0057] In one embodiment of the present invention, the non-guar galactomannan polymer derivatives have a molecular weight of about 1,000 to about 1,000,000 and / or about 5,000 to about 900,000.
[0058] The hair care composition may also include a galactomannan polymer derivative having a cationic charge density of about 0.5 meq / g to about 7 meq / g. In one embodiment, the galactomannan polymer derivative has a cationic charge density of about 1 meq / g to about 5 meq / g. The degree of substitution of cationic groups onto the galactomannan structure should be sufficient to provide the required cationic charge density.
[0059] The galactomannan polymer derivative may be a cationic derivative of a non-guar galactomannan polymer, obtained by reacting the hydroxyl groups of the polygalactomannan polymer with a reactive quaternary ammonium compound. Suitable quaternary ammonium compounds for use in forming the cationic galactomannan polymer derivative include those conforming to the general formulas 1-5 defined above.
[0060] The cationic non-guar galactomannan polymer derivatives formed from the above reagents are represented by general formula 6:
[0061] [ka] wherein R is a gum. The cationic galactomannan derivative can be gum hydroxypropyltrimethylammonium chloride, which can be more specifically represented by the following general formula 7:
[0062] [ka]
[0063] Alternatively, the galactomannan polymer derivative may be an amphoteric galactomannan polymer derivative having a net positive charge, which is obtained when the cationic galactomannan polymer derivative further comprises an anionic group.
[0064] Cationic non-guar galactomannans have a mannose to galactose ratio of greater than about 4:1, a molecular weight of 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 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 obtained from the cassia plant.
[0065] The hair care composition can comprise at least about 0.05% of the galactomannan polymer derivative, or alternatively, from about 0.05% to about 2% of the galactomannan polymer derivative, by weight of the composition.
[0066] The hair care composition can comprise a water-soluble cationically modified starch polymer.As used herein, the term "cationically modified starch" refers to starch to which cationic groups are added before the starch is decomposed into smaller molecular weights, or to starch to which cationic groups are added after the starch is modified to achieve a desired molecular weight.The definition of the term "cationically modified starch" also includes amphoterically modified starch.The term "amphoterically modified starch" refers to starch hydrolysate to which cationic and anionic groups are added.
[0067] The hair care composition may comprise cationically modified starch polymers in the range of from about 0.01% to about 10%, and / or from about 0.05% to about 5%, by weight of the composition.
[0068] The cationically modified starch polymers disclosed in the present invention have a percentage of bound nitrogen of from about 0.5% to about 4%.
[0069] The cationically modified starch polymers used in the hair care compositions can have a molecular weight of from about 50,000 g / mole to about 1,000,000 g / mole, and / or from about 100,000 g / mole to about 1,000,000 g / mole.
[0070] The hair care composition may include a cationically modified starch polymer having a charge density of about 0.2 meq / g to about 5 meq / g and / or about 0.2 meq / g to about 2 meq / g. Chemical modifications to achieve such charge densities include, but are not limited to, adding amino and / or ammonium groups to the starch molecule. Non-limiting examples of these ammonium groups include substituents such as hydroxypropyltrimonium 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. Cationic groups may be added to the starch before it is degraded to smaller molecular weights, or the cationic groups may be added after such modification.
[0071] Cationically modified starch polymers typically have a degree of substitution of cationic groups of about 0.2 to about 2.5. As used herein, the "degree of substitution" of a cationically modified starch polymer is the average number of hydroxyl groups on each anhydroglucose unit that are derivatized with a substituent. Because each anhydroglucose unit has three possible hydroxyl groups available for substitution, the maximum possible degree of substitution is 3. The degree of substitution is expressed on a molar average basis as the number of moles of substituent per mole of anhydroglucose unit. The degree of substitution can be determined using proton nuclear magnetic resonance spectroscopy ("H NMR") techniques well known in the art. Suitable .sup.1H NMR methods 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.
[0072] The source of starch before chemical modification can be selected from a variety of sources such as tubers, legumes, cereals, and grains, etc. Non-limiting examples of starch from this source can include corn starch, wheat starch, rice starch, waxy corn starch, oat starch, cassava starch, barley, waxy rice starch, glutenous rice starch, sweet rice starch, amioca, potato starch, tapioca starch, oat starch, sago starch, glutinous rice, or mixtures thereof.
[0073] The cationically modified starch polymers can be selected from degraded cationic corn starch, cationic tapioca, cationic potato starch, and mixtures thereof. Alternatively, the cationically modified starch polymers are cationic corn starch and cationic tapioca.
[0074] Starch may include one or more additional modifications before or after degradation to lower molecular weights. For example, these modifications may include cross-linking, stabilization, phosphorylation, and hydrolysis. Stabilization may include alkylation and esterification.
[0075] The cationically modified starch polymers may be incorporated into the composition in the form of hydrolyzed starch (e.g., acid, enzymatic, or alkaline degradation), oxidized starch (e.g., peroxide, peracid, hypochlorite, alkali, or any other oxidizing agent), physically / mechanically degraded starch (e.g., by the thermal mechanical energy input of processing equipment), or combinations thereof.
[0076] The optimal form of starch is one that dissolves easily in water to form a substantially transparent aqueous solution (transmittance at 600 nm of 80% or more). The transmittance of the composition is measured by ultraviolet / visible (UV / VIS) spectrophotometry, which measures the absorbance or transmittance of a sample of UV / VIS light using a Gretag Macbeth Colorimeter Color i 5 according to the relevant instructions. A light wavelength of 600 nanometers has been shown to be suitable for characterizing the transparency of cosmetic compositions.
[0077] The cationically modified starch suitable for use in hair care compositions can be obtained from known starch suppliers.Similarly, the nonionic modified starch suitable for use in hair care compositions can be further derivatized into the cationically modified starch known in the art.Other suitable modified starch starting materials can be quaternized as known in the art to produce the cationically modified starch polymer suitable for use in hair care compositions.
[0078] Starch Degradation Procedure: A starch slurry can be prepared by mixing granular starch in water. The temperature is raised to about 35°C. An aqueous solution of potassium permanganate is then added at a concentration of about 50 ppm based on starch. The pH is raised to about 11.5 with sodium hydroxide, and the slurry is stirred thoroughly to prevent starch precipitation. Next, an approximately 30% solution of hydrogen peroxide diluted in water is added until the peroxide concentration is about 1% based on starch. Additional sodium hydroxide is then added to return the pH to about 11.5. 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, washed, and dried.
[0079] The hair care composition can include a cationic copolymer of acrylamide monomers and cationic monomers, the copolymer having a charge density of from about 1.0 meq / g to about 3.0 meq / g. The cationic copolymer can be a synthetic cationic copolymer of acrylamide monomers and cationic monomers.
[0080] The cationic copolymer may include: (i) an acrylamide monomer of formula AM:
[0081] [ka] In the formula, R 9 is H or C 1~4 alkyl, and R 10 and R11 are independently H, C 1~4 alkyl, CH2OCH3, CH2OCH2CH(CH3)2, and phenyl, or both of which are C 3~6 It is cycloalkyl. (ii) a cationic monomer conforming to the following formula C:
[0082] [ka] In the formula, k is 1; v, v', and v" are each independently an integer of 1 to 6; w is 0 or an integer of 1 to 10; and X - is an anion.
[0083] The cationic monomer conforms to the formula CM, where k=1, v=3, and w=0, z=1, and X - is Cl - and the following structure can be formed:
[0084] [ka]
[0085] The above structure is sometimes referred to as a diquat. Alternatively, the cationic monomer can conform to the formula CM, where v and v" are each 3, v'=1, w=1, y=1, and X - is Cl - and so it becomes:
[0086] [ka]
[0087] The above structure is sometimes referred to as a triquat.
