Patent Grant
11497691
The present disclosure generally relates to shampoo compositions which are formulated with sheet-like microcapsules.
Consumers desire a product which delivers both good in use benefits, and also has an aesthetically pleasing product appearance. It can be difficult to incorporate aesthetic materials like sheet-like microcapsules, while also maintaining a shampoo composition that can deliver the consumer desired benefits. The sheet-like microcapsules may roll up or fold over when being incorporated into the product. Additionally, for the sheet-like microcapsules to be easily visible, the shampoo composition can be clear. Clear shampoo compositions can be difficult to formulate such that they maintain good consumer use benefits such as dry and wet feel, and/or conditioning. Alternatively, the shampoo can be a conditioning, and opaque.
It has been surprisingly found that shampoo products delivering both good consumer use benefits, such as good dry and wet feel, as well as aesthetically pleasing product appearance in bottle can be achieved.
A shampoo composition comprising from about 5 wt % to about 35 wt % of a detersive surfactant selected from the group consisting of anionic surfactants, amphoteric surfactants, nonionic surfactants, and mixtures thereof; from about 0.05 wt % to about 10 wt % of sheet like microcapsules; from about 0.05 wt % to about 3 wt % of a cationic deposition polymer; wherein the shampoo composition has a yield stress of from about 0.01 to about 20 Pa at a shear rate of 10−2 to 10−4 s−1, a viscosity of from about 1.0 to about 15 Pa·s at a shear rate of 2 s−1, and a viscosity of from about 0.1 to about 4-Pa·s at a shear rate of 100 s−1.
Shampoo composition comprising from about 5 wt % to about 35 wt % of a detersive surfactant selected from the group consisting of anionic surfactants, amphoteric surfactants, nonionic surfactants, and mixtures thereof; from about 0.05 wt % to about 10 wt % of sheet like microcapsules; from about 0.05 wt % to about 3 wt % of a cationic deposition polymer; wherein the shampoo composition has a yield stress of from about 0.00001 to about 0.01 Pa at a shear rate of 10−-2 to 10−4 -s−1, a viscosity of from about 0.1 to about 15 Pa·s at a shear rate of 2 s−1, and a viscosity of from about 0.1 to about 4-Pa·s at a shear rate of 100 s−1.
While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the present disclosure will be better understood from the following description.
As used herein, the term “fluid” includes liquids and gels.
As used herein, the articles including “a” and “an” when used in a claim, are understood to mean one or more of what is claimed or described.
As used herein, “comprising” means that other steps and other ingredients which do not affect the end result can be added. This term encompasses the terms “consisting of” and “consisting essentially of”.
As used herein, “mixtures” is meant to include a simple combination of materials and any compounds that may result from their combination.
As used herein, “molecular weight” or “M.Wt.” refers to the weight average molecular weight unless otherwise stated. Molecular weight is measured using industry standard method, gel permeation chromatography (“GPC”). The molecular weight has units of grams/mol.
As used herein, “shampoo composition” includes shampoo products such as shampoos, shampoo conditioners, conditioning shampoos, and other surfactant-based liquid compositions.
As used herein, the terms “include,” “includes,” and “including,” are meant to be non-limiting and are understood to mean “comprise,” “comprises,” and “comprising,” respectively.
All percentages, parts and ratios are based upon the total weight of the compositions described herein, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and, therefore, do not include carriers or by-products that may be included in commercially available materials.
Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
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 will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
Shampoo Compositions
The shampoo composition has from about 5 wt % to about 35 wt % of a detersive surfactant selected from the group consisting of anionic surfactants, amphoteric surfactants, nonionic surfactants, and mixtures thereof, from about 0.1 wt % to about 10 wt % of sheet like microcapsules, and from about 0.05 wt % to about 3 wt % of a cationic deposition polymer wherein the shampoo composition has a yield stress of from about 0.01 to about 20 Pa at a shear rate of 10−2 to 10−4 s−1, a viscosity of from about 1.0 to about 15 Pa·s at a shear rate of 2 s−1, and a viscosity of from about 0.1 to about 4 -Pa·s at a shear rate of 100 s−1.
Sheet-Like Microcapsules
The shampoo product contains sheet like microcapsules having lamellar or strip-like, sheet or ribbon like form. The shampoo product comprises from about 0.05 wt % to about 10 wt %, alternatively from about 0.1 wt % to about 5 wt % of sheet like microcapsules. They have a thickness less than the width, with a thickness of from about 0.01 to about 1 mm, alternatively from about 0.4 to about 0.8 mm (measurement at the middle of the sheet). The sheet-like microcapsules are about 2 mm to about 20 mm in width and/or length, alternatively from about 5 mm to about 20 mm in width and/or length, alternatively from about 8 mm to about 15 mm in width and/or length. The shape can be any geometric shape, including but not limited to circular (
The sheet like microcapsules can be a gellan film and comprise from about 30 to about 40 parts of sodium alginate, from about 40 to about 50 parts gellan gum, from about 5 to about 10 parts polyvinyl alcohol, from about 5 to about 10 parts hydroxyl methyl cellulose sodium. The microcapsules may also comprise menthol, peppermint oil, menthyl lactate, jojoba oil, Vitamin E as well as dyes, other extracts and/or perfumes. The microcapsules, Dream Petals, are available from Sandream Impact LLC, Fairfield N.J.
Rheology
Incorporation of sheet-like microcapsules into the shampoo product can be complex. The sheet-like microcapsules can fold, break, roll or otherwise fail to maintain the desired shape. This results in a less than desirable appearance in the bottle. Maintaining the proper rheology of the product results in sheet-like microcapsules distributed in the shampoo product while maintaining the desired shape. For example, as shown in
To suspend the sheet-like microcapsules in the shampoo composition the shampoo composition has a yield stress, as determined using the Herschel-Bulkley model at a shear rate from 10−2 to 10−4 -s−1, of from about 0.01 to about 20 Pa, alternatively from about 0.01 to about 10 Pa, alternatively from about 0.01 to about 5 Pa. The shampoo composition (to suspend the sheet-like microcapsules throughout the product) has a viscosity, at a shear rate of 2 s−1, of from about 0.01 to about 15 Pa·s. Further to suspend the sheet-like microcapsules the shampoo composition has a viscosity, at a shear rate of 100 s−1, of from about 0.1 to about 4 Pa·s, alternatively from about 0.1 to about 2 Pa·s, alternatively from about 0.1 to about 1 Pa·s.
If the sheet-like microcapsules are not going to be suspended throughout the product, the shampoo composition can have a yield stress, as determined using the Herschel-Bulkley-model at a shear rate from 10−2 to 10−4 -s−1, of from about 0.00001 to about 0.01 Pa·s. The shampoo composition (without suspending the sheet-like microcapsules) has a viscosity at a shear rate of 2 s−1, of from about 0.1 to about 15 Pa·s. Further without suspending the sheet-like microcapsules the shampoo composition has a viscosity at 100 s−1 of from about 0.1 to about 4 Pa·s, alternatively from about 0.1 to about 2 Pa·s, alternatively from about 0.1 to about 1 Pa·s.
The shampoo composition can comprise from about 0.5 wt % to about 7 wt %, alternatively from about 1.5 wt % to about 5 wt % of a rheology modifier to achieve the desired rheology profile. The rheology modifier can be selected from the group consisting of polyacrylates, gellan gum, sodium polyacrylate starch and mixtures thereof.
Surfactant
The shampoo compositions described herein can include one or more surfactants in the surfactant system. The one or more surfactants can be selected from the group consisting of anionic surfactants, amphoteric surfactants, nonionic surfactants and mixtures thereof. The one or more surfactants can be substantially free of sulfate-based surfactants. As can be appreciated, surfactants provide a cleaning benefit to soiled articles such as hair, skin, and hair follicles by facilitating the removal of oil and other soils. Surfactants generally facilitate such cleaning due to their amphiphilic nature which allows for the surfactants to break up, and form micelles around, oil and other soils which can then be rinsed out, thereby removing them from the soiled article. Suitable surfactants for a shampoo composition can include anionic moieties to allow for the formation of a coacervate with a cationic polymer. The surfactant can be selected from anionic surfactants, amphoteric surfactants, zwitterionic surfactants, non-ionic surfactants, and combinations thereof.
The shampoo composition comprises one or more detersive surfactants in the shampoo base. The detersive surfactant component is included in shampoo compositions to provide cleansing performance. The detersive surfactant may be selected from anionic detersive surfactant, zwitterionic, or amphoteric detersive surfactant, or a combination thereof. Such surfactants should be physically and chemically compatible with the components described herein, or should not otherwise unduly impair product stability, aesthetics or performance. Particularly suitable herein is sodium laureth-n-sulfate, wherein n=1 (“SLE1S”). SLE1S enables more efficient lathering and cleaning when compared to higher mole ethoxylate equivalents, especially in a shampoo composition that contains high levels of conditioning actives.
Suitable anionic detersive surfactants include those which are known for use in hair care or other personal care shampoo compositions. The anionic detersive surfactant may be a combination of sodium lauryl sulfate and sodium laureth-n sulfate. The concentration of the anionic surfactant in the composition should be sufficient to provide the desired cleaning and lather performance, and generally range from about 5% to about 50%, alternatively from about 8% to about 30%, alternatively from about 9% to about 25%, and alternatively from about 10% to about 17%, by weight of the composition.
Suitable zwitterionic or amphoteric detersive surfactants include those which are known for use in hair care or other personal shampoo compositions. Concentration of such amphoteric detersive surfactants range from about 0.5% to about 20%, alternatively from about 1% to about 10%. Non-limiting examples of suitable zwitterionic or amphoteric surfactants are described in U.S. Pat. Nos. 5,104,646 and 5,106,609.
Additional anionic surfactants suitable for use herein include alkyl and alkyl ether sulfates of the formula ROSO3M and RO(C2H4O)xSO3M, wherein R is alkyl or alkenyl of from about 8 to about 18 carbon atoms, x is 1 to 10, and M is a water-soluble cation such as ammonium, sodium, potassium, and triethanolamine cation or salts of the divalent magnesium ion with two anionic surfactant anions. The alkyl ether sulfates may be made as condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 24 carbon atoms. The alcohols can be derived from fats such as coconut oil, palm oil, palm kernel oil, or tallow, or can be synthetic.
Other suitable anionic surfactants include water-soluble salts of the organic, sulfonic acids of the general formula [R1—SO3M]. R1 being a straight chain aliphatic hydrocarbon radical having from 13 to 17 carbon atoms, alternatively from 13 to 15 carbon atoms. M is a water soluble cation such as ammonium, sodium, potassium, and triethanolamine cation or salts of the divalent magnesium ion with two anionic surfactant anions. These materials are produced by the reaction of SO2 and O2 with suitable chain length normal paraffins (C14-C17) and are sold commercially as sodium paraffin sulfonates.
Examples of additional anionic surfactants suitable for use include, but are not limited to, 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, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth 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, monoethanolamine cocoyl sulfate, sodium trideceth sulfate, sodium tridecyl sulfate, sodium methyl lauroyl taurate, sodium methyl cocoyl taurate, sodium lauroyl isethionate, sodium cocoyl isethionate, sodium laurethsulfosuccinate, sodium laurylsulfosuccinate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, and mixtures thereof.
The shampoo composition may further comprise additional surfactants for use in combination with the anionic detersive surfactant component described herein. Suitable additional surfactants include cationic and nonionic surfactants.
Non-limiting examples of other anionic, zwitterionic, amphoteric, cationic, nonionic, or optional additional surfactants suitable for use in the compositions are described in McCutcheon's, Emulsifiers and Detergents, 1989 Annual, published by M. C. Publishing Co., and U.S. Pat. Nos. 3,929,678; 2,658,072; 2,438,091; and 2,528,378.
The shampoo compositions described herein can be substantially free of sulfate-based surfactants. “Substantially free” of sulfate based surfactants as used herein means from about 0 wt % to about 3 wt %, alternatively from about 0 wt % to about 2 wt %, alternatively from about 0 wt % to about 1 wt %, alternatively from about 0 wt % to about 0.5 wt %, alternatively from about 0 wt % to about 0.25 wt %, alternatively from about 0 wt % to about 0.1 wt %, alternatively from about 0 wt % to about 0.05 wt %, alternatively from about 0 wt % to about 0.01 wt %, alternatively from about 0 wt % to about 0.001 wt %, and/or alternatively free of sulfates. As used herein, “free of” means 0 wt %.
The one or more additional anionic surfactants may be selected from the group consisting of isethionates, sarcosinates, sulfonates, sulfosuccinates, sulfoacetates, acyl glycinates, acyl alaninates, acyl glutamates, lactates, lactylates, glucose carboxylates, amphoacetates, taurates, phosphate esters, and mixtures thereof. In that case, alkyl is defined as a saturated or unsaturated, straight or branched alkyl chain with 7 to 17 carbon atoms, alternatively with 9 to 13 carbon atoms. In that case, acyl is defined as of formula R—C(O)—, wherein R is a saturated or unsaturated, straight or branched alkyl chain with 7 to 17 carbon atoms, alternatively with 9 to 13 carbon atoms.
Suitable isethionate surfactants can include the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Suitable fatty acids for isethionate surfactants can be derived from coconut oil or palm kernel oil including amides of methyl tauride. Non-limiting examples of isethionates can be selected from the group consisting of sodium lauroyl methyl isethionate, sodium cocoyl isethionate, ammonium cocoyl isethionate, sodium hydrogenated cocoyl methyl isethionate, sodium lauroyl isethionate, sodium cocoyl methyl isethionate, sodium myristoyl isethionate, sodium oleoyl isethionate, sodium oleyl methyl isethionate, sodium palm kerneloyl isethionate, sodium stearoyl methyl isethionate, and mixtures thereof.
Non-limiting examples of sarcosinates can be selected from the group consisting of sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium myristoyl sarcosinate, TEA-cocoyl sarcosinate, ammonium cocoyl sarcosinate, ammonium lauroyl sarcosinate, dimer dilinoleyl bis-lauroylglutamate/lauroylsarcosinate, disodium lauroamphodiacetate, lauroyl sarcosinate, isopropyl lauroyl sarcosinate, potassium cocoyl sarcosinate, potassium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium lauroyl sarcosinate, sodium myristoyl sarcosinate, sodium oleoyl sarcosinate, sodium palmitoyl sarcosinate, TEA-cocoyl sarcosinate, TEA-lauroyl sarcosinate, TEA-oleoyl sarcosinate, TEA-palm kernel sarcosinate, and combinations thereof.
Non-limiting examples of sulfosuccinate surfactants can include disodium N-octadecyl sulfosuccinate, disodium lauryl sulfosuccinate, diammonium lauryl sulfosuccinate, sodium lauryl sulfosuccinate, disodium laureth sulfosuccinate, tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinnate, diamyl ester of sodium sulfosuccinic acid, dihexyl ester of sodium sulfosuccinic acid, dioctyl esters of sodium sulfosuccinic acid, and combinations thereof.
Non-limiting examples of sulfoacetates can include sodium lauryl sulfoacetate, ammonium lauryl sulfoacetate and combination thereof.
Non-limiting examples of acyl glycinates can include sodium cocoyl glycinate, sodium lauroyl glycinate and combination thereof.
Non-limiting example of acyl alaninates can include sodium cocoyl alaninate, sodium lauroyl alaninate, sodium N-dodecanoyl-1-alaninate and combinations thereof.
Non-limiting examples of acyl glutamates can be selected from the group consisting of sodium cocoyl glutamate, disodium cocoyl glutamate, ammonium cocoyl glutamate, diammonium cocoyl glutamate, sodium lauroyl glutamate, disodium lauroyl glutamate, sodium cocoyl hydrolyzed wheat protein glutamate, disodium cocoyl hydrolyzed wheat protein glutamate, potassium cocoyl glutamate, dipotassium cocoyl glutamate, potassium lauroyl glutamate, dipotassium lauroyl glutamate, potassium cocoyl hydrolyzed wheat protein glutamate, dipotassium cocoyl hydrolyzed wheat protein glutamate, sodium capryloyl glutamate, disodium capryloyl glutamate, potassium capryloyl glutamate, dipotassium capryloyl glutamate, sodium undecylenoyl glutamate, disodium undecylenoyl glutamate, potassium undecylenoyl glutamate, dipotassium undecylenoyl glutamate, disodium hydrogenated tallow glutamate, sodium stearoyl glutamate, disodium stearoyl glutamate, potassium stearoyl glutamate, dipotassium stearoyl glutamate, sodium myristoyl glutamate, disodium myristoyl glutamate, potassium myristoyl glutamate, dipotassium myristoyl glutamate, sodium cocoyl/hydrogenated tallow glutamate, sodium cocoyl/palmoyl/sunfloweroyl glutamate, sodium hydrogenated tallowoyl glutamate, sodium olivoyl glutamate, disodium olivoyl glutamate, sodium palmoyl glutamate, disodium palmoyl glutamate, TEA-cocoyl glutamate, TEA-hydrogenated tallowoyl glutamate, TEA-lauroyl glutamate, and mixtures thereof.
Non-limiting examples of acyl glycinates can include sodium cocoyl glycinate, sodium lauroyl glycinate and combination thereof.
Non-limiting example of lactates can include sodium lactate.
Non-limiting examples of lactylates can include sodium lauroyl lactylate, sodium cocoyl lactylate and combination thereof.
Non-limiting examples of glucose carboxylates can include sodium lauryl glucoside carboxylate, sodium cocoyl glucoside carboxylate and combinations thereof.
Non-limiting examples of alkylamphoacetates can include sodium cocoyl amphoacetate, sodium lauroyl amphoacetate and combination thereof.
Non-limiting examples of acyl taurates can include sodium methyl cocoyl taurate, sodium methyl lauroyl taurate, sodium methyl oleoyl taurate and combination thereof.
Co-Surfactant
Co-surfactants are materials which are combined with the undecyl sulfate surfactant and optionally anionic surfactants to enhance lather volume and/or to modify lather texture. Typically these materials can be selected from a variety of families of structures including, but not limited to, amphoteric, zwitterionic, cationic, and nonionic. They are typically used with anionic surfactants in a weight ratio of 1:20 to 1:4, and alternatively in the 1:12 to 1:7 weight ratio.
The shampoo composition may comprise from about 0.5 wt % to about 10 wt %, alternatively from about 0.5 wt % to about 5 wt %, alternatively from about 0.5 wt % to about 3 wt %, alternatively from about 0.5 wt % to about 2 wt %, and alternatively from about 0.5 wt % to about 1.75 wt % by weight of the composition of at least one suitable co-surfactant. The co-surfactant may serve to produce faster lather, facilitate easier rinsing, and/or mitigate harshness on the keratinous tissue. The co-surfactant further may aid in producing lather having more desirable texture, volume and/or other properties.
Amphoteric surfactants suitable for use herein include, but are not limited to derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one substituent of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples include sodium 3-dodecyl-aminopropionate, sodium 3-dodecylaminopropane sulfonate, sodium lauryl sarcosinate, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 2,658,072, N-higher alkyl aspartic acids such as those produced according to the teaching of U.S. Pat. No. 2,438,091, and the products described in U.S. Pat. No. 2,528,378, and mixtures thereof. The amphoteric surfactants may selected from the family of betaines such as lauryolamphoacetate.
Zwitterionic surfactants suitable for use herein include, but are not limited to derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one substituent contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Other zwitterionic surfactants suitable for use herein include betaines, including high alkyl betaines such as coco dimethyl carboxymethyl betaine, cocoamidopropyl betaine, cocobetaine, lauryl amidopropyl betaine, oleyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl)alpha-carboxyethyl betaine, and mixtures thereof. The sulfobetaines may include coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine and mixtures thereof. Other suitable amphoteric surfactants include amidobetaines and amidosulfobetaines, wherein the RCONH(CH2)3 radical, wherein R is a C11-C17 alkyl, is attached to the nitrogen atom of the betaine.
Nonionic co-surfactants suitable for use in the composition for enhancing lather volume or texture include water soluble materials like lauryl dimethylamine oxide, cocodimethylamine oxide, cocoamidopropylamine oxide, laurylamidopropyl amine oxide, etc. or alkylpolyethoxylates like laureth-4 to laureth-7 and water insoluble components such as cocomonoethanol amide, cocodiethanol amide, lauroylmonoethanol amide, alkanoyl isopropanol amides, and fatty alcohols like cetyl alcohol and oleyl alcohol, and 2-hydroxyalkyl methyl ethers, etc.
Further suitable materials as co-surfactants herein include 1,2-alkylepoxides, 1,2-alkanediols, branched or straight chain alkyl glyceryl ethers (e.g., as disclosed in EP 1696023A1), 1,2-alkylcyclic carbonates, and 1,2-alkyl cyclicsulfites, particularly those wherein the alkyl group contains 6 to 14 carbon atoms in linear or branched configuration. Other examples include the alkyl ether alcohols derived from reacting C10 or C12 alpha olefins with ethylene glycol (e.g., hydroxyethyl-2-decyl ether, hydroxyethyl-2-dodecyl ether), as can be made according to U.S. Pat. Nos. 5,741,948; 5,994,595; 6,346,509; and 6,417,408.
Other nonionic surfactants may be selected from the group consisting of glucose amides, alkyl polyglucosides, sucrose cocoate, sucrose laurate, alkanolamides, ethoxylated alcohols and mixtures thereof. The nonionic surfactant is selected from the group consisting of glyceryl monohydroxystearate, isosteareth-2, trideceth-3, hydroxystearic acid, propylene glycol stearate, PEG-2 stearate, sorbitan monostearate, glyceryl laurate, laureth-2, cocamide monoethanolamine, lauramide monoethanolamine, and mixtures thereof.
The co-surfactant can be selected from the group consisting of Cocomonoethanol Amide, Cocoamidopropyl Betaine, Laurylamidopropyl Betaine, Cocobetaine, lauryl betaine, lauryl amine oxide, sodium lauryl amphoacetate; alkyl glyceryl ethers, alkyl-di-glyceryl ethers, 1,2-alkyl cyclic sulfites, 1,2-alkyl cyclic carbonates, 1,2-alkyl-epoxides, alkyl glycidylethers, and alkyl-1,3-dioxolanes, wherein the alkyl group contains 6 to 14 carbon atoms in linear or branched configuration; 1,2-alkane diols where the total carbon content is from 6 to 14 carbon atoms linear or branched, methyl-2-hydroxy-decyl ethers, hydroxyethyl-2-dodecyl ether, hydroxyethyl-2-decyl ether, and mixtures thereof.
Cationic surfactants may be derived from amines that are protonated at the pH of the formulation, e.g. bis-hydroxyethyl lauryl amine, lauryl dimethylamine, lauroyl dimethyl amidopropyl amine, cocoylamidopropyl amine, and the like. The cationic surfactants may also be derived from fatty quaternary ammonium salts such as lauryl trimethylammonium chloride and lauroylamidopropyl trimethyl ammonium chloride.
Alkylamphoacetates are suitable surfactants used in the compositions herein for improved product mildness and lather. The most commonly used alkylamphoacetates are lauroamphoacetate and cocoamphoacetate. Alkylamphoacetates can be comprised of monoacetates and diacetates. In some types of alkylamphoacetates, diacetates are impurities or unintended reaction products. However, the presence of diacetate can cause a variety of unfavorable composition characteristics when present in amounts over 15% of the alkylamphoacetates.
Suitable nonionic surfactants for use herein are those selected from the group consisting of glucose amides, alkyl polyglucosides, sucrose cocoate, sucrose laurate, alkanolamides, ethoxylated alcohols and mixtures thereof. In one embodiment the nonionic surfactant is selected from the group consisting of glyceryl monohydroxystearate, isosteareth-2, trideceth-3, hydroxystearic acid, propylene glycol stearate, PEG-2 stearate, sorbitan monostearate, glyceryl laurate, laureth-2, cocamide monoethanolamine, lauramide monoethanolamine, and mixtures thereof.
Non-limiting examples of suitable structurants are described in U.S. Pat. No. 5,952,286, and include unsaturated and/or branched long chain (C8-C24) liquid fatty acids or ester derivative thereof; unsaturated and/or branched long chain liquid alcohol or ether derivatives thereof, and mixtures thereof. The surfactant also may comprise short chain saturated fatty acids such as capric acid and caprylic acid. Without being limited by theory, it is believed that the unsaturated part of the fatty acid of alcohol or the branched part of the fatty acid or alcohol acts to “disorder” the surfactant hydrophobic chains and induce formation of lamellar phase. Examples of suitable liquid fatty acids include oleic acid, isostearic acid, linoleic acid, linolenic acid, ricinoleic acid, elaidic acid, arichidonic acid, myristoleic acid, palmitoleic acid, and mixtures thereof. Examples of suitable ester derivatives include propylene glycol isostearate, propylene glycol oleate, glyceryl isostearate, glyceryl oleate, polyglyceryl diisostearate and mixtures thereof. Examples of alcohols include oleyl alcohol and isostearyl alcohol. Examples of ether derivatives include isosteareth or oleth carboxylic acid; or isosteareth or oleth alcohol. The structuring agent may be defined as having melting point below about 25° C.
If present, the composition may comprise a rheology modifier, wherein said rheology modifier comprises cellulosic rheology modifiers, cross-linked acrylates, cross-linked maleic anhydride co-methylvinylethers, hydrophobically modified associative polymers, or a mixture thereof.
An electrolyte, if used, can be added per se to the composition or it can be formed in situ via the counterions included in one of the raw materials. The electrolyte may include an anion comprising phosphate, chloride, sulfate or citrate and a cation comprising sodium, ammonium, potassium, magnesium or mixtures thereof. The electrolyte may be sodium chloride, ammonium chloride, sodium or ammonium sulfate. The electrolyte may be added to the composition in the amount of from about 0.1 wt % to about 15 wt % by weight, alternatively from about 1 wt % to about 6 wt % by weight, and alternatively from about 3 wt % to about 6 wt %, by weight of the composition.
Cationic Polymer
A shampoo composition can include a cationic polymer to allow formation of a coacervate. As can be appreciated, the cationic charge of a cationic polymer can interact with an anionic charge of a surfactant to form the coacervate. Suitable cationic polymers can include: (a) a cationic guar polymer, (b) a cationic non-guar galactomannan polymer, (c) a cationic starch polymer, (d) a cationic copolymer of acrylamide monomers and cationic monomers, (e) a synthetic, non-crosslinked, cationic polymer, which may or may not form lyotropic liquid crystals upon combination with the detersive surfactant, (f) cationic synthetic homopolymers, (g) a cationic cellulose polymer, and (h) combinations thereof. In certain examples, more than one cationic polymer can be included. The cationic polymer can be selected from guar hydroxypropyltrimonium chloride, Polyquaterium 10, Polyquaternium 6, and combinations thereof.