[0088] Suitable acrylamide monomers include, but are not limited to, either acrylamide or methacrylamide.
[0089] In an alternative embodiment, the cationic copolymer is an acrylamide monomer and a cationic monomer, wherein the cationic monomer is selected from the group consisting of dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ditertiobutylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide; ethyleneimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine; trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methyl sulfate, dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyldimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamido chloride, trimethylammonium propyl (meth)acrylamido chloride, vinylbenzyl trimethylammonium chloride, diallyldimethylammonium chloride, and mixtures thereof.
[0090] The cationic copolymer can comprise a cationic monomer selected from the group consisting of cationic monomers including trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methyl sulfate, dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamide chloride, trimethylammonium propyl (meth)acrylamide chloride, vinylbenzyl trimethylammonium chloride, and mixtures thereof.
[0091] The cationic copolymer may be water-soluble. The cationic copolymer may be formed from (1) a copolymer of (meth)acrylamide and a (meth)acrylamide-based cationic monomer, and / or a hydrolytically stable cationic monomer, or (2) a terpolymer of (meth)acrylamide, a cationic (meth)acrylic acid ester-based monomer, and a (meth)acrylamide-based monomer, and / or a hydrolytically stable cationic monomer. The cationic (meth)acrylic acid ester-based monomer may be a cationized ester of (meth)acrylic acid containing a quaternized nitrogen atom. In one embodiment, the cationized ester of (meth)acrylic acid containing a quaternized nitrogen atom is a dialkylaminoalkyl (meth)acrylate quaternized at C1 to C3 in the alkyl and alkylene groups. Suitable cationized esters of (meth)acrylic acid containing a quaternized nitrogen atom can be selected from the group consisting of ammonium salts of dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminomethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and diethylaminopropyl (meth)acrylate, all quaternized with methyl chloride. In one embodiment, the cationized ester of (meth)acrylic acid containing a quaternized nitrogen atom is dimethylaminoethyl acrylate (ADAME-Quat), quaternized with an alkyl halide, or with methyl chloride, benzyl chloride, or dimethyl sulfate. When the cationic monomer is based on (meth)acrylamide, it can be a dialkylaminoalkyl (meth)acrylamide quaternized at C1 to C3 in the alkyl and alkylene groups, or a dimethylaminopropyl acrylamide quaternized with an alkyl halide, methyl chloride, benzyl chloride, or dimethyl sulfate.
[0092] Suitable (meth)acrylamide-based cationic monomers include dialkylaminoalkyl(meth)acrylamides quaternized at C1 to C3 in the alkyl and alkylene groups. The (meth)acrylamide-based cationic monomer can be dimethylaminopropylacrylamide quaternized with an alkyl halide, in particular methyl chloride or benzyl chloride or dimethyl sulfate.
[0093] The cationic monomer may be a hydrolytically stable cationic monomer. In addition to dialkylaminoalkyl (meth)acrylamide, the hydrolytically stable cationic monomer may be any monomer that can be considered stable to the OECD hydrolysis test. The cationic monomer may be hydrolytically stable, and the hydrolytically stable cationic monomer may be selected from the group consisting of diallyldimethylammonium chloride and water-soluble cationic styrene derivatives.
[0094] The cationic copolymer can be a terpolymer of acrylamide, 2-dimethylammoniumethyl(meth)acrylate quaternized with methyl chloride (ADAME-Q), and 3-dimethylammoniumpropyl(meth)acrylamide quaternized with methyl chloride (DIMAPA-Q). The cationic copolymer can be formed from acrylamide and acrylamidopropyltrimethylammonium chloride, which has a charge density of about 1.0 meq / g to about 3.0 meq / g.
[0095] The cationic copolymer can have a charge density of from about 1.1 meq / g to about 2.5 meq / g, or from about 1.1 meq / g to about 2.3 meq / g, or from about 1.2 meq / g to about 2.2 meq / g, or from about 1.2 meq / g to about 2.1 meq / g, or from about 1.3 meq / g to about 2.0 meq / g, or from about 1.3 meq / g to about 1.9 meq / g.
[0096] The cationic copolymer can have a molecular weight of from about 10,000 g / mol to about 1,000,000 g / mol, or from about 25,000 g / mol to about 1,000,000 g / mol, or from about 50,000 g / mol to about 1,000,000 g / mol, or from about 100,000 g / mol to about 1,000,000 g / mol, or from about 150,000 g / mol to about 1,000,000 g / mol.
[0097] The hair care composition may comprise a cationic synthetic polymer, which may be formed from one or more cationic monomer units, and optionally one or more monomer units having a negative charge, and / or a nonionic monomer, the next charge of the copolymer being a positive charge. The ratio of these three monomers is represented by "m", "p" and "q", where "m" is the number of cationic monomers, "p" is the number of monomers having a negative charge, and "q" is the number of nonionic monomers.
[0098] The cationic polymer may be a water-soluble or dispersible, non-crosslinked synthetic cationic polymer having the structure:
[0099] [ka] wherein A may be one or more of the following cationic moieties:
[0100] [ka] wherein @ is an amide, alkylamide, ester, ether, alkyl, or alkylaryl; Y is C1-C22 alkyl, alkoxy, alkylidene, alkyl, or aryloxy; ? is C1 to C22 alkyl, alkyloxy, alkylaryl, or alkylaryloxy, Z is C1-C22 alkyl, alkyloxy, aryl or aryloxy; R1 is H, C1-C4 straight or branched chain alkyl; s is 0 or 1, n is 0 or ≧1, T and R7 are C1-C22 alkyl; X - is a halogen, hydroxide, alkoxide, sulfate or alkyl sulfate.
[0101] In the above structure, the negatively charged monomer is defined by R2' being H, C1-C4 straight or branched chain alkyl, and R3 being:
[0102] [ka] wherein D is O, N, or S; Q is NH or O; u is 1 to 6; t is between 0 and 1, and J is an oxygenated functional group containing the elements P, S, C.
[0103] In the above structure, the nonionic monomer is defined by R2″ being H, C1-C4 linear or branched alkyl, and R6 being linear or branched alkyl, alkylaryl, aryloxy, alkyloxy, alkylaryloxy, and β being defined as follows:
[0104] [ka] wherein G′ and G″ are independently O, S, or NH; and L is 0 or 1.
[0105] Examples of cationic monomers include aminoalkyl(meth)acrylates, (meth)aminoalkyl(meth)acrylamides; monomers containing at least one secondary, tertiary, or quaternary amine functional group, or a heterocyclic group containing a nitrogen atom, vinylamine, or ethyleneimine; diallyldialkylammonium salts; mixtures thereof, salts thereof, and macromonomers derived therefrom.
[0106] Further examples of cationic monomers include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ditertiobutylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, ethyleneimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine, trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methyl sulfate, dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyldimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamido chloride, trimethylammonium propyl (meth)acrylamido chloride, vinylbenzyltrimethylammonium chloride, and diallyldimethylammonium chloride.
[0107] Suitable cationic monomers include those of the formula -NR3 + (wherein R is the same or different and represents a hydrogen atom, an alkyl group containing 1 to 10 carbon atoms, or a benzyl group, optionally having a hydroxyl group), and includes a quaternary ammonium group having an anion (counter ion). Examples of anions include halides such as chloride and bromide, sulfate, hydrosulfate, alkyl sulfate (e.g., containing 1 to 6 carbon atoms), phosphate, citrate, formate, and acetate.
[0108] Suitable cationic monomers include trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methyl sulfate, dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyldimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamide chloride, trimethylammonium propyl (meth)acrylamide chloride, vinylbenzyl trimethylammonium chloride.
[0109] Further suitable cationic monomers include trimethylammonium propyl (meth)acrylamide chloride.
[0110] Examples of negatively charged monomers include alpha-ethylenically unsaturated monomers containing a phosphate or phosphonate group, alpha-ethylenically unsaturated monocarboxylic acids, monoalkyl esters of alpha-ethylenically unsaturated dicarboxylic acids, monoalkyl amides of alpha-ethylenically unsaturated dicarboxylic acids, alpha-ethylenically unsaturated compounds containing a sulfonic acid group, and salts of alpha-ethylenically unsaturated compounds containing a sulfonic acid group.
[0111] Suitable negatively charged monomers include acrylic acid, methacrylic acid, vinyl sulfonic acid, salts of vinyl sulfonic acid, vinylbenzene sulfonic acid, salts of vinylbenzene sulfonic acid, α-acrylamidomethylpropane sulfonic acid, salts of α-acrylamidomethylpropane sulfonic acid, 2-sulfoethyl methacrylate, salts of 2-sulfoethyl methacrylate, acrylamido-2-methylpropane sulfonic acid (AMPS), salts of acrylamido-2-methylpropane sulfonic acid, and styrene sulfonate (SS).
[0112] Examples of nonionic monomers include vinyl acetate, amides of alpha-ethylenically unsaturated carboxylic acids, esters of alpha-ethylenically unsaturated monocarboxylic acids with hydrogenated or fluorinated alcohols, polyethylene oxide (meth)acrylates (i.e., polyethoxylated (meth)acrylic acids), monoalkyl esters of alpha-ethylenically unsaturated dicarboxylic acids, monoalkyl amides of alpha-ethylenically unsaturated dicarboxylic acids, vinyl nitriles, vinylamine amides, vinyl alcohol, vinylpyrrolidone, and vinyl aromatic compounds.
[0113] 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.
[0114] The anionic counterion (X-) associated with the synthetic cationic polymers can be any known counterion, so long as the polymer remains soluble or dispersible in water, the hair care composition, or the coacervate phase of 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 the performance, stability, or aesthetics of the product. Non-limiting examples of such counterions include halides (e.g., chlorine, fluorine, bromine, iodine), sulfate, and methylsulfate.
[0115] The concentration of the cationic polymer ranges 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.
[0116] A suitable cationic cellulose polymer is a salt of hydroxyethyl cellulose reacted with trimethylammonium-substituted epoxide, referred to in the art (CTFA) as Polyquaternium 10, available from Dow / Amerchol Corp. (Edison, NJ, USA) in the Polymer LR, JR, and KG series of polymers. Another suitable type of cationic cellulose is a polymeric quaternary ammonium salt of hydroxyethyl cellulose reacted with lauryldimethylammonium-substituted epoxide, referred to in the art (CTFA) as Polyquaternium 24. These materials are available from Dow / Amerchol Corp. under the trade name Polymer LM-200. Another suitable type of cationic cellulose is a polymeric quaternary ammonium salt of hydroxyethyl cellulose reacted with lauryldimethylammonium-substituted epoxide and trimethylammonium-substituted epoxide, referred to in the art (CTFA) as Polyquaternium 67. These materials are available from Dow / Amerchol Corp. under the trade names 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.
[0117] Thickening Polymer The hair care composition may include a thickening polymer to increase the viscosity of the composition. Any suitable thickening polymer may be used. The hair care composition may include about 0.1% to about 5% of a thickening polymer, or about 0.2% to about 2% of a thickening polymer. The thickening polymer modifier may be a polyacrylate or polyacrylamide thickener. The thickening polymer may be an anionic thickening polymer.
[0118] The hair care composition may include a thickening polymer that is a homopolymer based on acrylic acid, methacrylic acid, or other related derivatives, non-limiting examples of which include polyacrylates, polymethacrylates, polyethylacrylates, and polyacrylamides.
[0119] The thickening polymer may be an alkali-swellable and hydrophobically modified alkali-swellable acrylic or methacrylate copolymer, non-limiting examples of which include acrylic acid / acrylonitrile copolymer, acrylates / steareth-20 itaconate copolymer, acrylates / ceteth-20 itaconate copolymer, acrylates / aminoacrylate / C10-30 alkyl PEG-20 itaconate copolymer, acrylates / aminoacrylate copolymer, acrylates / steareth-20 methacrylate ... 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 / Palmetha-25 Acrylate Copolymer, Acrylic Acid / Acrylamidomethyl Propanesulfonic Acid Copolymer, and Acrylates / C10-C30 Alkyl Acrylate Crosspolymer.
[0120] The thickening polymer may be a soluble crosslinked acrylic polymer, a non-limiting example of which is carbomer.
[0121] The thickening polymer may be an associative polymeric 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, which may have a hydrophobe selected from cetyl, stearyl, oleayl, and combinations thereof.
[0122] The thickening polymer can be used in combination with polyvinylpyrrolidone, cross-linked polyvinylpyrrolidone, and derivatives. The thickening polymer may be combined with polyvinyl alcohol and derivatives. The thickening polymer may be combined with polyethyleneimine and derivatives.
[0123] Thickening polymers may be combined with alginate-based materials, non-limiting examples of which include sodium alginate and propylene glycol alginate.
[0124] Thickening polymers can 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.
[0125] Thickening polymers may be combined with associative polymeric thickeners, non-limiting examples of which include hydrophobically modified cellulose derivatives and hydrophilic moieties of repeating ethylene oxide groups with repeating units of 10 to 300, 30 to 200, and 40 to 150. Non-limiting examples of this class include PEG-120-methyl glucose dioleate, PEG-(40 or 60) sorbitan tetraoleate, PEG-150 pentaerythrityl tetrastearate, PEG-55 propylene glycol oleate, PEG-150 distearate.
[0126] The thickening polymer may be combined with cellulose and derivatives, non-limiting examples of which include microcrystalline cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, ethyl cellulose; nitrocellulose; cellulose sulfate; cellulose powder; hydrophobically modified cellulose.
[0127] The thickening polymer may be combined with guar and guar derivatives, non-limiting examples of which include hydroxypropyl guar and hydroxypropyl guar hydroxypropyltrimonium chloride.
[0128] The thickening polymer may be combined with polyethylene oxide, polypropylene oxide, and POE-PPO copolymers.
[0129] The thickening polymer may be combined with a polyalkylene glycol characterized by the general formula:
[0130] [ka] where R is hydrogen, methyl, or a mixture thereof, preferably hydrogen, and n is an integer averaging 2,000 to 180,000, or 7,000 to 90,000, or 7,000 to 45,000. Non-limiting examples of this class include PEG-7M, PEG-14M, PEG-23M, PEG-25M, PEG-45M, PEG-90M, and PEG-100M.
[0131] The thickening polymer may be combined with silica, non-limiting examples of which include fumed silica, precipitated silica, and silicone surface treated silica.
[0132] The thickening polymer may be combined with a water-swellable clay, non-limiting examples of which include laponite, bentonite, montmorillonite, smectite, and hectonite.
[0133] The thickening polymer may be combined with a gum, non-limiting examples of which include xanthan gum, guar gum, hydroxyprolyl guar gum, gum arabic, tragacanth, galactan, carob gum, karaya gum, and locust bean gum.
[0134] The thickening polymers may be combined with dibenzylidene sorbitol, carrageenan, pectin, agar, quince seed (Cydonia oblonga Mill), starch (obtained from rice, corn, potato, wheat, etc.), starch derivatives (e.g., carboxymethyl starch, methylhydroxypropyl starch), algae extracts, dextran, succinoglucan, and prelan.