A cationic polymer can be included by weight of the shampoo composition at about 0.05% to about 3%, about 0.075% to about 2.0%, or at about 0.1% to about 1.0%. Cationic polymers can have cationic charge densities of about 0.9 meq/g or more, about 1.2 meq/g or more, and about 1.5 meq/g or more. However, cationic charge density can also be about 7 meq/g or less and alternatively about 5 meq/g or less. The charge densities can be measured at the pH of intended use of the shampoo composition. (e.g., at about pH 3 to about pH 9; or about pH 4 to about pH 8). The average molecular weight of cationic polymers can generally be between about 10,000 and 10 million, between about 50,000 and about 5 million, and between about 100,000 and about 3 million, and between about 300,000 and about 3 million and between about 100,000 and about 2.5 million. Low molecular weight cationic polymers can be used. Low molecular weight cationic polymers can have greater translucency in the liquid carrier of a shampoo composition. The cationic polymer can be a single type, such as the cationic guar polymer guar hydroxypropyltrimonium chloride having a weight average molecular weight of about 2.5 million g/mol or less, and the shampoo composition can have an additional cationic polymer of the same or different types.
Cationic Guar Polymer
The cationic polymer can be a cationic guar polymer, which is a cationically substituted galactomannan (guar) gum derivative. Suitable guar gums for guar gum derivatives can be obtained as a naturally occurring material from the seeds of the guar plant. As can be appreciated, the guar molecule is a straight chain mannan which is branched at regular intervals with single membered galactose units on alternative mannose units. The mannose units are linked to each other by means of β(1-4) glycosidic linkages. The galactose branching arises by way of an α(1-6) linkage. Cationic derivatives of the guar gums can be obtained through reactions between the hydroxyl groups of the polygalactomannan and reactive quaternary ammonium compounds. The degree of substitution of the cationic groups onto the guar structure can be sufficient to provide the requisite cationic charge density described above.
A cationic guar polymer can have a weight average molecular weight (“M.Wt.”) of less than about 3 million g/mol, and can have a charge density from about 0.05 meq/g to about 2.5 meq/g. Alternatively, the cationic guar polymer can have a weight average M.Wt. of less than 1.5 million g/mol, from about 150 thousand g/mol to about 1.5 million g/mol, from about 200 thousand g/mol to about 1.5 million g/mol, from about 300 thousand g/mol to about 1.5 million g/mol, and from about 700,000 thousand g/mol to about 1.5 million g/mol. The cationic guar polymer can have a charge density from about 0.2 meq/g to about 2.2 meq/g, from about 0.3 meq/g to about 2.0 meq/g, from about 0.4 meq/g to about 1.8 meq/g; and from about 0.5 meq/g to about 1.7 meq/g.
A cationic guar polymer can have a weight average M.Wt. of less than about 1 million g/mol, and can have a charge density from about 0.1 meq/g to about 2.5 meq/g. A cationic guar polymer can have a weight average M.Wt. of less than 900 thousand g/mol, from about 150 thousand to about 800 thousand g/mol, from about 200 thousand g/mol to about 700 thousand g/mol, from about 300 thousand to about 700 thousand g/mol, from about 400 thousand to about 600 thousand g/mol, from about 150 thousand g/mol to about 800 thousand g/mol, from about 200 thousand g/mol to about 700 thousand g/mol, from about 300 thousand g/mol to about 700 thousand g/mol, and from about 400 thousand g/mol to about 600 thousand g/mol. A cationic guar polymer has a charge density from about 0.2 meq/g to about 2.2 meq/g, from about 0.3 meq/g to about 2.0 meq/g, from about 0.4 meq/g to about 1.8 meq/g; and from about 0.5 meq/g to about 1.5 meq/g.
A shampoo composition can include from about 0.01% to less than about 0.7%, by weight of the shampoo composition of a cationic guar polymer, from about 0.04% to about 0.55%, by weight, from about 0.08% to about 0.5%, by weight, from about 0.16% to about 0.5%, by weight, from about 0.2% to about 0.5%, by weight, from about 0.3% to about 0.5%, by weight, and from about 0.4% to about 0.5%, by weight.
The cationic guar polymer can be formed from quaternary ammonium compounds which conform to general Formula II:
wherein where R3, R4 and R5 are methyl or ethyl groups; and R6 is either an epoxyalkyl group of the general Formula III:
or R6 is a halohydrin group of the general Formula IV:
wherein R7 is a C1 to C3 alkylene; X is chlorine or bromine, and Z is an anion such as Cl—, Br—, I— or HSO4—.
Suitable cationic guar polymers can conform to the general formula V:
wherein R8 is guar gum; and wherein R4, R5, R6 and R7 are as defined above; and wherein Z is a halogen. Suitable cationic guar polymers can conform to Formula VI:
wherein R8 is guar gum.
Suitable cationic guar polymers can also include cationic guar gum derivatives, such as guar hydroxypropyltrimonium chloride. Suitable examples of guar hydroxypropyltrimonium chlorides can include the Jaguar® series commercially available from Solvay S.A., Hi-Care Series from Rhodia, and N-Hance and AquaCat from Ashland Inc. Jaguar® C-500 has a charge density of 0.8 meq/g and a M.Wt. of 500,000 g/mole; Jaguar Optima has a cationic charge density of about 1.25 meg/g and a M.Wt. of about 500,000 g/moles; Jaguar® C-17 has a cationic charge density of about 0.6 meq/g and a M.Wt. of about 2.2 million g/mol; Jaguar® and a cationic charge density of about 0.8 meq/g; Hi-Care 1000 has a charge density of about 0.7 meq/g and a M.Wt. of about 600,000 g/mole; N-Hance 3269 and N-Hance 3270, have a charge density of about 0.7 meq/g and a M.Wt. of about 425,000 g/mole; N-Hance 3196 has a charge density of about 0.8 meq/g and a M.Wt. of about 1,100,000 g/mole; and AquaCat CG518 has a charge density of about 0.9 meq/g and a M.Wt. of about 50,000 g/mole. N-Hance BF-13 and N-Hance BF-17 are borate (boron) free guar polymers. N-Hance BF-13 has a charge density of about 1.1 meq/g and M.W.t of about 800,000 and N-Hance BF-17 has a charge density of about 1.7 meq/g and M.W.t of about 800,000. BF-17 has a charge density of about 1.7 meq/g and M.W.t of about 800,000. BF-17 has a charge density of about 1.7 meq/g and M.W.t of about 800,000. BF-17 has a charge density of about 1.7 meq/g and M.W.t of about 800,000. BF-17 has a charge density of about 1.7 meq/g and M.W.t of about 800,000.
Cationic Non-Guar Galactomannan Polymer
The cationic polymer can be a galactomannan polymer derivative. Suitable galactomannan polymer can have a mannose to galactose ratio of greater than 2:1 on a monomer to monomer basis and can be a cationic galactomannan polymer derivative or an amphoteric galactomannan polymer derivative having a net positive charge. As used herein, the term “cationic galactomannan” refers to a galactomannan polymer to which a cationic group is added. The term “amphoteric galactomannan” refers to a galactomannan polymer to which a cationic group and an anionic group are added such that the polymer has a net positive charge.
Galactomannan polymers can be present in the endosperm of seeds of the Leguminosae family. Galactomannan polymers are made up of a combination of mannose monomers and galactose monomers. The galactomannan molecule is a straight chain mannan branched at regular intervals with single membered galactose units on specific mannose units. The mannose units are linked to each other by means of β (1-4) glycosidic linkages. The galactose branching arises by way of an α (1-6) linkage. The ratio of mannose monomers to galactose monomers varies according to the species of the plant and can be affected by climate. Non Guar Galactomannan polymer derivatives can have a ratio of mannose to galactose of greater than 2:1 on a monomer to monomer basis. Suitable ratios of mannose to galactose can also be greater than 3:1 or greater than 4:1. Analysis of mannose to galactose ratios is well known in the art and is typically based on the measurement of the galactose content.
The gum for use in preparing the non-guar galactomannan polymer derivatives can be obtained from naturally occurring materials such as seeds or beans from plants. Examples of various non-guar galactomannan polymers include 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).
A non-guar galactomannan polymer derivative can have a M. Wt. from about 1,000 g/mol to about 10,000,000 g/mol, and a M.Wt. from about 5,000 g/mol to about 3,000,000 g/mol.
The shampoo compositions described herein can include galactomannan polymer derivatives which have a cationic charge density from about 0.5 meq/g to about 7 meq/g. The galactomannan polymer derivatives can have a cationic charge density from about 1 meq/g to about 5 meq/g. The degree of substitution of the cationic groups onto the galactomannan structure can be sufficient to provide the requisite cationic charge density.
A galactomannan polymer derivative can be a cationic derivative of the non-guar galactomannan polymer, which is obtained by reaction between the hydroxyl groups of the polygalactomannan polymer and reactive quaternary ammonium compounds. Suitable quaternary ammonium compounds for use in forming the cationic galactomannan polymer derivatives include those conforming to the general Formulas II to VI, as defined above.
Cationic non-guar galactomannan polymer derivatives formed from the reagents described above can be represented by the general Formula VII:
wherein R is the gum. The cationic galactomannan derivative can be a gum hydroxypropyltrimethylammonium chloride, which can be more specifically represented by the general Formula VIII:
The galactomannan polymer derivative can be an amphoteric galactomannan polymer derivative having a net positive charge, obtained when the cationic galactomannan polymer derivative further comprises an anionic group.
A cationic non-guar galactomannan can have a ratio of mannose to galactose which is greater than about 4:1, a M.Wt. of about 100,000 g/mol to about 500,000 g/mol, a M.Wt. of about 50,000 g/mol to about 400,000 g/mol, and a cationic charge density from about 1 meq/g to about 5 meq/g, and from about 2 meq/g to about 4 meq/g.
Shampoo compositions can include at least about 0.05% of a galactomannan polymer derivative by weight of the composition. The shampoo compositions can include from about 0.05% to about 2%, by weight of the composition, of a galactomannan polymer derivative.
Cationic Starch Polymers
Suitable cationic polymers can also be water-soluble cationically modified starch polymers. As used herein, the term “cationically modified starch” refers to a starch to which a cationic group is added prior to degradation of the starch to a smaller molecular weight, or wherein a cationic group is added after modification of the starch 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 a starch hydrolysate to which a cationic group and an anionic group are added.
The shampoo compositions described herein can include cationically modified starch polymers at a range of about 0.01% to about 10%, and/or from about 0.05% to about 5%, by weight of the composition.
The cationically modified starch polymers disclosed herein have a percent of bound nitrogen of from about 0.5% to about 4%.
The cationically modified starch polymers can have a molecular weight from about 850,000 g/mol to about 15,000,000 g/mol and from about 900,000 g/mol to about 5,000,000 g/mol.
Cationically modified starch polymers can have a charge density of from about 0.2 meq/g to about 5 meq/g, and from about 0.2 meq/g to about 2 meq/g. The chemical modification to obtain such a charge density can include the addition of amino and/or ammonium groups into the starch molecules. Non-limiting examples of such ammonium groups can include substituents such as hydroxypropyl trimmonium chloride, trimethylhydroxypropyl ammonium chloride, dimethylstearylhydroxypropyl ammonium chloride, and dimethyldodecylhydroxypropyl ammonium chloride. Further details are described in Solarek, D. B., Cationic Starches in Modified Starches: Properties and Uses, Wurzburg, O. B., Ed., CRC Press, Inc., Boca Raton, Fla. 1986, pp 113-125 which is hereby incorporated by reference. The cationic groups can be added to the starch prior to degradation to a smaller molecular weight or the cationic groups may be added after such modification.
A cationically modified starch polymer can have a degree of substitution of a cationic group from about 0.2 to about 2.5. As used herein, the “degree of substitution” of the cationically modified starch polymers is an average measure of the number of hydroxyl groups on each anhydroglucose unit which is derivatized by substituent groups. Since each anhydroglucose unit has three potential hydroxyl groups available for substitution, the maximum possible degree of substitution is 3. The degree of substitution is expressed as the number of moles of substituent groups per mole of anhydroglucose unit, on a molar average basis. The degree of substitution can be determined using proton nuclear magnetic resonance spectroscopy (“1H NMR”) methods well known in the art. Suitable 1H NMR techniques include those described in “Observation on NMR Spectra of Starches in Dimethyl Sulfoxide, Iodine-Complexing, and Solvating in Water-Dimethyl Sulfoxide”, Qin-Ji Peng and Arthur S. Perlin, Carbohydrate Research, 160 (1987), 57-72; and “An Approach to the Structural Analysis of Oligosaccharides by NMR Spectroscopy”, J. Howard Bradbury and J. Grant Collins, Carbohydrate Research, 71, (1979), 15-25.
The source of starch before chemical modification can be selected from a variety of sources such as tubers, legumes, cereal, and grains. For example, starch sources can include corn starch, wheat starch, rice starch, waxy corn starch, oat starch, cassaya starch, waxy barley, waxy rice starch, glutenous rice starch, sweet rice starch, amioca, potato starch, tapioca starch, oat starch, sago starch, sweet rice, or mixtures thereof. Suitable cationically modified starch polymers can be selected from degraded cationic maize starch, cationic tapioca, cationic potato starch, and mixtures thereof. Cationically modified starch polymers are cationic corn starch and cationic tapioca.
The starch, prior to degradation or after modification to a smaller molecular weight, can include one or more additional modifications. For example, these modifications may include cross-linking, stabilization reactions, phosphorylations, and hydrolyzations. Stabilization reactions can include alkylation and esterification.
Cationically modified starch polymers can be included in a shampoo composition in the form of hydrolyzed starch (e.g., acid, enzyme, or alkaline degradation), oxidized starch (e.g., peroxide, peracid, hypochlorite, alkaline, or any other oxidizing agent), physically/mechanically degraded starch (e.g., via the thermo-mechanical energy input of the processing equipment), or combinations thereof.
The starch can be readily soluble in water and can form a substantially translucent solution in water. The transparency of the composition is measured by Ultra-Violet/Visible (“UV/VIS”) spectrophotometry, which determines the absorption or transmission of UV/VIS light by a sample, using a Gretag Macbeth Colorimeter Color. A light wavelength of 600 nm has been shown to be adequate for characterizing the degree of clarity of shampoo compositions.
Cationic Copolymer of an Acrylamide Monomer and a Cationic Monomer
A shampoo composition can include a cationic copolymer of an acrylamide monomer and a cationic monomer, wherein the copolymer has a charge density of from about 1.0 meq/g to about 3.0 meq/g. The cationic copolymer can be a synthetic cationic copolymer of acrylamide monomers and cationic monomers.
Suitable cationic polymers can include:
(i) an acrylamide monomer of the following Formula IX:
where R9 is H or C1-4 alkyl; and R10 and R11 are independently selected from the group consisting of H, C1-4 alkyl, CH2OCH3, CH2OCH2CH(CH3)2, and phenyl, or together are C3-6 cycloalkyl; and
(ii) a cationic monomer conforming to Formula X:
where k=1, each of v, v′, and v″ is independently an integer of from 1 to 6, w is zero or an integer of from 1 to 10, and X− is an anion.
A cationic monomer can conform to Formula X where k=1, v=3 and w=0, z=1 and X− is Cl− to form the following structure (Formula XI):
As can be appreciated, the above structure can be referred to as diquat.
A cationic monomer can conform to Formula X wherein v and v″ are each 3, v′=1, w=1, y=1 and X− is Cl−, to form the following structure of Formula XII:
The structure of Formula XII can be referred to as triquat.
The acrylamide monomer can be either acrylamide or methacrylamide.
The cationic copolymer can be AM:TRIQUAT which is a copolymer of acrylamide and 1,3-Propanediaminium,N-[2-[[[dimethyl[3-[(2-methyl-1-oxo-2-propenyl) amino]propyl]ammonio]acetyl]amino]ethyl]2-hydroxy-N,N,N′,N′,N′-pentamethyl-, trichloride. AM:TRIQUAT is also known as polyquaternium 76 (PQ76). AM:TRIQUAT can have a charge density of 1.6 meq/g and a M.Wt. of 1.1 million g/mol.
The cationic copolymer can include 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; ethylenimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine; trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methyl sulphate, dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethyl ammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl (meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride, diallyldimethyl ammonium chloride, and mixtures thereof.
The cationic copolymer can include a cationic monomer selected from the group consisting of: trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methyl sulphate, dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethyl ammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl (meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride, and mixtures thereof.
The cationic copolymer can be formed from (1) copolymers of (meth)acrylamide and cationic monomers based on (meth)acrylamide, and/or hydrolysis-stable cationic monomers, (2) terpolymers of (meth)acrylamide, monomers based on cationic (meth)acrylic acid esters, and monomers based on (meth)acrylamide, and/or hydrolysis-stable cationic monomers. Monomers based on cationic (meth)acrylic acid esters can be cationized esters of the (meth)acrylic acid containing a quaternized N atom. Cationized esters of the (meth)acrylic acid containing a quaternized N atom can be quaternized dialkylaminoalkyl (meth)acrylates with C1 to C3 in the alkyl and alkylene groups. The cationized esters of the (meth)acrylic acid containing a quaternized N 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 quaternized with methyl chloride. The cationized esters of the (meth)acrylic acid containing a quaternized N atom can be dimethylaminoethyl acrylate, which is quaternized with an alkyl halide, or with methyl chloride or benzyl chloride or dimethyl sulfate (ADAME-Quat). The cationic monomer when based on (meth)acrylamides are quaternized dialkylaminoalkyl(meth)acrylamides with C1 to C3 in the alkyl and alkylene groups, or dimethylaminopropylacrylamide, which is quaternized with an alkyl halide, or methyl chloride or benzyl chloride or dimethyl sulfate.
The cationic monomer based on a (meth)acrylamide can be a quaternized dialkylaminoalkyl(meth)acrylamide with C1 to C3 in the alkyl and alkylene groups. The cationic monomer based on a (meth)acrylamide can be dimethylaminopropylacrylamide, which is quaternized with an alkyl halide, especially methyl chloride or benzyl chloride or dimethyl sulfate.
The cationic monomer can be a hydrolysis-stable cationic monomer. Hydrolysis-stable cationic monomers can be, in addition to a dialkylaminoalkyl(meth)acrylamide, any monomer that can be regarded as stable to the OECD hydrolysis test. The cationic monomer can be hydrolysis-stable and the hydrolysis-stable cationic monomer can be selected from the group consisting of: diallyldimethylammonium chloride and water-soluble, cationic styrene derivatives.
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, wherein the acrylamidopropyltrimethylammonium chloride has a charge density of from about 1.0 meq/g to about 3.0 meq/g.
The cationic copolymer can have a charge density of from about 1.1 meq/g to about 2.5 meq/g, from about 1.1 meq/g to about 2.3 meq/g, from about 1.2 meq/g to about 2.2 meq/g, from about 1.2 meq/g to about 2.1 meq/g, from about 1.3 meq/g to about 2.0 meq/g, and from about 1.3 meq/g to about 1.9 meq/g.
The cationic copolymer can have a M.Wt. from about 100 thousand g/mol to about 2 million g/mol, from about 300 thousand g/mol to about 1.8 million g/mol, from about 500 thousand g/mol to about 1.6 million g/mol, from about 700 thousand g/mol to about 1.4 million g/mol, and from about 900 thousand g/mol to about 1.2 million g/mol.
The cationic copolymer can be a trimethylammoniopropylmethacrylamide chloride-N-Acrylamide copolymer, which is also known as AM:MAPTAC. AM:MAPTAC can have a charge density of about 1.3 meq/g and a M.Wt. of about 1.1 million g/mol. The cationic copolymer can be AM:ATPAC. AM:ATPAC can have a charge density of about 1.8 meq/g and a M.Wt. of about 1.1 million g/mol.
Synthetic Polymers
A cationic polymer can be a synthetic polymer that is formed from:
The cationic polymers can be water soluble or dispersible, non-crosslinked, and synthetic cationic polymers which have the structure of Formula XIII:
where A, may be one or more of the following cationic moieties:
where @=amido, alkylamido, ester, ether, alkyl or alkylaryl;
where Y=C1-C22 alkyl, alkoxy, alkylidene, alkyl or aryloxy;
where Ψ=C1-C22 alkyl, alkyloxy, alkyl aryl or alkyl arylox;.
where Z=C1-C22 alkyl, alkyloxy, aryl or aryloxy;
where R1=H, C1-C4 linear or branched alkyl;
where s=0 or 1, n=0 or ≥1;
where T and R7=C1-C22 alkyl; and
where X−=halogen, hydroxide, alkoxide, sulfate or alkylsulfate.
Where the monomer bearing a negative charge is defined by R2′=H, C1-C4 linear or branched alkyl and R3 is:
where D=O, N, or S;
where Q=NH2 or O;
where u=1-6;
where t=0-1; and
where J=oxygenated functional group containing the following elements P, S, C.
Where the nonionic monomer is defined by R2″=H, C1-C4 linear or branched alkyl, R6=linear or branched alkyl, alkyl aryl, aryl oxy, alkyloxy, alkylaryl oxy and β is defined as
and
where G′ and G″ are, independently of one another, O, S or N—H and L=0 or 1.
Suitable monomers can include aminoalkyl (meth)acrylates, (meth)aminoalkyl (meth)acrylamides; monomers comprising at least one secondary, tertiary or quaternary amine function, or a heterocyclic group containing a nitrogen atom, vinylamine or ethylenimine; diallyldialkyl ammonium salts; their mixtures, their salts, and macromonomers deriving from therefrom.
Further examples of suitable cationic monomers can include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ditertiobutylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, ethylenimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine, trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methyl sulphate, dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethyl ammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl (meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride, diallyldimethyl ammonium chloride.
Suitable cationic monomers can include quaternary monomers of formula —NR3+, wherein each R can be identical or different, and can be a hydrogen atom, an alkyl group comprising 1 to 10 carbon atoms, or a benzyl group, optionally carrying a hydroxyl group, and including an anion (counter-ion). Examples of suitable anions include halides such as chlorides, bromides, sulphates, hydrosulphates, alkylsulphates (for example comprising 1 to 6 carbon atoms), phosphates, citrates, formates, and acetates.
Suitable cationic monomers can also include trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methyl sulphate, dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethyl ammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl (meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride. Additional suitable cationic monomers can include trimethyl ammonium propyl (meth)acrylamido chloride.
Examples of monomers bearing a negative charge include alpha ethylenically unsaturated monomers including a phosphate or phosphonate group, alpha ethylenically unsaturated monocarboxylic acids, monoalkylesters of alpha ethylenically unsaturated dicarboxylic acids, monoalkylamides of alpha ethylenically unsaturated dicarboxylic acids, alpha ethylenically unsaturated compounds comprising a sulphonic acid group, and salts of alpha ethylenically unsaturated compounds comprising a sulphonic acid group.
Suitable monomers with a negative charge can include acrylic acid, methacrylic acid, vinyl sulphonic acid, salts of vinyl sulfonic acid, vinylbenzene sulphonic acid, salts of vinylbenzene sulphonic acid, alpha-acrylamidomethylpropanesulphonic acid, salts of alpha-acrylamidomethylpropanesulphonic acid, 2-sulphoethyl methacrylate, salts of 2-sulphoethyl methacrylate, acrylamido-2-methylpropanesulphonic acid (AMPS), salts of acrylamido-2-methylpropanesulphonic acid, and styrenesulphonate (SS).
Examples of nonionic monomers can include vinyl acetate, amides of alpha ethylenically unsaturated carboxylic acids, esters of an alpha ethylenically unsaturated monocarboxylic acids with an hydrogenated or fluorinated alcohol, polyethylene oxide (meth)acrylate (i.e. polyethoxylated (meth)acrylic acid), monoalkylesters of alpha ethylenically unsaturated dicarboxylic acids, monoalkylamides of alpha ethylenically unsaturated dicarboxylic acids, vinyl nitriles, vinylamine amides, vinyl alcohol, vinyl pyrolidone, and vinyl aromatic compounds.
Suitable nonionic monomers can also include styrene, acrylamide, methacrylamide, acrylonitrile, methylacrylate, ethylacrylate, n-propylacrylate, n-butylacrylate, methylmethacrylate, ethylmethacrylate, n-propylmethacrylate, n-butylmethacrylate, 2-ethyl-hexyl acrylate, 2-ethyl-hexyl methacrylate, 2-hydroxyethylacrylate and 2-hydroxyethylmethacrylate.
The anionic counterion (X−) in association with the synthetic cationic polymers can be any known counterion so long as the polymers remain soluble or dispersible in water, in the shampoo composition, or in a coacervate phase of the shampoo composition, and so long as the counterions are physically and chemically compatible with the essential components of the shampoo composition or do not otherwise unduly impair product performance, stability or aesthetics. Non limiting examples of suitable counterions can include halides (e.g., chlorine, fluorine, bromine, iodine), sulfate, and methylsulfate.
The cationic polymer described herein can also aid in repairing damaged hair, particularly chemically treated hair by providing a surrogate hydrophobic F-layer. The microscopically thin F-layer provides natural weatherproofing, while helping to seal in moisture and prevent further damage. Chemical treatments damage the hair cuticle and strip away its protective F-layer. As the F-layer is stripped away, the hair becomes increasingly hydrophilic. It has been found that when lyotropic liquid crystals are applied to chemically treated hair, the hair becomes more hydrophobic and more virgin-like, in both look and feel. Without being limited to any theory, it is believed that the lyotropic liquid crystal complex creates a hydrophobic layer or film, which coats the hair fibers and protects the hair, much like the natural F-layer protects the hair. The hydrophobic layer can return the hair to a generally virgin-like, healthier state. Lyotropic liquid crystals are formed by combining the synthetic cationic polymers described herein with the aforementioned anionic detersive surfactant component of the shampoo composition. The synthetic cationic polymer has a relatively high charge density. It should be noted that some synthetic polymers having a relatively high cationic charge density do not form lyotropic liquid crystals, primarily due to their abnormal linear charge densities. Such synthetic cationic polymers are described in PCT Patent App. No. WO 94/06403 which is incorporated by reference. The synthetic polymers described herein can be formulated in a stable shampoo composition that provides improved conditioning performance, with respect to damaged hair.
Cationic synthetic polymers that can form lyotropic liquid crystals have a cationic charge density of from about 2 meq/gm to about 7 meq/gm, and/or from about 3 meq/gm to about 7 meq/gm, and/or from about 4 meq/gm to about 7 meq/gm. The cationic charge density is about 6.2 meq/gm. The polymers also have a M. Wt. of from about 1,000 to about 5,000,000, and/or from about 10,000 to about 2,000,000, and/or from about 100,000 to about 2,000,000.
Cationic synthetic polymers that provide enhanced conditioning and deposition of benefit agents but do not necessarily form lyotropic liquid crystals can have a cationic charge density of from about 0.7 meq/gm to about 7 meq/gm, and/or from about 0.8 meq/gm to about 5 meq/gm, and/or from about 1.0 meq/gm to about 3 meq/gm. The polymers also have a M.Wt. of from about 1,000 g/mol to about 5,000,000 g/mol, from about 10,000 g/mol to about 2,000,000 g/mol, and from about 100,000 g/mol to about 2,000,000 g/mol.