[0135] Non-limiting examples of thickening polymers include acrylamide / ammonium acrylate copolymer (and) polyisobutene (and) polysorbate 20; acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80, ammonium acryloyldimethyltaurate / VP copolymer, sodium acrylate / sodium acryloyldimethyltaurate copolymer, acrylate copolymer, acrylate crosspolymer-4, acrylate crosspolymer-3, acrylates / beheneth-25 methacrylate copolymer, acrylates / C10-C30 alkyl acrylate crosspolymer, acrylates / steareth-20 itaconate copolymer, polyacrylate, Ammonium acrylate / isohexadecane / PEG-40 castor oil; carbomer, sodium carbomer, cross-linked polyvinylpyrrolidone (PVP), 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 / sodium acryloyldimethyltaurate / dimethylacrylamide crosspolymer (and) isohexadecane (and) polysorbate 60, sodium polyacrylate.Exemplary commercially available thickening polymers include ACULYN™ 28, ACULYN™ 88, ACULYN™ 33, ACULYN™ 22, ACULYN™ Excel, Carbopol® Aqua SF-1, Carbopol® ETD 2020, Carbopol® Ultrez 20, Carbopol® Ultrez 21, Carbopol® Ultrez 10, Carbopol® Ultrez 30, Carbopol® 1342, Carbopol® Aqua SF-2 Polymer, Sepigel™ 305, Simulgel™ 600, Sepimax Zen, and Carbopol® SMART 1000, Rheocare® TTA, Rheomer® SC-Plus, STRUCTURE® PLUS, Aristoflex® AVC, Stabylen 30, and combinations thereof.
[0136] Scalp health supplement In the present invention, one or more scalp health agents may be added to provide scalp benefits in addition to the antifungal / antidandruff benefits provided by the surfactant-soluble antidandruff agent. This group of materials is diverse and provides a wide range of benefits, including moisturizing, barrier improvement, antifungal, antibacterial, antioxidant, anti-itch, and sensate effects. Non-limiting examples of additional antidandruff agents, such as polyvalent metal salts of pyrithione, include zinc pyrithione (ZPT) and copper pyrithione, sulfur, or selenium sulfide. Such scalp health agents include vitamins E and F, salicylic acid, niacinamide, caffeine, panthenol, zinc oxide, zinc carbonate, zinc carbonate basic, glycol, glycolic acid, PCA, PEG, erythritol, glycerin, triclosan, lactate, hyaluronate, allantoin and other ureas, betaine, sorbitol, glutamate, xylitol, menthol, menthyl lactate, isocyclomone, benzyl alcohol, and compounds containing the following structure:
[0137] [ka] (R1 is selected from H, alkyl, aminoalkyl, alkoxy; Q=H2, O, -OR1, -N(R1)2, -OPO(OR1) x , -PO(OR1) x , -P(OR1) x (in the formula, x=1~2); V=NR1, O, -OPO(OR1) x , -PO(OR1) x , -P(OR1) x (in the formula, x=1~2); W=H2, O; When n=0, X and Y are independently selected from H, aryl, and naphthyl; When n≧1, X, Y are aliphatic CH or aromatic CH, and Z is selected from aliphatic CH, aromatic CH, or a heteroatom; A=lower alkoxy, lower alkylthio, aryl, substituted aryl, or fused aryl; * At the marked positions, the stereochemistry is variable.) and natural extracts / oils including, but not limited to, peppermint, spearmint, argan, jojoba and aloe.
[0138] foaming agent The hair care compositions described herein may comprise from about 1% to about 15% foaming agent, from about 3% to about 10%, or from about 4% to about 7% foaming agent, by weight of the hair care composition.
[0139] The foaming agent may comprise one or more volatile substances, which, in their gaseous state, can carry other components of the hair care composition in the form of particles or droplets. The foaming agent may have a boiling point within the range of about -45°C to about 5°C. The foaming agent may liquefy when packaged in a conventional aerosol container under pressure. The rapid boiling of the foaming agent upon exiting the aerosol foam dispenser may aid in atomizing the other components of the hair care composition.
[0140] Aerosol blowing agents that may be used in the aerosol composition include chemically inert hydrocarbons such as propane, n-butane, isobutane, cyclopropane, and mixtures thereof, CO2 / carbon dioxide, and halogenated hydrocarbons such as dichlorodifluoromethane, 1,1-dichloro-1,1,2,2-tetrafluoroethane, 1-chloro-1,1-difluoro-2,2-trifluoroethane, 1-chloro-1,1-difluoroethylene, 1,1-difluoroethane, dimethyl ether, monochlorodifluoromethane, trans-1,3,3,3-tetrafluoropropene, and mixtures thereof. Non-limiting examples of blowing agents can be Honey Well propellant A46 (isobutane and propane) (18), Diversified Cpc International (Channahon US) and HF0 (trans-1,3,3,3-tetrafluoropropane) (19). Blowing agents can also include hydrocarbons such as isobutane, propane, and butane; these materials can be used due to their low ozone reactivity and can be used as individual components when their vapor pressure at 21.1°C ranges from about 1.17 bar to about 7.45 bar, alternatively from about 1.17 bar to about 4.83 bar, alternatively from about 2.14 bar to about 3.79 bar.
[0141] Optional Ingredients The hair care compositions described herein may further comprise one or more optional ingredients, including benefit agents. Suitable benefit agents include, but are not limited to, conditioning agents, cationic polymeric silicone emulsions, antidandruff actives, gel networks, chelating agents, and natural oils such as sunflower oil or castor oil. Further suitable optional ingredients include, but are not limited to, perfumes, perfume microcapsules, colorants, particles, antimicrobial agents, foam busters, antistatic agents, rheology modifiers and thickeners, suspending materials and structuring agents, pH adjusters and buffers, preservatives, pearlescent agents, solvents, diluents, antioxidants, vitamins, and combinations thereof.
[0142] Such optional ingredients must be physically and chemically compatible with the components of the composition and must not unduly impair product stability, aesthetics, or performance. The CTFA Cosmetic Ingredient Handbook, Tenth Edition (published by the Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, DC) (2004) (hereinafter referred to as "CTFA") describes a variety of non-limiting materials that may be added to the compositions herein.
[0143] Conditioning Agent The conditioning agent of the hair care composition may be a silicone conditioning agent. The silicone conditioning agent may include a volatile silicone, a non-volatile silicone, or a combination 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 No. 34,584, U.S. Pat. No. 5,104,646, and U.S. Pat. No. 5,106,609, which are incorporated herein by reference.
[0144] Silicone conditioning agents suitable for use may have a viscosity of from about 20 to about 2,000,000 centistokes ("csk"), from about 1,000 to about 1,800,000 csk, from about 50,000 to about 1,500,000 csk, and / or from about 100,000 to about 1,500,000 csk, when measured at 25°C.
[0145] The dispersed silicone conditioning agent particles typically have a volume average particle size ranging from about 0.01 micrometers to about 10 micrometers. When small particles are applied to hair, the volume average particle size typically ranges from about 0.01 micrometers to about 4 micrometers, from about 0.01 micrometers to about 2 micrometers, or from about 0.01 micrometers to about 0.5 micrometers.
[0146] Further information on silicones, including sections discussing silicone fluids, rubbers, and resins, and the manufacture of silicones, can be found in Encyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., pp 204-308, John Wiley & Sons, Inc. (1989), which is incorporated herein by reference.
[0147] Suitable silicone emulsions for use include, but are not limited to, emulsions of insoluble polysiloxanes prepared according to the instructions in U.S. Patent No. 4,476,282 and U.S. Patent Application Publication No. 2007 / 0276087. Accordingly, suitable insoluble polysiloxanes include polysiloxanes such as α,ω hydroxy-terminated or α,ω alkoxy-terminated polysiloxanes having a molecular weight in the range of about 50,000 to about 500,000 g / mol. The average molecular weight of the insoluble polysiloxane can be in the range of about 50,000 to about 500,000 g / mol. For example, the average molecular weight of the insoluble polysiloxane may be in the range of about 60,000 to about 400,000; about 75,000 to about 300,000; about 100,000 to about 200,000, or the average molecular weight may be about 150,000 g / mol. The insoluble polysiloxane may have an average particle size in the range of about 30 nm to about 10 microns. The average particle size may be, for example, in the range of about 40 nm to about 5 microns, about 50 nm to about 1 micron, about 75 nm to about 500 nm, or about 100 nm.
[0148] The average molecular weight of the insoluble polysiloxane, the viscosity of the silicone emulsion, and the size of particles comprising the insoluble polysiloxane are measured by methods commonly used by those skilled in the art, such as the method disclosed in Smith, A.L., 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 equipped with spindle 6 at 2.5 rpm. The silicone emulsion may further contain an additional emulsifier along with the anionic surfactant.
[0149] Other classes of silicones suitable for use include: 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 when measured at 25°C; ii) aminosilicones, which contain at least one primary, secondary, or tertiary amine; iii) cationic silicones, which contain at least one quaternary ammonium functional group; iv) silicone rubbers (including materials having a viscosity of 1,000,000 csk or greater when measured at 25°C); v) silicone resins, which include highly crosslinked polymeric siloxane systems; vi) high refractive index silicones, which have a refractive index of at least 1.46, and vii) mixtures thereof.
[0150] The conditioning agent of the hair care composition may also include at least one organic conditioning material, such as an oil or wax, either alone or in combination with other conditioning agents, such as silicones, as described above. The organic material may be non-polymeric, oligomeric, or polymeric. The organic material may be in the form of an oil or wax and may be added to the formulation as is or in a pre-emulsified form. Some non-limiting examples of organic conditioning materials include: 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; and viii) polyethylene glycols and polypropylene glycols having a molecular weight of up to about 2,000,000, such as those designated by the CTFA designations PEG-200, PEG-400, PEG-600, PEG-1000, PEG-2M, PEG-7M, PEG-14M, PEG-45M, and mixtures thereof.
[0151] emulsifier Various anionic and nonionic emulsifiers may be used in hair care compositions. Anionic and nonionic emulsifiers can be either monomeric or polymeric in nature. Examples of monomers include, but are not limited to, alkyl ethoxylates, alkyl sulfates, soaps, and fatty acid esters, and derivatives thereof. Examples of polymers include, but are not limited to, polyacrylates, polyethylene glycols, and block copolymers, and derivatives thereof. Natural emulsifiers such as lanolin, lecithin, and lignin, and derivatives thereof, are also non-limiting examples of useful emulsifiers.
[0152] Water-based carrier The hair care composition may be in the form of a pourable liquid (under ambient conditions). Accordingly, such compositions typically include a carrier, which is present in a concentration of about 40% to about 80%, alternatively about 45% to about 75%, alternatively about 50% to about 70% by weight of the hair care composition. The carrier may include water or a miscible mixture of water and an organic solvent, although in one embodiment, the carrier may include water with minimal or no significant concentrations of organic solvent, except when incidentally incorporated into the composition as a minor component of other essential or optional ingredients.
[0153] Carriers useful in hair care compositions include water and aqueous solutions of lower alkyl alcohols and polyhydric alcohols. Lower alkyl alcohols useful herein are monohydric alcohols having 1 to 6 carbon atoms, in one embodiment, ethanol and isopropanol. Exemplary polyhydric alcohols useful herein include propylene glycol, hexylene glycol, glycerin, and propanediol.
[0154] Foam dispenser The hair care compositions described herein may be delivered in a foam dispenser. The foam dispenser may be an aerosol foam dispenser, a bag-on-valve type, a dip tube type, a piston type, or other conventional type. The aerosol foam dispenser may include a reservoir for holding the hair treatment composition. The reservoir may be made of any suitable material selected from the group consisting of plastic, metal, alloy, laminate, and combinations thereof. The reservoir may be for single use only. The reservoir may be detachable from the aerosol foam dispenser. Alternatively, the reservoir may be integral with the aerosol foam dispenser. Furthermore, there may be more than one reservoir.
[0155] Test Method In vivo scalp deposition (depo) The deposition of anti-dandruff active substance on scalp is measured by washing individual's hair with a composition containing anti-dandruff active substance, for example, the composition according to the present invention.A trained hairdresser applies 5g of liquid shampoo control to half of the scalp of panelist, and washes according to conventional washing protocol.Then, 2.5g of foam is applied to the other half of the head of panelist, and washes according to conventional washing protocol.Then, the hair is divided on the scalp area, and an open-ended glass cylinder is held on the surface, and at the same time, an aliquot of extraction solution is added and stirred, and the content of anti-dandruff active substance is collected, and analytical measurement is carried out according to conventional methods such as HPLC.
[0156] Sebum cleansing method For testing, obtain a clean hair switch. Warm the artificial sebum and mix with Uvitex OB. Apply the oil and Uvitex OB mixture to a designated 3.5 inch area along the body of the hair switch. A consistent oil treatment occurs as each hair switch is treated. The amount of shampoo applied to the hair is approximately 0.1 cc per gram of hair. Wet the hair switch for 15 seconds. Apply the product from top to bottom to the hair. Milk the shampoo into the hair by pulling it with both hands for approximately 30 seconds. Rinse the hair switch and squeeze to remove excess water. Then dry the hair switch in a heat box. Apply an oil-absorbing sheet with one hand and wrap it around the back of the hair switch. Apply medium pressure while pulling the oil-absorbing sheet under the hair strand. Expose the oil-absorbing sheet to a black light and rate it based on its glow level (0 = no glow, 5 = full glow).
[0157] Wet Feel Sensory Wet feel sensory testing is performed by trained panelists. Hair switches are pre-wetted and squeezed to remove excess water. Product is applied to the front and back of the switch with a given relevant weight of shampoo per weight of switch. Foam product is applied at 1 / 2 dose to the full dose of liquid control Example 17. To evaluate the effect of foam vs. liquid form of the same formula, 1 / 2 of Example 13 is applied as a foam versus 1 / 2 of Example 13 as a liquid. The product is spread in a controlled manner to saturate the switch. An established sensory protocol is followed, addressing wet feel attributes in the following order: rinse count drag, coated feel, slippery feel, and combing force. A rating scale of 0 to 14 is used for each rating.
[0158] Dry Feel Sensory Dry feel sensory testing is performed by trained panelists. Panelists clean their fingers with alcohol before and between each tactile evaluation. The hair switches are subjected to a wet sensory treatment protocol for application before evaluation. The hair is allowed to dry in a hot box. Panelists rate smoothness, body combing, and end combing. Smoothness is rated from least smooth to smoothest. Body and end combing are rated from least to most combing.
[0159] The percentage of agent deposited can be calculated using the following equation:
[0160]
number
[0161] Sample calculation of % Piroctone Olamine attached: Grams of agent deposited = 1.7 x 10 -6 g Extracted scalp area = 1cm 2 Weight % of piroctone olamine in shampoo = 1.0% Grams of shampoo applied = 5g Treated scalp area = 300cm 2
[0162]
number
[0163] The deposition efficiency can be calculated using the following equation:
[0164]
number
[0165] Sample calculation of deposition efficiency: Percentage of piroctone olamine attached by the formulation of the example (%) = 1.92% Percentage of piroctone olamine deposited by the control formulation (%) = 1.02%
[0166]
number
[0167] Adhesion results Examples (1 and 2) high surfactant formulation (24% total surfactant) demonstrates deposition efficiency 1.4 times higher than Liquid Method Control Example 15 when applied at half the weight of foam relative to the control liquid, so that the delivered piroctone olamine accounts for the same percentage as Liquid Method Control Example 15. Sample 3 demonstrates deposition efficiency 1.2 times higher than Method Control Example 15 when the formulation concentration is reduced from 1% to 0.8% PO, but the dose is adjusted to deliver a PO concentration equivalent to the 0.5% Liquid Method Control to the scalp, yet remains more efficient. As observed in Examples (4, 5, and 6), reducing the total surfactant to 23% results in deposition that is 1.7 times more efficient than Liquid Method Control Example 15.