Cationic Cellulose Polymer
Suitable cationic polymers can be cellulose polymers. Suitable cellulose polymers can include salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 10 and available from Dwo/Amerchol Corp. (Edison, N.J., USA) in their Polymer LR, JR, and KG series of polymers. Other suitable types of cationic cellulose can include the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from Dow/Amerchol Corp. under the tradename Polymer LM-200. Other suitable types of cationic cellulose can include the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide and trimethyl ammonium substituted epoxide referred to in the industry (CTFA) as Polyquaternium 67. These materials are available from Dow/Amerchol Corp. under the tradename 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.
Additional cationic polymers are also described in the CTFA Cosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Crosley, and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C. (1982)), which is incorporated herein by reference.
Techniques for analysis of formation of complex coacervates are known in the art. For example, microscopic analyses of the compositions, at any chosen stage of dilution, can be utilized to identify whether a coacervate phase has formed. Such coacervate phase can be identifiable as an additional emulsified phase in the composition. The use of dyes can aid in distinguishing the coacervate phase from other insoluble phases dispersed in the composition. Additional details about the use of cationic polymers and coacervates are disclosed in U.S. Pat. No. 9,272,164 which is incorporated by reference.
C. Liquid Carrier
As can be appreciated, shampoo compositions can desirably be in the form of pourable liquid under ambient conditions. Inclusion of an appropriate quantity of a liquid carrier can facilitate the formation of a shampoo composition having an appropriate viscosity and rheology. A shampoo composition can include, by weight of the composition, about 20% to about 95%, by weight, of a liquid carrier, and about 60% to about 85%, by weight, of a liquid carrier. The liquid carrier can be an aqueous carrier such as water.
D. Optional Components
As can be appreciated, shampoo compositions described herein can include a variety of optional components to tailor the properties and characteristics of the composition. As can be appreciated, suitable optional components are well known and can generally include any components which are physically and chemically compatible with the essential components of the shampoo compositions described herein. Optional components should not otherwise unduly impair product stability, aesthetics, or performance. Individual concentrations of optional components can generally range from about 0.001% to about 10%, by weight of a shampoo composition. Optional components can be further limited to components which will not impair the clarity of a translucent shampoo composition.
Suitable optional components which can be included in a shampoo composition can include co-surfactants, deposition aids, conditioning agents (including hydrocarbon oils, fatty esters, silicones), anti-dandruff agents, suspending agents, viscosity modifiers, dyes, nonvolatile solvents or diluents (water soluble and insoluble), pearlescent aids, foam boosters, pediculocides, pH adjusting agents, perfumes, preservatives, chelants, proteins, skin active agents, sunscreens, UV absorbers, and vitamins The CTFA Cosmetic Ingredient Handbook, Tenth Edition (published by the Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C.) (2004) (hereinafter “CTFA”), describes a wide variety of non-limiting materials that can be added to the composition herein.
Conditioning Agents
A shampoo composition can include a silicone conditioning agent. Suitable silicone conditioning agents can include volatile silicone, non-volatile silicone, or combinations thereof. If including a silicone conditioning agent, the agent can be included from about 0.01% to about 10%, by weight of the composition, from about 0.1% to about 8%, from about 0.1% to about 5%, and/or from about 0.2% to about 3%. Examples of suitable silicone conditioning agents, and optional suspending agents for the silicone, are described in U.S. Reissue Pat. No. 34,584, U.S. Pat. Nos. 5,104,646, and 5,106,609, each of which is incorporated by reference herein. Suitable silicone conditioning agents can have a viscosity, as measured at 25° C., from about 20 centistokes (“csk”) to about 2,000,000 csk, from about 1,000 csk to about 1,800,000 csk, from about 50,000 csk to about 1,500,000 csk, and from about 100,000 csk to about 1,500,000 csk.
The dispersed silicone conditioning agent particles can have a volume average particle diameter ranging from about 0.01 micrometer to about 50 micrometer. For small particle application to hair, the volume average particle diameters can range from about 0.01 micrometer to about 4 micrometer, from about 0.01 micrometer to about 2 micrometer, from about 0.01 micrometer to about 0.5 micrometer. For larger particle application to hair, the volume average particle diameters typically range from about 5 micrometer to about 125 micrometer, from about 10 micrometer to about 90 micrometer, from about 15 micrometer to about 70 micrometer, and/or from about 20 micrometer to about 50 micrometer.
Additional material on silicones including sections discussing silicone fluids, gums, and resins, as well as manufacture of silicones, are 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.
Silicone emulsions suitable for the shampoo compositions described herein can include emulsions of insoluble polysiloxanes prepared in accordance with the descriptions provided in U.S. Pat. No. 4,476,282 and U.S. Patent Application Publication No. 2007/0276087 each of which is incorporated herein by reference. Suitable insoluble polysiloxanes include polysiloxanes such as alpha, omega hydroxy-terminated polysiloxanes or alpha, omega alkoxy-terminated polysiloxanes having a molecular weight within the range from about 50,000 to about 500,000 g/mol. The insoluble polysiloxane can have an average molecular weight within the range from about 50,000 to about 500,000 g/mol. For example, the insoluble polysiloxane may have an average molecular weight within the range from about 60,000 to about 400,000; from about 75,000 to about 300,000; from about 100,000 to about 200,000; or the average molecular weight may be about 150,000 g/mol. The insoluble polysiloxane can have an average particle size within the range from about 30 nm to about 10 micron. The average particle size may be within the range from about 40 nm to about 5 micron, from about 50 nm to about 1 micron, from about 75 nm to about 500 nm, or about 100 nm, for example.
Other classes of silicones suitable for the shampoo compositions described herein can include i) silicone fluids, including silicone oils, which are flowable materials having viscosity less than about 1,000,000 csk as 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 gums; which include materials having viscosity greater or equal to 1,000,000 csk as measured at 25° C.; v) silicone resins, which include highly cross-linked polymeric siloxane systems; vi) high refractive index silicones, having refractive index of at least 1.46, and vii) mixtures thereof.
Alternatively, the shampoo composition can be substantially free of silicones. As used herein, substantially free of silicones means from about 0 to about 0.2 wt. %.
Organic Conditioning Materials
The conditioning agent of the shampoo compositions described herein can also include at least one organic conditioning material such as oil or wax, either alone or in combination with other conditioning agents, such as the silicones described above. The organic material can be non-polymeric, oligomeric or polymeric. The organic material can be in the form of an oil or wax and can be added in the shampoo formulation neat or in a pre-emulsified form. Suitable examples of organic conditioning materials can 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; viii) polyethylene glycols and polypropylene glycols having a molecular weight of up to about 2,000,000 including those with CTFA names PEG-200, PEG-400, PEG-600, PEG-1000, PEG-2M, PEG-7M, PEG-14M, PEG-45M and mixtures thereof.
Emulsifiers
A variety of anionic and nonionic emulsifiers can be used in the shampoo composition. The anionic and nonionic emulsifiers can be either monomeric or polymeric in nature. Monomeric examples include, by way of illustrating and not limitation, alkyl ethoxylates, alkyl sulfates, soaps, and fatty esters and their derivatives. Polymeric examples include, by way of illustrating and not limitation, polyacrylates, polyethylene glycols, and block copolymers and their derivatives. Naturally occurring emulsifiers such as lanolins, lecithin and lignin and their derivatives are also non-limiting examples of useful emulsifiers.
Chelating Agents
The shampoo composition can also comprise a chelant. Suitable chelants include those listed in A E Martell & R M Smith, Critical Stability Constants, Vol. 1, Plenum Press, New York & London (1974) and A E Martell & R D Hancock, Metal Complexes in Aqueous Solution, Plenum Press, New York & London (1996) both incorporated herein by reference. When related to chelants, the term “salts and derivatives thereof” means the salts and derivatives comprising the same functional structure (e.g., same chemical backbone) as the chelant they are referring to and that have similar or better chelating properties. This term include alkali metal, alkaline earth, ammonium, substituted ammonium (i.e. monoethanolammonium, diethanolammonium, triethanolammonium) salts, esters of chelants having an acidic moiety and mixtures thereof, in particular all sodium, potassium or ammonium salts. The term “derivatives” also includes “chelating surfactant” compounds, such as those exemplified in U.S. Pat. No. 5,284,972, and large molecules comprising one or more chelating groups having the same functional structure as the parent chelants, such as polymeric EDDS (ethylenediaminedisuccinic acid) disclosed in U.S. Pat. No. 5,747,440. U.S. Pat. Nos. 5,284,972 and 5,747,440 are each incorporated by reference herein. Suitable chelants can further include histidine.
Levels of an EDDS chelant or histidine chelant in the shampoo compositions can be low. For example, an EDDS chelant or histidine chelant can be included at about 0.01%, by weight. Above about 10% by weight, formulation and/or human safety concerns can arise. The level of an EDDS chelant or histidine chelant can be at least about 0.01%, by weight, at least about 0.05%, by weight, at least about 0.1%, by weight, at least about 0.25%, by weight, at least about 0.5%, by weight, at least about 1%, by weight, or at least about 2%, by weight, by weight of the shampoo composition.
Gel Network
A shampoo composition can also include a fatty alcohol gel network. Gel networks are formed by combining fatty alcohols and surfactants in the ratio of from about 1:1 to about 40:1, from about 2:1 to about 20:1, and/or from about 3:1 to about 10:1. The formation of a gel network involves heating a dispersion of the fatty alcohol in water with the surfactant to a temperature above the melting point of the fatty alcohol. During the mixing process, the fatty alcohol melts, allowing the surfactant to partition into the fatty alcohol droplets. The surfactant brings water along with it into the fatty alcohol. This changes the isotropic fatty alcohol drops into liquid crystalline phase drops. When the mixture is cooled below the chain melt temperature, the liquid crystal phase is converted into a solid crystalline gel network. Gel networks can provide a number of benefits to shampoo compositions. For example, a gel network can provide a stabilizing benefit to cosmetic creams and hair conditioners. In addition, gel networks can provide conditioned feel benefits to hair conditioners and shampoos.
A fatty alcohol can be included in the gel network at a level by weight of from about 0.05%, by weight, to about 14%, by weight. For example, the fatty alcohol can be included in an amount ranging from about 1%, by weight, to about 10%, by weight, and/or from about 6%, by weight, to about 8%, by weight.
Suitable fatty alcohols include those having from about 10 to about 40 carbon atoms, from about 12 to about 22 carbon atoms, from about 16 to about 22 carbon atoms, and/or about 16 to about 18 carbon atoms. These fatty alcohols can be straight or branched chain alcohols and can be saturated or unsaturated. Nonlimiting examples of fatty alcohols include cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof. Mixtures of cetyl and stearyl alcohol in a ratio of from about 20:80 to about 80:20 are suitable.
A gel network can be prepared by charging a vessel with water. The water can then be heated to about 74° C. Cetyl alcohol, stearyl alcohol, and surfactant can then be added to the heated water. After incorporation, the resulting mixture can passed through a heat exchanger where the mixture is cooled to about 35° C. Upon cooling, the fatty alcohols and surfactant crystallized can form crystalline gel network. Table 1 provides the components and their respective amounts for an example gel network composition.
To prepare the gel network pre-mix of Table 1, water is heated to about 74° C. and the fatty alcohol and gel network surfactant are added to it in the quantities depicted in Table 1. After incorporation, this mixture is passed through a mill and heat exchanger where it is cooled to about 32° C. As a result of this cooling step, the fatty alcohol, the gel network surfactant, and the water form a crystalline gel network.
Table 1 includes Examples of a gel network premix, prior to incorporation with the detersive surfactant and other components of the final shampoo composition. It is intended that each of the following gel network premix examples could be incorporated as a dispersed phase into a shampoo composition. A broader selection of suitable gel network premixes may be found in U.S. Pat. No. 8,361,448B2.
(1) available from Sigma Aldrich
(2) available from Clariant Int. Ltd.
1For anionic gel networks, suitable gel network surfactants above include surfactants with a net negative charge including sulfonates, carboxylates and phosphates among others and mixtures thereof.
For cationic gel networks, suitable gel network surfactants above include surfactants with a net positive charge including quaternary ammonium surfactants and mixtures thereof.
For Amphoteric or Zwitterionic gel networks, suitable gel network surfactants above include surfactants with both a positive and negative charge at product usage pH including betaines, amine oxides, sultaines, amino acids among others and mixtures thereof.
Benefit Agents
A shampoo composition can further include one or more benefit agents. Exemplary benefit agents include, but are not limited to, particles, colorants, perfume microcapsules, gel networks, and other insoluble skin or hair conditioning agents such as skin silicones, natural oils such as sun flower oil or castor oil. The benefit agent can be selected from the group consisting of: particles; colorants; perfume microcapsules; gel networks; other insoluble skin or hair conditioning agents such as skin silicones, natural oils such as sun flower oil or castor oil; and mixtures thereof.
Suspending Agent
A shampoo composition can include a suspending agent at concentrations effective for suspending water-insoluble material in dispersed form in the compositions or for modifying the viscosity of the composition. Such concentrations range from about 0.05% to about 10%, and from about 0.3% to about 5.0%, by weight of the compositions. As can be appreciated however, suspending agents may not be necessary when certain glyceride ester crystals are included as certain glyceride ester crystals can act as suitable suspending or structuring agents.