[0168] As observed in Examples 7-14 and 18, decreasing surfactant concentration (from 12.5 to 9%) tends to increase deposition efficiency in the range of 1.9- to 2.7-fold relative to the liquid control (Example 15). This result for the low-surfactant formulations is likely due to PO activity approaching the solubility limit within a given surfactant system. The closer the solubility limit can be approached, the greater the potential ability of the formulation to deliver piroctone olamine upon dilution. Therefore, the selection of the surfactant system is crucial for piroctone olamine delivery. In addition, the selection of the propellant type can also aid or hinder the ability of PO to deposit. Depending on whether the propellant type and concentration are hydrophilic or hydrophobic, the propellant can swell micelles, elongate micelles, or fail to enter micelles. Therefore, the selection of the propellant is also crucial when attempting to effectively deliver soluble drug actives to the scalp.
[0169] In the present invention, the foaming composition may have a deposition efficiency greater than 1.7 times that of a control composition that deposits about 1% by weight of the applied surfactant-soluble anti-dandruff active.
[0170] Sequential Monadic Team Test (n=9) method The low-surfactant and high-surfactant foam shampoos are placed between panelists. Panelists receive one bottle of foam shampoo labeled for the consumer test, printed instructions with visuals, and a printed questionnaire. Panelists are asked to use the first foam shampoo product at least three times in a row before answering questions on the provided questionnaire. Then, during the use period of the second product, they are asked to return the first product to avoid any confusion. They are instructed to use the second product in the same way as the first product before answering the provided questionnaire.
[0171] [Table 1]
[0172] result The data show that more respondents rated the low surfactant (Example 9) lather as equal to or better than the high surfactant (Example 3) for the attributes "leaves hair and scalp feeling clean when wet, ability to cleanse scalp, and ability to cleanse hair."
[0173] Hair Sensory Data for Wet and Dry Sensory Conditioning Key (1 Most Conditioned to 3 Least Conditioned)
[0174] [Table 2]
[0175] [Table 3]
[0176] result: The data show that foam Example 13 applied at half the weight provides the most conditioning compared to the full weight of the high-conditioning liquid commercial control shampoo Example 17. The liquid version of Example 13 (without added propellant) is applied at half the weight to test the foam form as a single variable against the liquid form applied at the same weight. It is observed that the liquid version of Example 13 does not provide as much conditioning in terms of wet feel via sensory response. The formulation of Example 9 is another example showing that increasing the surfactant from 9% of Example 13 to 12.5% total surfactant still maintains more dry conditioning compared to the commercial liquid control Example 17. The foam of Example 13 maintains the highest dry conditioning compared to Examples 17 and 9.
[0177] Manufacturing method The following examples illustrate non-limiting examples of the invention described herein. The exemplified hair care compositions can be made by mixing water, polymer, and surfactant with sodium xylene sulfonate or a rheology modifier to thin the surfactant phase. The ingredients are thoroughly mixed at ambient temperature. Additional ingredients, including foaming agents, electrolytes, silicone emulsions, preservatives, and fragrances, may be added to the product. It will be understood that other modifications of the hair care composition within the skill of one of ordinary skill in the formulation arts can be made without departing from the spirit and scope of the present invention. All parts, percentages (%), and ratios herein are by weight unless otherwise specified. Some ingredients may be supplied by the supplier as a dilute solution. The amounts stated represent the weight percent of actives unless otherwise specified.
[0178] The following examples illustrate non-limiting examples of the invention described herein. All parts, percentages (%), and ratios herein are by weight unless otherwise specified. Some ingredients may be provided by the supplier as a diluted solution. The amounts stated represent the weight percent of active material unless otherwise specified. The following table is a non-limiting example of the hair care composition described herein:
[0179] [Table 4]
[0180] [Table 5]
[0181] [Table 6]
[0182] [Table 7] 1. Sodium Laureth-1 Sulfate (Stepan Company) 2. Sodium Laureth-3 Sulfate (Stepan Company) 3. Sodium lauryl sulfate (Stepan Company) 4. Sodium tridecyl ether sulfate - 2 moles (Solvay (Blue Island US)) 5. Cocamidopropyl Betaine High pH (Stepan Co. Millsdale, Elwood, US) 6. Cocamide monoethanolamine, CMEA (Stepan Company) 7. Amaze XT Dehydroxyxanthan Gum (Akzo Nobel) 8. Glycol Distearate (Golschmidt Chemical Company) 9. Glycerin (P&G Chemicals) 10. Piroctone olamine (Octopirox, manufactured by Clariant) 11. Zinc Pyrithione, U2 ZPT (Lonza) 12. Zinc Carbonate (Bruggeman Group) 13. Air fresheners supplied by P&G 14. Guar Hydroxypropyltrimonium Chloride, BF 17 HMW Guar (Ashland) 15. Guar hydroxypropyltrimonium chloride, NHance™ 3196 (Ashland) having a MW of 1,700,000 g / mol and a charge density of 0.7 meq / g 16. Guar hydroxypropyltrimonium chloride, Jaguar C500 (Solvay) having a MW of 500,000 g / mol and a charge density of 0.8 meq / g 17. Polyquaternium 10 (Dow Chemical) 18. Polyethylene glycol, PEG 23M Polyox WSR N-1 2 K (Amerchol Corp., Piscataway, NJ) 19. Dimethicone DM5500 (Wacker Silicone) 20. Hydrochloric acid (Mallinckrodt Baker Inc.) 21. Kathon CG (Akzo Nobel) Preservative 22. Sodium xylene sulfonate (Stepan Company) 23. Citric Acid (Cargill Inc.) 24. Sodium Benzoate (Kalama Chemical) 25. Dimethicone DC330M Momentive 26. Tetrasodium EDTA tetrahydrate 27. Water (Misty Mountain Spring Water) 28. Blowing Agent A46 (Isobutane and Propane) (Diversified Cpc International (Channahon US)) 29. Blowing agent HF0 (trans 1,3,3,3 tetrafluoroprop-1-ene) (Honey Well)
[0183] Foam rheology method (yield point) The foam shampoo is applied to an AR1000 rheometer for a foam oscillatory stress sweep. A 60 mm smooth acrylic plate is used for shear stress measurements. Measurements are performed at 25°C. The plate head is lowered to 1200 microns, and excess foam is removed with a spatula to prevent resistance during the measurement. The measurement gap height is then lowered to 1000 microns. Sweeps are performed from 0.1 to 400 Pa. Data are analyzed via TA Rheology Advantage Data Analysis software. The yield point is determined when the oscillatory shear stress begins to deviate from its tangent. Yield point measurements are reported in Pa.
[0184] The dose of foam may have a yield point of from about 10 Pa to about 50 Pa, alternatively from about 15 Pa to about 30 Pa, alternatively from about 20 Pa to about 30 Pa.
[0185] The dosage of foam is also about 0.01 g / cm 3 ~about 0.02g / cm 3 , or about 0.05 g / cm3 ~about 0.1g / cm 3 , or about 0.07 g / cm 3 ~about 0.1g / cm 3 The foam density may be
[0186] Kruss bubble analyzer (bubble size) The initial Sauter mean radius R was measured using a commercially available Kruss foam analyzer DFA100 supplied by Kruss. 32 Foam shampoo is analyzed for bubble size. Shampoo foam is dispensed into a CY4571 column containing a rectangular pillar. An internal stopper is placed in the column approximately 100 mL from the top of the chamber. The camera height is set to 244 mm, and the camera position is positioned within slot 3. Foam structure is captured for 120 seconds at 2 frames per second. Data analysis is performed with Kruss Advance 1.5.1.0 software application version.
[0187] The dose of foam may also have a radius of about 5 μm to about 100 μm, alternatively about 5 μm to about 90 μm, alternatively about 10 μm to about 60 μm, alternatively about 15 μm to about 50 μm, alternatively about 25 μm to about 40 μm. 32 The cell size distribution may have:
[0188] [Table 8]
[0189] result The results for Examples 3, 9, 18, and 19 all show similar bubble size measurements within the range (29-33 um for R32 initial), indicating that the high and low surfactant foams have similar foam structures. The yield point result for the high surfactant foam of Example 3 is a yield point of 36 (Pa). The low surfactant formulations Examples 9, 18, and 19 all show lower rheology (19, 25, and 27 Pa, respectively), indicating that the low surfactant spreads or shears more easily than the more viscoelastic Example 3.
[0190] [Table 9]
[0191] [Table 10]
[0192] [Table 11] 1. Sodium decyl sulfate (P&G Chemical) 2. Sodium deceth sulfate (P&G Chemical) 3. Sodium Laureth-1 Sulfate (Stepan Company) 4. Sodium Laureth-3 Sulfate (Stepan Company) 5. Sodium lauryl sulfate (Stepan Company) 6. Sodium tridecyl ether sulfate - 2 moles (Solvay (Blue Island US)) 7. Cocamidopropyl Betaine High pH (Stepan Co. Millsdale, Elwood, US) 8. Cocamide monoethanolamine, CMEA (Stepan Company) 9. Sodium Laureth Sulfosuccinate (Stepan Company) 10. Sodium Cocoyl Alanine (Sino Lion) 11. Sodium Lauroyl Sarcosinate (Stepan Company) 12. Dehydroxyxanthan Gum Amaze XT (Akzo Nobel) 13. Glycol Distearate (Golschmidt Chemical Company) 14. Glycerin (P&G Chemicals) 15. Piroctone olamine (Octopirox, manufactured by Clariant) 16. Zinc Pyrithione, U2 ZPT (Lonza) 17. Zinc Carbonate (Bruggeman Group) 18. Air freshener (P&G Chemical) 19. Guar Hydroxypropyltrimonium Chloride, BF 17 HMW Guar (Ashland) 20. Guar hydroxypropyltrimonium chloride, NHance™ 3196 (Ashland) having a MW of 1,700,000 g / mol and a charge density of 0.7 meq / g 21. Guar hydroxypropyltrimonium chloride, Jaguar C500 (Solvay) having a MW of 500,000 g / mol and a charge density of 0.8 meq / g 22. Polyquaternium 10 (Dow Chemical) 23. Polyethylene glycol, PEG 23M Polyox WSR N-1 2 K (Amerchol Corp., Piscataway, NJ) 24. Dimethicone DM5500 (Wacker Silicone) 25. Hydrochloric acid (Mallinckrodt Baker Inc.) 26. Kathon CG (Akzo Nobel) Preservative 27. Sodium xylene sulfonate (Stepan Company) 28. Citric Acid (Cargill Inc.) 29. Sodium Benzoate (Kalama Chemical) 30. Dimethicone, DC330M Momentive 31. Tetrasodium EDTA tetrahydrate 32. Water (Misty Mountain Spring Water) 33. Blowing Agent A46 (Isobutane and Propane) (Diversified Cpc International (Channahon US)) 34. Blowing agent HF0 (trans 1,3,3,3 tetrafluoroprop-1-ene) (manufactured by Honey Well) 35.
[0193] method A single-product, context-assisted, blinded study is conducted to test a low-surfactant foaming anti-dandruff shampoo. The control for this study is a high-surfactant foaming shampoo formula containing 24% total surfactant. This summary includes data from panelists' post-use questionnaires. Panelists are asked to rate performance on a 5-point scale from 100 to 0. Data are reported as mean scores or percentages (uppercase letters indicate significantly better than the reference; gray shading = significantly worse than the control). Table 3 below contains details of the formula by leg. All tables are at the 90% confidence level.
[0194] [Table 12]
[0195] These data show that for key attributes of low-surfactant foam shampoos, Examples 9 and 19 provide "overall clean" responses comparable to high-surfactant foam shampoo Example 3. Example 18, containing PEG23M and low surfactant, demonstrates directionally higher responses than all foams and significantly higher responses than Example 19, which contains silicone, which can lead to a greasy, sticky scalp / hair feel for consumers. Similar responses are also observed for "overall clean hair and scalp feel over time" and "overall mildness on hair and scalp" on hair and scalp. Consumer responses help confirm that low-surfactant foams Examples 9, 18, and 19 (12.5%) provide a mild cleansing experience while simply cleaning similarly to the foam of high-surfactant Example 3 (24%). During application, lathering, and rinsing, consumers perceived the low-surfactant foam as easy to spread and rinse from hair, similar to the high-surfactant foam. After rinsing Examples 9 and 18, consumers felt that their scalps were as clean as the high-surfactant lather. Only Example 19, which contained a high concentration of silicone, yielded a significantly lower score, indicating a less clean scalp. Low-surfactant Formula 18 was observed to be equivalent to high-surfactant Example 3 in leaving the roots feeling clean. Again, it can be assumed that PEG23M helps provide a cleaner feel. All formulas are found to be significantly better than low-surfactant Example 19, which contains a high silicone concentration, in terms of "scalp and hair feeling clean after shampoo rinsing without leaving unwanted residue." All formulas demonstrate comparable results to the high-surfactant control in terms of "ease of fingering / combing hair after shampoo rinsing." Responses for these formulas indicate good combability and thorough cleansing. When dampened after showering, panelists rate low-surfactant PEG23M-containing Example 18 as equivalent to high-surfactant Example 3 in terms of leaving the scalp and roots feeling clean after showering and rinsing. Example 9, which contains no PEG23M, and Example 19, which contains PEG23M and silicone, perform significantly worse on these questions.Finally, all formulas show comparable finger / combability on damp hair after shower, again indicating clean, conditioned, and easy-to-comb hair.