Suitable suspending agents can include anionic polymers and nonionic polymers. Useful herein are vinyl polymers such as cross linked acrylic acid polymers with the CTFA name Carbomer, cellulose derivatives and modified cellulose polymers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, nitro cellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, arabia gum, tragacanth, galactan, carob gum, guar gum, karaya gum, carragheenin, pectin, agar, quince seed (Cydonia oblonga Mill), starch (rice, corn, potato, wheat), algae colloids (algae extract), microbiological polymers such as dextran, succinoglucan, pulleran, starch-based polymers such as carboxymethyl starch, methylhydroxypropyl starch, alginic acid-based polymers such as sodium alginate, alginic acid propylene glycol esters, acrylate polymers such as sodium polyacrylate, polyethylacrylate, polyacrylamide, polyethyleneimine, and inorganic water soluble material such as bentonite, aluminum magnesium silicate, laponite, hectonite, and anhydrous silicic acid.
Other suitable suspending agents can include crystalline suspending agents which can be categorized as acyl derivatives, long chain amine oxides, and mixtures thereof. Examples of such suspending agents are described in U.S. Pat. No. 4,741,855, which is incorporated herein by reference. Suitable suspending agents include ethylene glycol esters of fatty acids having from 16 to 22 carbon atoms. The suspending agent can be an ethylene glycol stearates, both mono and distearate, but particularly the distearate containing less than about 7% of the mono stearate. Other suitable suspending agents include alkanol amides of fatty acids, having from about 16 to about 22 carbon atoms, alternatively from about 16 to about 18 carbon atoms, suitable examples of which include stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanolamide and stearic monoethanolamide stearate. Other long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., stearyl stearate, cetyl palmitate, etc.); long chain esters of long chain alkanol amides (e.g., stearamide diethanolamide distearate, stearamide monoethanolamide stearate); and glyceryl esters as previously described. Long chain acyl derivatives, ethylene glycol esters of long chain carboxylic acids, long chain amine oxides, and alkanol amides of long chain carboxylic acids can also be used as suspending agents.
Other long chain acyl derivatives suitable for use as suspending agents include N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g., Na, K), particularly N,N-di(hydrogenated) C16, C18 and tallow amido benzoic acid species of this family, which are commercially available from Stepan Company (Northfield, Ill., USA).
Examples of suitable long chain amine oxides for use as suspending agents include alkyl dimethyl amine oxides, e.g., stearyl dimethyl amine oxide.
Other suitable suspending agents include primary amines having a fatty alkyl moiety having at least about 16 carbon atoms, examples of which include palmitamine or stearamine, and secondary amines having two fatty alkyl moieties each having at least about 12 carbon atoms, examples of which include dipalmitoylamine or di(hydrogenated tallow)amine. Still other suitable suspending agents include di(hydrogenated tallow)phthalic acid amide, and crosslinked maleic anhydride-methyl vinyl ether copolymer.
Other suitable suspending agents include crystallizable glyceride esters. For example, suitable glyceride esters are hydrogenated castor oils such as trihydroxystearin or dihydroxystearin. Examples of additional crystallizable glyceride esters can include the substantially pure triglyceride of 12-hydroxystearic acid. 12-hydroxystearic acid is the pure form of a fully hydrogenated triglyceride of 12-hydrox-9-cis-octadecenoic acid. As can be appreciated, many additional glyceride esters are possible. For example, variations in the hydrogenation process and natural variations in castor oil can enable the production of additional suitable glyceride esters from castor oil.
Viscosity Modifiers
Viscosity modifiers can be used to modify the rheology of a shampoo composition. Suitable viscosity modifiers can include Carbomers with tradenames Carbopol 934, Carbopol 940, Carbopol 950, Carbopol 980, and Carbopol 981, all available from B. F. Goodrich Company, acrylates/steareth-20 methacrylate copolymer with tradename ACRYSOL 22 available from Rohm and Hass, nonoxynyl hydroxyethylcellulose with tradename AMERCELL POLYMER HM-1500 available from Amerchol, methylcellulose with tradename BENECEL, hydroxyethyl cellulose with tradename NATROSOL, hydroxypropyl cellulose with tradename KLUCEL, cetyl hydroxyethyl cellulose with tradename POLYSURF 67, all supplied by Hercules, ethylene oxide and/or propylene oxide based polymers with tradenames CARBOWAX PEGs, POLYOX WASRs, and UCON FLUIDS, all supplied by Amerchol. Sodium chloride can also be used as a viscosity modifier. Other suitable rheology modifiers can include cross-linked acrylates, cross-linked maleic anhydride co-methylvinylethers, hydrophobically modified associative polymers, and mixtures thereof.
The shampoo composition can have a viscosity of about 1 cP to about 20,000 cP, or from about 100 cps to about 15,000 cps, or from 2,500 cP to about 12,000 cP, or from 1 cP to about 5000 cP, or from about 3,500 cP to about 8,500 cP, measured at 26.6° C. with a Brookfield R/S Plus Rheometer at 2 s−1. cP means centipoises.
Dispersed Particles
Dispersed particles as known in the art can be included in a shampoo composition. If including such dispersed particles, the particles can be incorporated, by weight of the composition, at levels of about 0.025% or more, about 0.05% or more, about 0.1% or more, about 0.25% or more, and about 0.5% or more. However, the shampoo compositions can also contain, by weight of the composition, about 20% or fewer dispersed particles, about 10% or fewer dispersed particles, about 5% or fewer dispersed particles, about 3% or fewer dispersed particles, and about 2% or fewer dispersed particles.
As can be appreciated, a shampoo composition can include still further optional components. For example, amino acids can be included. Suitable amino acids can include water soluble vitamins such as vitamins B1, B2, B6, B12, C, pantothenic acid, pantothenyl ethyl ether, panthenol, biotin, and their derivatives, water soluble amino acids such as asparagine, alanin, indole, glutamic acid and their salts, water insoluble vitamins such as vitamin A, D, E, and their derivatives, water insoluble amino acids such as tyrosine, tryptamine, and their salts.
Anti-dandruff agents can be included. As can be appreciated, the formation of a coacervate can facilitate deposition of the anti-dandruff agent to the scalp.
A shampoo composition can optionally include pigment materials such as inorganic, nitroso, monoazo, disazo, carotenoid, triphenyl methane, triaryl methane, xanthene, quinoline, oxazine, azine, anthraquinone, indigoid, thionindigoid, quinacridone, phthalocianine, botanical, natural colors, including: water soluble components such as those having C. I. Names. The compositions can also include antimicrobial agents which are useful as cosmetic biocides and antidandruff agents including: water soluble components such as piroctone olamine, water insoluble components such as 3,4,4′-trichlorocarbanilide (trichlosan), triclocarban and zinc pyrithione.
One or more stabilizers can be included. For example, one or more of ethylene glycol distearate, citric, citrate, a preservative such as kathon, sodium benzoate, sodium salicylate and ethylenediaminetetraacetic acid (“EDTA”) can be included to improve the lifespan of a shampoo composition.
Method of Making a Shampoo Composition
A shampoo composition described herein can be formed similarly to known shampoo compositions. For example, the process of making a shampoo composition can include the step of mixing the surfactant, cationic polymer, and liquid carrier together to form a shampoo composition.
A. Clarity Assessment
Measurement of % Transmittance (% T)
Techniques for analysis of formation of complex coacervates are known in the art. One method to assess coacervate formation upon dilution for a transparent or translucent composition is to use a spectrophotometer to measure the percentage of light transmitted through the diluted sample (% T). As percent light transmittance (% T) values measured of the dilution decrease, typically higher levels of coacervate are formed. Dilutions samples at various weight ratios of water to composition can be prepared, for example 2 parts of water to 1 part composition (2:1), or 7.5 parts of water to 1 part composition (7.5:1), or 16 parts of water to 1 part composition (16:1), or 34 parts of water to 1 part composition (34:1), and the % T measured for each dilution ratio sample. Examples of possible dilution ratios may include 2:1, 3:1, 5:1, 7.5:1, 11:1, 16:1, 24:1, or 34:1. By averaging the % T values for samples that span a range of dilution ratios, it is possible to simulate and ascertain how much coacervate a composition on average would form as a consumer applies the composition to wet hair, lathers, and then rinses it out. Average % T can be calculated by taking the numerical average of individual % T measurements for the following dilution ratios: 2:1, 3:1, 5:1, 7.5:1, 11:1, 16:1, 24:1, and 34:1.
% T can be measured using Ultra-Violet/Visible (UV/VI) spectrophotometry which determines the transmission of UV/VIS light through a sample. A light wavelength of 600 nm has been shown to be adequate for characterizing the degree of light transmittance through a sample. Typically, it is best to follow the specific instructions relating to the specific spectrophotometer being used. In general, the procedure for measuring percent transmittance starts by setting the spectrophotometer to 600 nm. Then a calibration “blank” is run to calibrate the readout to 100 percent transmittance. A single test sample is then placed in a cuvette designed to fit the specific spectrophotometer and care is taken to insure no air bubbles are within the sample before the % T is measured by the spectrophotometer at 600 nm. Alternatively, multiple samples can be measured simultaneously by using a spectrophotometer such as the SpectraMax M-5 available from Molecular Devices. Multiple dilution samples can be prepared within a 96 well plate (VWR catalog #82006-448) and then transferred to a 96 well visible flat bottom plate (Greiner part #655-001), ensuring that no air bubbles are within the sample. The flat bottom plate is placed within the SpectraMax M-5 and % T measured using the Software Pro v.5™ software available from Molecular Devices.
The compositions illustrated in the following Examples illustrate specific embodiments of the composition but are not intended to be limiting thereof. Other modifications can be undertaken by the skilled artisan without departing from the spirit and scope of this invention.
All exemplified amounts are listed as weight percents and exclude minor materials such as diluents, preservatives, color solutions, imagery ingredients, botanicals, and so forth, unless otherwise specified. All percentages are based on weight unless otherwise specified.
(1) Sodium Laureth-n Sulfate, where n ≥1 and ≤3
(2) Jaguar C17 (Rhodia)
(3) ADPP-5043H1VPW (with Mol. W. of - 1,200,000 and Char. Den. of 2.0 meq/g) available from Aqualon/Hercules
(4) Polymer LR30M (Dow Chemical Company)
(5) Mirapol 100S (Solvay)
(6) Cf330m (Momentive Performance Materials)
(7) Belsil ® DM 5500 E (Wacker)
(8) Dow Corning 1872 (Dow Corning Corporation)
(9) Trihydroxystearin-PrimG (Elementis Specialties Inc.)
(10) Carbopol Aqua SF 1 (Lubrizol Advanced Materials)
(11) Jaguar Excel (Solvay)
(12) Polymer KG30M (Dow Chemical Company)
(13) Carbopol Aqua SF 2 (Lubrizol Advanced Materials)
(14) Kelcogel CG-LA (CP Kelco)
(15) Sodium C10-15 Pareth Sulfate (Beijing, HuaMeiHuLiBiological Chemical)
(16) Makimousse 12 (Kobo Products, Inc.)
(17) Mackam ® DAB ULS (Solvay)
(18) Jordapon ® CI Prill (BASF)
(19) Crodasinic LS30/NP (Croda)
(20) Sodium Cocoyl Glutamate, Hostapon CGN - low salt (Clariant)
(21) Chemccinate ™ DSLS (Lubrizol)
(22) Iselux ® (Innospec)
(23) N-Hance 3196 (Ashland Chemical)
(24) N-Hance BF17 (Ashland Chemical)
(25) Dream Petals (Sandream Impact LLC)
It will be appreciated that other modifications of the present disclosure are within the skill of those in the hair care formulation art can be undertaken without departing from the spirit and scope of this invention. All parts, percentages, and ratios herein are by weight unless otherwise specified. Some components may come from suppliers as dilute solutions. The levels given reflect the weight percent of the active material, unless otherwise specified. A level of perfume and/or preservatives may also be included in the following examples.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, 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 “about 40 mm.”
Every document cited herein, including any cross referenced or related patent or application, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests, or discloses any such invention. Further, 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.
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.
| Number | Name | Date | Kind |
|---|---|---|---|
| 1094935 | Schenck et al. | Apr 1914 | A |
| 2326733 | Fisher | Aug 1943 | A |
| 2396278 | Otto | Mar 1946 | A |
| 2438091 | Lynch | Mar 1948 | A |
| 2486921 | Byerly | Nov 1949 | A |
| 2486922 | Bruce | Nov 1949 | A |
| 2528378 | McCabe, Jr. | Oct 1950 | A |
| 2658072 | Kosmin | Nov 1953 | A |
| 2694668 | Fricke | Nov 1954 | A |
| 2786847 | Cislak | Mar 1957 | A |
| 2798053 | Brown | Jul 1957 | A |
| 2809971 | Jack | Oct 1957 | A |
| 2826551 | Geen | Mar 1958 | A |
| 3152046 | Maria | Oct 1964 | A |
| 3155591 | Harry | Nov 1964 | A |
| 3236733 | Karsten | Feb 1966 | A |
| 3332880 | Adriaan | Jul 1967 | A |
| 3589999 | Mcrae | Jun 1971 | A |
| 3590035 | Damico | Jun 1971 | A |
| 3655096 | Easter | Apr 1972 | A |
| 3753196 | Kurtz | Aug 1973 | A |
| 3761418 | Parran | Sep 1973 | A |
| 3773770 | Damico | Nov 1973 | A |
| 3852441 | Kooistra | Dec 1974 | A |
| 3929678 | Laughlin et al. | Dec 1975 | A |
| 3940482 | Grand | Feb 1976 | A |
| 3958581 | Abegg | May 1976 | A |
| 3959461 | Bailey | May 1976 | A |
| 3964500 | Drakoff | Jun 1976 | A |
| 4055655 | Maurer | Oct 1977 | A |
| 4089945 | Brinkman | May 1978 | A |
| 4152416 | Marra | May 1979 | A |
| 4161426 | Kneer | Jul 1979 | A |
| 4197865 | Jacquet | Apr 1980 | A |
| 4217914 | Jacquet | Aug 1980 | A |
| 4323683 | Bolich, Jr. | Apr 1982 | A |
| 4345080 | Bolich, Jr. | Aug 1982 | A |
| 4364387 | Larkin | Dec 1982 | A |
| 4379753 | Bolich, Jr. | Apr 1983 | A |
| 4381919 | Jacquet | May 1983 | A |
| 4387090 | Bolich, Jr. | Jun 1983 | A |
| 4422853 | Jacquet | Dec 1983 | A |
| 4470982 | Winkler | Sep 1984 | A |
| 4507280 | Pohl | Mar 1985 | A |
| 4529586 | De | Jul 1985 | A |
| 4565647 | Llenado | Jan 1986 | A |
| 4604272 | Kratel | Aug 1986 | A |
| 4608183 | Rossmoore | Aug 1986 | A |
| 4663158 | Wolfram | May 1987 | A |
| 4666616 | Rossmoore | May 1987 | A |
| 4670430 | Imamura | Jun 1987 | A |
| 4686254 | Lochhead | Aug 1987 | A |
| 4704272 | Oh | Nov 1987 | A |
| 4708863 | Bews | Nov 1987 | A |
| 4726915 | Verdicchio | Feb 1988 | A |
| 4788006 | Bolich, Jr. | Nov 1988 | A |
| 4834767 | Helioff | May 1989 | A |
| 4885107 | Wetzel | Dec 1989 | A |
| 4898585 | Borsanyi | Feb 1990 | A |
| 5034218 | Duvel | Jul 1991 | A |
| 5057153 | Ruggiero | Oct 1991 | A |
| 5104646 | Bolich, Jr. | Apr 1992 | A |
| 5106609 | Bolich, Jr. | Apr 1992 | A |
| 5106613 | Hartnett | Apr 1992 | A |
| 5114898 | Pinnavaia | May 1992 | A |
| 5154847 | Lapetina | Oct 1992 | A |
| 5186928 | Birtwistle | Feb 1993 | A |
| 5202048 | Bartolo | Apr 1993 | A |
| 5227156 | Wiese | Jul 1993 | A |
| 5248445 | Rizvi | Sep 1993 | A |
| RE34584 | Grote | Apr 1994 | E |
| 5358667 | Bergmann | Oct 1994 | A |
| 5360581 | Rizvi | Nov 1994 | A |
| 5462589 | Nicholas | Oct 1995 | A |
| 5466425 | Adams | Nov 1995 | A |
| 5478501 | Rau | Dec 1995 | A |
| 5495538 | Fan | Feb 1996 | A |
| 5518774 | Kappock | May 1996 | A |
| 5540954 | Nicholas | Jul 1996 | A |
| 5562995 | Kappock | Oct 1996 | A |
| 5609862 | Chen et al. | Mar 1997 | A |
| 5614538 | Nelson, Jr. | Mar 1997 | A |
| 5674478 | Dodd et al. | Oct 1997 | A |
| 5696169 | Otsu | Dec 1997 | A |
| 5710114 | Pyles | Jan 1998 | A |
| 5726137 | Patel | Mar 1998 | A |
| 5750122 | Evans | May 1998 | A |
| 5756076 | Cervantes | May 1998 | A |
| 5776444 | Birtwistle et al. | Jul 1998 | A |
| 5785962 | Hinz | Jul 1998 | A |
| 5798121 | Cauwet | Aug 1998 | A |
| 5811487 | Schulz, Jr. et al. | Sep 1998 | A |
| 5836479 | Klima et al. | Nov 1998 | A |
| 5837661 | Evans | Nov 1998 | A |
| 5853707 | Wells | Dec 1998 | A |
| 5854319 | Olenick, Jr. | Dec 1998 | A |
| 5874476 | Hsu | Feb 1999 | A |
| 5876705 | Uchiyama | Mar 1999 | A |
| 5880076 | Vermeer | Mar 1999 | A |
| 5883154 | Kappock | Mar 1999 | A |
| 5885948 | Glenn, Jr. et al. | Mar 1999 | A |
| 5939059 | Franklin | Aug 1999 | A |
| 5939203 | Kappock | Aug 1999 | A |
| 5955066 | Sako | Sep 1999 | A |
| 5965515 | Rau | Oct 1999 | A |
| 5977036 | Guskey | Nov 1999 | A |
| 5997036 | Hamada | Dec 1999 | A |
| 5997851 | Cox | Dec 1999 | A |
| 6017562 | Kaufman | Jan 2000 | A |
| 6034043 | Fujiwara | Mar 2000 | A |
| 6183766 | Sine et al. | Feb 2001 | B1 |
| 6303109 | Foerster | Oct 2001 | B1 |
| 6309628 | Ansmann | Oct 2001 | B1 |
| 6333040 | Boyxen | Dec 2001 | B1 |
| RE37793 | Domenico | Jul 2002 | E |
| 6432420 | Ellis | Aug 2002 | B2 |
| 6451300 | Dunlop et al. | Sep 2002 | B1 |
| 6521238 | Muller | Feb 2003 | B1 |
| 6521239 | Breton | Feb 2003 | B1 |
| RE38130 | Adams | Jun 2003 | E |
| 6598762 | Mckune | Jul 2003 | B2 |
| 6719967 | Brown | Apr 2004 | B1 |
| 6774096 | Paye | Aug 2004 | B1 |
| 6878368 | Ohta et al. | Apr 2005 | B2 |
| 6908912 | Rioux | Jun 2005 | B2 |
| 6991799 | Pham et al. | Jan 2006 | B2 |
| 7040311 | Hochrainer et al. | May 2006 | B2 |
| 7303744 | Wells | Dec 2007 | B2 |
| 7531497 | Midha et al. | May 2009 | B2 |
| 7560125 | Ananthapadmanabhan et al. | Jul 2009 | B2 |
| 7776347 | Kerschner et al. | Aug 2010 | B2 |
| 8252271 | Singer et al. | Aug 2012 | B2 |
| 8349300 | Wells | Jan 2013 | B2 |
| 8349301 | Wells et al. | Jan 2013 | B2 |
| 8349302 | Johnson et al. | Jan 2013 | B2 |
| 8361448 | Johnson | Jan 2013 | B2 |
| 8361449 | Wells et al. | Jan 2013 | B2 |
| 8361450 | Johnson et al. | Jan 2013 | B2 |
| 8367048 | Wells et al. | Feb 2013 | B2 |
| 8470305 | Johnson et al. | Jun 2013 | B2 |
| 8635014 | Jung | Jan 2014 | B2 |
| 8653014 | Hilvert et al. | Feb 2014 | B2 |
| 8655819 | Burkard et al. | Feb 2014 | B1 |
| 8663612 | Gamez-Garcia et al. | Mar 2014 | B2 |
| 8901062 | De Meirleir et al. | Dec 2014 | B2 |
| 8932569 | Garrison et al. | Jan 2015 | B2 |
| 8940285 | Leray et al. | Jan 2015 | B2 |
| 8969261 | Talingting Pabalan | Mar 2015 | B2 |
| 9005585 | Deckner et al. | Apr 2015 | B2 |
| 9138429 | Wise et al. | Sep 2015 | B2 |
| 9381382 | Schwartz et al. | Jul 2016 | B2 |
| 9393188 | Deckner et al. | Jul 2016 | B2 |
| 9539444 | Kinoshita | Jan 2017 | B2 |
| 9587209 | De Meirleir et al. | Mar 2017 | B2 |
| 9724283 | Rizk | Aug 2017 | B2 |
| 9877909 | Cetti et al. | Jan 2018 | B2 |
| 10143632 | Dihora | Dec 2018 | B2 |
| 10912719 | Gulbin | Feb 2021 | B2 |
| 10945935 | Brown | Mar 2021 | B2 |
| 20010047039 | Mcmanus | Nov 2001 | A1 |
| 20020119113 | Ellis | Aug 2002 | A1 |
| 20020131946 | Pham et al. | Sep 2002 | A1 |
| 20020169283 | Lu | Nov 2002 | A1 |
| 20020183300 | Fliss | Dec 2002 | A1 |
| 20030012646 | Liao | Jan 2003 | A1 |
| 20030017126 | Mahadeshwar | Jan 2003 | A1 |
| 20030044471 | Sakuma | Mar 2003 | A1 |
| 20030095938 | Casero | May 2003 | A1 |
| 20030119806 | Lindell | Jun 2003 | A1 |
| 20030130145 | Patel | Jul 2003 | A1 |
| 20030138497 | Sakuma | Jul 2003 | A1 |
| 20030171231 | Shana | Sep 2003 | A1 |
| 20030185779 | Mitsumatsu | Oct 2003 | A1 |
| 20030215522 | Johnson | Nov 2003 | A1 |
| 20030223952 | Wells et al. | Dec 2003 | A1 |
| 20030224954 | Wells et al. | Dec 2003 | A1 |
| 20030224955 | Ribery | Dec 2003 | A1 |
| 20040058855 | Schwartz | Mar 2004 | A1 |
| 20040092897 | Macedo, Jr. | May 2004 | A1 |
| 20040157754 | Geary et al. | Aug 2004 | A1 |
| 20040167114 | Fliss | Aug 2004 | A1 |
| 20040191331 | Schwartz | Sep 2004 | A1 |
| 20040197294 | Seipel | Oct 2004 | A1 |
| 20040223941 | Schwartz | Nov 2004 | A1 |
| 20040223991 | Wei et al. | Nov 2004 | A1 |
| 20040234471 | Corbella | Nov 2004 | A1 |
| 20040266886 | Seipel | Dec 2004 | A1 |
| 20050031569 | Seipel | Feb 2005 | A1 |
| 20050100570 | Wei et al. | May 2005 | A1 |
| 20050112083 | Wells et al. | May 2005 | A1 |
| 20050143268 | Midha | Jun 2005 | A1 |
| 20050181067 | Yokoyama | Aug 2005 | A1 |
| 20050196368 | Laurent et al. | Sep 2005 | A1 |
| 20050202984 | Schwartz | Sep 2005 | A1 |
| 20050267258 | Rajaraman et al. | Dec 2005 | A1 |
| 20060024256 | Wells | Feb 2006 | A1 |
| 20060024381 | Schwartz | Feb 2006 | A1 |
| 20060025256 | Wake | Feb 2006 | A1 |
| 20060045861 | Bejger | Mar 2006 | A1 |
| 20060078524 | Midha et al. | Apr 2006 | A1 |
| 20060078527 | Midha et al. | Apr 2006 | A1 |
| 20060079419 | Wagner et al. | Apr 2006 | A1 |
| 20060079420 | Wagner et al. | Apr 2006 | A1 |
| 20060079421 | Wagner et al. | Apr 2006 | A1 |
| 20060250658 | Jurgensen | Nov 2006 | A1 |
| 20060251605 | Belmar | Nov 2006 | A1 |
| 20060269501 | Johnson | Nov 2006 | A1 |
| 20060269502 | Johnson | Nov 2006 | A1 |
| 20070110696 | Johnson | May 2007 | A1 |
| 20070110700 | Wells | May 2007 | A1 |
| 20070128147 | Schwartz et al. | Jun 2007 | A1 |
| 20080039352 | Wells et al. | Feb 2008 | A1 |
| 20080096786 | Holt et al. | Apr 2008 | A1 |
| 20080152611 | Wells | Jun 2008 | A1 |
| 20080187507 | Johnson | Aug 2008 | A1 |
| 20100061952 | Wells et al. | Mar 2010 | A1 |
| 20100226868 | Gamez-Garcia et al. | Sep 2010 | A1 |
| 20100234260 | Sekine et al. | Sep 2010 | A1 |
| 20100322878 | Stella et al. | Dec 2010 | A1 |
| 20100330018 | Lorant et al. | Dec 2010 | A1 |
| 20110053818 | Chuchotiros et al. | Mar 2011 | A1 |
| 20110065624 | Boutique et al. | Mar 2011 | A1 |
| 20110067720 | Ranade et al. | Mar 2011 | A1 |
| 20110070180 | Ranade et al. | Mar 2011 | A1 |
| 20110081392 | de Arruda et al. | Apr 2011 | A1 |
| 20110110991 | Garrison et al. | May 2011 | A1 |
| 20120164198 | Johnson et al. | Jun 2012 | A1 |
| 20120308502 | Wise et al. | Dec 2012 | A1 |
| 20120329768 | Wise et al. | Dec 2012 | A1 |
| 20130090279 | Hilvert et al. | Apr 2013 | A1 |
| 20130131188 | Beckedahl et al. | May 2013 | A1 |
| 20130143784 | Rizk | Jun 2013 | A1 |
| 20130174863 | Marsh et al. | Jul 2013 | A1 |
| 20130243717 | Catalan et al. | Sep 2013 | A1 |
| 20130243835 | Tanner et al. | Sep 2013 | A1 |
| 20140018276 | Coffindaffer et al. | Jan 2014 | A1 |
| 20140099276 | Yang et al. | Apr 2014 | A1 |
| 20140112964 | Wu | Apr 2014 | A1 |
| 20140162931 | De Meirleir et al. | Jun 2014 | A1 |
| 20140335041 | Peffly et al. | Nov 2014 | A1 |
| 20150010487 | Snyder | Jan 2015 | A1 |
| 20150011450 | Carter et al. | Jan 2015 | A1 |
| 20150044157 | Kulkarni et al. | Feb 2015 | A1 |
| 20150059795 | Vatter et al. | Mar 2015 | A1 |
| 20150093422 | Garrison et al. | Apr 2015 | A1 |
| 20150342842 | Wise et al. | Dec 2015 | A1 |
| 20150374609 | Cetti et al. | Dec 2015 | A1 |
| 20160067172 | Burch et al. | Mar 2016 | A1 |
| 20160106663 | Gulbin | Apr 2016 | A1 |
| 20160143827 | Castan Barberan et al. | May 2016 | A1 |
| 20160256365 | Dihora | Sep 2016 | A1 |