[0196] Examples / Combinations A. a. about 5% to about 13% total surfactants having one or more anionic surfactants; b. 0.1% to about 2% of a surfactant-soluble anti-dandruff active; c. A foaming composition comprising about 3% to about 15% foaming agent and having a pH of about 3.5 to 6.5. B. The foaming composition of paragraph A, wherein the total surfactant comprising one or more anionic surfactants is from about 9% to about 13%. C. The foaming composition of paragraph A or B, wherein the total surfactant, having one or more anionic surfactants, is from about 10% to about 13%. D. The foaming composition of paragraphs A-C, wherein the total surfactant comprising one or more anionic surfactants is from about 11% to about 13%. E. The foaming composition of paragraphs A-D, wherein the total surfactant comprising one or more anionic surfactants is about 12% to about 13%. F. The foaming composition of paragraphs A-E, wherein the pH is from about 4 to about 6. G. The foaming composition of paragraphs A-F, wherein the pH is from about 5 to about 6. H. The foaming composition of paragraphs A through G, wherein the surfactant-soluble anti-dandruff active is from about 0.6% to about 1%. I. The foaming composition of paragraphs AH, wherein the surfactant-soluble anti-dandruff active is from about 0.5% to about 0.8%. J. Anti-dandruff adhesion, 0.8 micrograms / cm 2 The foamable composition according to paragraphs AI, II, III, IIIa, IIIb, IIIc, IIId, IIIe, IIIg, IIIg, IIIh, IIIh, IIIh, IIIi ... K. Foam density is 0.01g / cm 3 ~about 0.2g / cm 3 The foamable composition of paragraphs A-G, wherein L. Foam density is 0.05g / cm 3~about 0.1g / cm 3 The foamable composition of paragraphs A-G, wherein M. The bubbles are about 5 μm to about 90 μm in diameter. 32 The foamable composition of paragraphs A-L, having a bubble size distribution having: N. The foamable composition of paragraphs A through M, wherein the foam has a yield point of from about 10 Pa to about 50 Pa. O. The foamable composition of paragraphs A-N, having a viscosity (measured at 25° C.) of less than 3,000 cps. P. The foaming composition of paragraphs A-O, further comprising from about 1% to about 5% of one or more amphoteric / zwitterionic or nonionic co-surfactants, and mixtures thereof. Q. The foamable composition of paragraphs A-P, wherein the viscosity modifier has a molecular weight of from about 75 g / mole to about 350 g / mole. R. The foamable composition of paragraphs A-Q, wherein the foaming agent is from about 1% to about 15%. S. The foaming composition of paragraphs A-R, further comprising 0.1% to 5% of a stabilizer. T. The foamable composition of paragraphs A-S, wherein the stabilizer is selected from the group consisting of trihydroxystearin, ethylene glycol distearate polymer, and mixtures thereof. U. The foamable composition of paragraphs A-T, wherein the viscosity modifier is selected from the group consisting of ethanol, dipropylene glycol, sodium xylene sulfonate, sodium chloride, alkoxylated silicone / ethoxylated silicone / propoxylated silicone / polyoxyethylene silicone / polyoxypropylene silicone / polyethylene glycol silicone / PEG-8 silicone / PEG-9 silicone / PEG-n silicone / silicone ether (where n can be another integer), and mixtures thereof. V. The foaming composition of paragraphs A-U, further comprising anti-dandruff particles selected from the group consisting of pyridinethione salts, selenium sulfide, granular sulfur, and mixtures thereof. W. The foaming composition of paragraphs A-V, wherein the surfactant-soluble agent is selected from the group consisting of azoles, piroctone olamine, N-hydroxy-6-octyloxypyridin-2(1H)one, hexamidine diisethionate, and mixtures thereof. X. The foaming composition of paragraphs A-W, wherein the co-surfactant is selected from the group consisting of lauramidopropyl betaine, cocoamidopropyl betaine, lauryl hydroxysultaine, sodium lauroamphoacetate, coco monoethanolamide, and mixtures thereof. Y. The foamable composition of paragraphs A-X, wherein the blowing agent is selected from the group consisting of propane, n-butane, isobutane, cyclopropane, and mixtures thereof, and halogenated hydrocarbons such as dichlorodifluoromethane, 1,1-dichloro-1,1,2,2-tetrafluoroethane, 1-chloro-1,1-difluoro-2,2-trifluoroethane, 1-chloro-1,1-difluoroethylene, 1,1-difluoroethane, dimethyl ether, monochlorodifluoromethane, trans-1,3,3,3-tetrafluoropropene, CO2, and combinations thereof. Z. The foamable composition of paragraphs A-Y, wherein the blowing agent is selected from the group consisting of propane and isobutene, trans-1,3,3,3-tetrafluoropropene, and mixtures thereof. AA. The foaming composition of paragraphs A-Z, further comprising a cationic polymer. BB. The foaming composition of paragraphs A-AA, further comprising a conditioning agent. CC. The foamable composition of paragraphs A-BB, wherein the conditioning agent is a silicone. DD. The foaming composition of paragraphs A-CC, having a deposition efficiency greater than 1.7 times that of a control composition depositing about 1% by weight of the applied surfactant-soluble anti-dandruff active.
[0197] Dimensions and values disclosed herein should not be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "approximately 40 mm."
[0198] All documents cited in this application, including all cross-referenced or related patents or patent applications, and any patent application or patent to which this application claims priority or benefit, are incorporated herein by reference in their entirety, unless expressly stated to the contrary. The citation of any document shall not be deemed to be prior art to any invention disclosed or claimed herein, or to teach, suggest, or disclose such invention, either alone or in combination with any other reference(s). Furthermore, to the extent that any meaning or definition of a term in this document 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 document shall govern.
[0199] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims
1. 1. A foamable composition comprising: a. 5% to 13% total surfactants having one or more anionic surfactants; b. 0.1% to 2% of a surfactant-soluble anti-dandruff active; and c. 3% to 15% of a blowing agent; Including, the surfactant-soluble anti-dandruff active is piroctone olamine; the foaming composition has a pH of 3.5 to 6.5; The foaming composition has a deposition efficiency greater than 1.7 times that of the liquid control composition; The liquid control composition contained 8% sodium laureth sulfate, 7% sodium lauryl sulfate, 2% cocamidopropyl betaine, 1.5% glycol distearate, 0.5% piroctone olamine, 0.85% fragrance, 0.25% guar hydroxypropyltrimonium chloride (N-Hance 3196), 0.8% dimethicone DM5500, 0.033% preservative (Kathon CG), 0.6% citric acid, sodium xylene sulfonate (qs) to a viscosity target of less than 3000 cps when measured at 25° C., 0.15% sodium benzoate, 0.15% tetrasodium EDTA tetrahydrate, and water (qs) to 100% (Misty Mountain Spring Water), and had a pH of 6. Foaming composition.
2. The amount of surfactant-soluble anti-dandruff active agent deposited on the scalp is 0.8 micrograms / cm 2 The foamable composition according to claim 1, wherein
3. The foam density is 0.01 g / cm 3 ~0.2 g / cm 3 3. The foamable composition according to claim 1 or 2, wherein
4. The foam has a Sauter mean particle size R of 15 μm to 50 μm as measured with a Kruss foam analyzer DFA100. 32 4. The foamable composition of claim 1, having a bubble size distribution having:
5. 5. The foamable composition of claim 4, wherein the foam has a yield point of 10 Pa to 50 Pa.
6. 6. The foamable composition of claim 1, having a viscosity measured at 25°C of less than 3,000 cps.
7. 7. The foamable composition of any one of claims 1 to 6, further comprising a viscosity modifier having a molecular weight of from 75 g / mole to 350 g / mole.
8. 8. The foamable composition of any one of claims 1 to 7, further comprising 0.1% to 5% of a stabilizer selected from the group consisting of trihydroxystearin, ethylene glycol distearate polymers, and mixtures thereof.
9. 8. The foamable composition of claim 7, wherein the viscosity modifier is selected from the group consisting of ethanol, dipropylene glycol, sodium xylene sulfonate, sodium chloride, alkoxylated silicones / ethoxylated silicones / propoxylated silicones / polyoxyethylene silicones / polyoxypropylene silicones / polyethylene glycol silicones / PEG-8 silicones / PEG-9 silicones / PEG-n silicones / silicone ethers (where n can be another integer), and mixtures thereof.
10. 10. The foaming composition of any one of claims 1 to 9, further comprising anti-dandruff particles selected from the group consisting of pyridinethione salts, selenium sulfide, granular sulfur, and mixtures thereof.
11. 11. The foamable composition of any one of claims 1 to 10, wherein the blowing agent is selected from the group consisting of propane, n-butane, isobutane, cyclopropane, and mixtures thereof, and halogenated hydrocarbons such as dichlorodifluoromethane, 1,1-dichloro-1,1,2,2-tetrafluoroethane, 1-chloro-1,1-difluoro-2,2-trifluoroethane, 1-chloro-1,1-difluoroethylene, 1,1-difluoroethane, dimethyl ether, monochlorodifluoromethane, trans-1,3,3,3-tetrafluoropropene, CO2, and combinations thereof.
Citation Information
Patent Citations
Water-less shampoo composition of aerosol spray-type
KR1020080111280A