| 20170216158 | Deckner et al. | Aug 2017 | A1 |
| 20170333734 | Mauer et al. | Nov 2017 | A1 |
| 20170367955 | Brown | Dec 2017 | A1 |
| 20180071185 | Cochran et al. | Mar 2018 | A1 |
| 20180098923 | Hutton, III | Apr 2018 | A1 |
| 20190201925 | Toh et al. | Jul 2019 | A1 |
| 20190290554 | Yokogi et al. | Sep 2019 | A1 |
| 20190290555 | Yokogi et al. | Sep 2019 | A1 |
| 20190290562 | Yokogi et al. | Sep 2019 | A1 |
| 20190290567 | Yokogi et al. | Sep 2019 | A1 |
| 20190290568 | Yokogi et al. | Sep 2019 | A1 |
| 20190307665 | Yokogi et al. | Oct 2019 | A1 |
| 20190365611 | Brown et al. | Dec 2019 | A1 |
| 20210045979 | Dunlop et al. | Feb 2021 | A1 |
| 20210121903 | Yamaguchi et al. | Apr 2021 | A1 |
| 20210253303 | Bartolucci et al. | Aug 2021 | A1 |
| Number | Date | Country |
|---|---|---|
| 2012337567 | Apr 2017 | AU |
| 2143558 | Aug 1996 | CA |
| 10532660 | Apr 2018 | CN |
| 105395378 | Jul 2018 | CN |
| 105395378 | Jul 2018 | CN |
| 105395378 | Jul 2018 | CN |
| 0037318 | Oct 1981 | EP |
| 0077630 | Apr 1983 | EP |
| 0627216 | Dec 1994 | EP |
| 1123693 | Aug 2001 | EP |
| 1066024 | Oct 2002 | EP |
| 1384467 | May 2007 | EP |
| 2593801 | May 1986 | FR |
| 1971709 | Aug 2012 | FR |
| 849433 | Sep 1960 | GB |
| 1582529 | Jan 1981 | GB |
| 2177108 | Jul 1989 | GB |
| 5209881 | Aug 1977 | JP |
| 06134227 | May 1994 | JP |
| H07179887 | Nov 1994 | JP |
| H07118103 | May 1995 | JP |
| 07258039 | Oct 1995 | JP |
| 2001181145 | Jul 2001 | JP |
| 2002104940 | Apr 2002 | JP |
| 2004262805 | Sep 2004 | JP |
| 2004292387 | Oct 2004 | JP |
| 2004292390 | Oct 2004 | JP |
| 2004307463 | Nov 2004 | JP |
| 2005022983 | Jan 2005 | JP |
| 2005187342 | Jul 2005 | JP |
| 2006063044 | Mar 2006 | JP |
| 2006525232 | Nov 2006 | JP |
| 4016238 | Sep 2007 | JP |
| 2007527921 | Oct 2007 | JP |
| 4069228 | Jan 2008 | JP |
| 4129645 | May 2008 | JP |
| 2008524263 | Jul 2008 | JP |
| 2016516674 | Jun 2016 | JP |
| WO9308787 | May 1993 | WO |
| WO9410973 | May 1994 | WO |
| WO9625144 | Aug 1996 | WO |
| WO9625913 | Aug 1996 | WO |
| WO9726854 | Jul 1997 | WO |
| WO9847372 | Oct 1998 | WO |
| WO9938489 | Aug 1999 | WO |
| WO9959540 | Nov 1999 | WO |
| WO0100149 | Jan 2001 | WO |
| WO0117492 | Mar 2001 | WO |
| WO0139735 | Jun 2001 | WO |
| WO0222091 | Mar 2002 | WO |
| WO02076422 | Oct 2002 | WO |
| WO2004022681 | Mar 2004 | WO |
| WO2004022682 | Mar 2004 | WO |
| 2007031884 | Mar 2007 | WO |
| WO2010006866 | Jan 2010 | WO |
| WO2010034736 | Apr 2010 | WO |
| 2010111266 | Sep 2010 | WO |
| WO2011120799 | Oct 2011 | WO |
| WO2011134832 | Nov 2011 | WO |
| 2012004126 | Jan 2012 | WO |
| 2012138696 | Oct 2012 | WO |
| WO2012175677 | Dec 2012 | WO |
| WO20121756821 | Dec 2012 | WO |
| 2013073849 | May 2013 | WO |
| 2013092719 | Jun 2013 | WO |
| 2017088459 | Jun 2017 | WO |
| WO-2017088459 | Jun 2017 | WO |
| WQ2017088459 | Jun 2017 | WO |
| 2018005453 | Jan 2018 | WO |
| WO-2018005453 | Jan 2018 | WO |
| Entry |
|---|
| “Herbal Essence Shampoo”, Mintel, Jun. 1, 2014. |
| 1—Eccleston, G.M., Application of Emulsion Stability Theories to Mobile and Semisolid o/w Emulsions, Cosmetics Magazine, vol. 101, 1986. |
| 2—Eccleston, G.M., Application of Emulsion Theory to Complex and Real Systems, International Journal of Cosmetic Science, 1985. |
| 3—Eccleston, G.M., Formulating Cosmetic Emulsions, Cosmetics Magazine, vol. 112, 1997. |
| 4—Eccleston, G.M., Functions of Mixed Emulsifiers and Emulsifying Waxes in Dermatological Lotions and Creams, Colloids and Surfaces, vol. 123, 1997. |
| 5—Eccleston, G.M., Microstructural Changes During Storage of Cetostearyl Alcohol/Polyoxyethylene Alkyl Ether Surfactants, University of Strathclyde, 1988. |
| 6—Eccleston, G.M., Multiple Phase Oil and Water Emulsions, Journal of Cosmetic Chemists, 1990. |
| 7—Eccleston, G.M., Structure and Rheology of Semisolid o/w Creams Containing Cetyl Alcohol/Non-ionic Surfactant Mixed Emulsifier and Different Polymers, International Journal of Cosmetic Science, 2004. |
| 8—Eccleston, G.M., Synchrotron X-ray Investigations into the Lamellar Gel Phase Formed in Creams Prepared with Fatty Alcohols, International Journal of Pharmaceuticals, 2000. |
| 9—Eccleston, G.M., The Influence of Fatty Alcohols on the Structure and Stability of Creams Preapred with Fatty Mcohols, International Journal of Cosmetic Science, 1982. |
| All final and non-final office actions for U.S. Appl. No. 13/646,227. |
| All final and non-final office actions for U.S. Appl. No. 14/322,573. |
| All final and non-final office actions for U.S. Appl. No. 14/478,013. |
| All final and non-final office actions for U.S. Appl. No. 14/881,714. |
| All final and non-final office actions for U.S. Appl. No. 15/635,633. |
| All final and non-final office actions for U.S. Appl. No. 15/703,046. |
| All final and non-final office actions for U.S. Appl. No. 15/728,663. |
| Barry & Rowe, The Characterization by Small Angle X-Ray Scattering of a Gel with a Lamellar Structure, International Journal of Pharmaceuticals, 1989. |
| Barry & Saunders, Kinetics of Structure Build-up in Self Bodied Emulsions Stabalized by Mixed Emulsifiers, Journal of Colloid Science, vol. 41, 1972. |
| Barry, B.W., Structure and Rheology of Emulsions Stabalized by Mixed Emulsifiers, British Society of Rheology, 1970. |
| Benton et al., Phase Behavior and Network Formation in a Cationic Surfactant-Fatty Alcohol System, JAOCS, vol. 64, 1987. |
| Burgess, J.D., Practical Analysis of Complex Coacervate Systems, Journal of Colloid Science, vol. 140, 1990. |
| CTFA Cosmetic Ingredient Dictionary, 1982, 3rd Edition, The Cosmetic, Toiletry & Fragrance Association, Inc., Nashington, DC (book not included). |
| Encyclopedia of Polymer Science and Engineering, John Wiley & Sons, vol. 15, 1989 (book not included). |
| Giiffin, W.C., Calculation of HLB Values of Non-lonic Surfactants, Journal of the Society of Cosmetic Chemists; 1954. vol. 5, pp. 249-235. |
| Korhonen et al., Rheological Properties of Three Component Creams Containing Sorbitan Monoesters as Surfactants, International Journal of Pharmaceuticals, 2002. |
| Louden et al., A Preliminary Examination of the Structure of Gels and Emulsions Containing Cetostearyl Alcohol, International Journal of Pharmaceuticals, 1985. |
| McCutcheon, Emulsifiers and Detergents, MC Pub Company, 1989 (book not included). |
| Meirleir Niels De et al., “The rheological properties of hydrogenated castor oil crystals”, Colloid & Polymer Science, Springer Verlag, Heidelberg, DE, vol. 292, No. 10, Jun. 12, 2014, pp. 2539-2547. |
| Momentive SFE839 product brochure, https://www.momentive.com/products/showtechnicaldatasheet.aspx?d=14443available Sep. 2008; accessed Jul. 17, 2015. |
| Noll, W., Chemistry and Technology of Silicones, Academic Press, 1968 (book not included). |
| Patel et al., Properties of Cetrimide / Cetostearyl Alcohol Ternary Gels; Preparation Effects, International Journal of Pharmaceuticals, 1985. |
| PCT International Search Report and Written Opinion for PCT/US2014/045197 dated Oct. 7, 2014. |
| PCT International Search Report and Written Opinion for PCT/US2014/054294 dated Nov. 11, 2014. |
| PCT International Search Report and Written Opinion for PCT/US2015/056423 dated Jan. 8, 2016. |
| PCT International Search Report and Written Opinion for PCT/US2017/039444 dated Aug. 28, 2017. |
| PCT International Search Report and Written Opinion for PCT/US2017/051249 dated Nov. 10, 2017. |
| PCT International Search Report and Written Opinion for PCT/US2017/055821 dated Dec. 6, 2017. |
| Savic et al., Colloidal Microstructure of Binary Systems and Model Creams Stablized with an Alkylpolyglucoside Emulsifier, Colloid Polymer Science, vol. 283, 2004. |
| Saxton, C., Antiplaque Effects and Mode of Action of a Combination of Zinc Citrate and a Nonionic Antimicrobial Agent, Scandinavian Journal, vol. 96, 1988. |
| Suzuki et al., Secondary Droplet Emulsion: Mechanism & Effects of Liquid Crystal Formation in o/w Emulsion, Journal of Dispersion Science, 1984. |
| Van Cutsem, Journal of the American Academy of Dermatology, XP-002288119, 1998. |
| Van Oss, C.J., Coacervation, Complex Coacervation and Flocculation, Journal of Dispersion Science, vol. 9, 1989. |
| Yoon et al., A Study of Gel Structure in the Nonionic Surfactant / Cetostearyl Alcohol / Water Ternary Systems by Differential Scanning Calorimeter, Journal of Dispersion Science, 1999. |
| All Office Actions; U.S. Appl. No. 17/184,814, filed Feb. 25, 2021. |
| All Office Actions; U.S. Appl. No. 16/432,371, filed Jun. 5, 2019. |
| All Office Actions; U.S. Appl. No. 17/174,713, filed Feb. 12, 2021. |
| All Office Actions; U.S. Appl. No. 17/174,427, filed Feb. 12, 2021. |
| All Office Actions; U.S. Appl. No. 17/326,910, filed May 21, 2021. |
| All Office Actions; U.S. Appl. No. 17/327,972, filed May 24, 2021. |
| Database WPI Week 201634Thomson Scientific, London, GB;AN 2016-184949XP002798128,& CN 105 395 373 A (Cuongqing Pellets Coltd), Mar. 16, 2016 (Mar. 16, 2016))abstract, 3 pages. |
| Database WPI Week 201644Thomson Scientific, London, GB;AN 2016-14284BXP002798127,& CN 105 326 660 A (Chongqjng Pellets Colid), Feb. 17, 2016 (Feb. 17, 2016)abstract, 3 pages. |
| INCi: Ricinus Communis (Castor) Seed Oil, 3 pages. |
| Unpublished U.S. Appl. No. 17/184,814, filed Feb. 25, 2021, to Mark Anthony Brown et al. |
| Unpublished U.S. Appl. No. 17/326,910, filed May 21, 2021, to Howard David Hutton. |
| Unpublished U.S. Appl. No. 17/327,972, filed May 24, 2021, to Howard David Hutton. |
| Unpublished U.S. Appl. No. 17/174,713, filed Feb. 12, 2021, to Mark Anthony Brown et al. |
| U.S. Appl. No. 16/902,629, filed Jun. 16, 2020, Cochran et al. |
| “Polyelectrolyte-Micelle—Coacervation—Effect of coacervate on the properties of shampoo”, Yoshiko Kiwatari et al., J Soc. Cosmet. Chem. Japan, vol. 38, No. 3, 2004, pp. 211-219. |
| All final and non-final office actions for U.S. Appl. No. 16/902,629. |
| All final and non-final office actions for U.S. Appl. No. 16/907,711. |
| PCT International Search Report and Written Opinion for PCT/US2019/065452 dated Mar. 20, 2020. |
| PCT International Search Report and Written Opinion for PCT/US2020/070185 dated Oct. 30, 2020. |
| Number | Date | Country | |
|---|---|---|---|
| 20200188243 A1 | Jun 2020 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62779685 | Dec 2018 | US |
