The present invention relates to hair conditioner compositions, more particularly to hair conditioner compositions comprising a surfactant system that includes sodium benzoate and glycols and/or glyceryl esters.
A variety of approaches have been developed to condition the hair. These approaches range from post-shampoo application of hair conditioners such as leave-on and rinse-off products, to hair conditioning shampoos which attempt to both clean and condition the hair from a single product.
Although some consumers prefer the ease and convenience of a shampoo which includes conditioners, a substantial proportion of consumers prefer the more conventional conditioner formulations which are applied to the hair as a separate step from shampooing, usually subsequent to shampooing. Conditioning formulations can be in the form of rinse-off products or leave-on products, and can be in the form of an emulsion, cream, gel, spray, and mousse. Such consumers who prefer the conventional conditioner formulations value the relatively higher conditioning effect, or convenience of changing the amount of conditioning depending on the condition of hair or amount of hair.
It is known that conditioning compositions, like most cosmetic products, contain preservatives to prevent product spoilage by microorganisms. Preservatives can help keep the product stable throughout the life of the product including during shipping, handling, storage, and while the consumer is using the product. During use, the consumer can inadvertently introduce microorganisms as they open and close the aqueous product and these microorganisms can proliferate in the warm, humid environment of the shower. Therefore, cosmetic products generally contain preservation systems. Common preservatives in conditioner products can include isothiazolinones, parabens, benzyl alcohol, phenoxyethanol, and ethylenediaminetetraacetic acid (EDTA) and salts thereof.
However, some consumers want cosmetic products with preservation systems that are EWG VERIFIED™, do not contain any of the ingredients that Whole Foods® lists as unacceptable, and is categorized as “risk-free” (green dot) by the Yuka® Application. Modifying the preservation system to reduce or eliminate certain preservatives can have a negative impact on microbiological safety requirements.
Therefore, there is a need for a conditioner composition with an effective preservation system that that is EWG VERIFIED™, does not contain any of the ingredients that Whole Foods® Market lists as unacceptable, and is categorized as “risk-free” by the Yuka® Application.
A hair conditioner composition comprising: (a) from about 50% to about 95% of an aqueous carrier, by weight of the composition; (b) from about 0.1 wt % to about 10 wt % of a cationic surfactant; (c) from about 1.5 wt % to about 15 wt % of a high melting point fatty compound; (d) a preservation system comprising: (i) from about 0.1% to about 0.5% sodium benzoate, by weight of the composition; (ii) from about 0.3% to about 1.5% of a second composition selected from the group consisting of glycol, glyceryl ester, and combinations thereof; wherein the ratio of sodium benzoate to the second composition is from about 1:4 to about 1:1; wherein the conditioner composition comprises a gel network.
A hair conditioner composition comprising: (a) from about 50% to about 95% of an aqueous carrier, by weight of the composition; (b) from about 0.1 wt % to about 10 wt % of a cationic surfactant selected from the group consisting of wherein the cationic surfactant is selected from the group consisting of behenamidopropyl dimethylamine (BAPDMA), behentrimonium chloride, cetrimonium chloride, stearamidopropyl dimethylamine, and combinations thereof; (c) from about 1.5 wt % to about 15 wt % of a fatty alcohol selected from the group consisting of cetyl alcohol, stearyl alcohol, behenyl alcohol, brassica alcohol; (d) a preservation system comprising: (i) from about 0.1% to less than 0.4% sodium benzoate, by weight of the composition; (ii) from about 0.3% to about 1.5% of a glycol selected from the group consisting of glycols can include butylene glycol, pentylene glycol, hexylene glycol, 1,2-hexanediol, caprylyl glycol, decylene glycol, and mixtures thereof; wherein the ratio of sodium benzoate to the glycol is less than 1:1; wherein the conditioner composition comprises a gel network.
A hair conditioner composition comprising: (a) from about 50% to about 95% of an aqueous carrier, by weight of the composition; (b) from about 0.1 wt % to about 10 wt % of a cationic surfactant selected from the group consisting of wherein the cationic surfactant is selected from the group consisting of behenamidopropyl dimethylamine (BAPDMA), behentrimonium chloride, cetrimonium chloride, stearamidopropyl dimethylamine, and combinations thereof; (c) from about 1.5 wt % to about 15 wt % of a fatty alcohol selected from the group consisting of cetyl alcohol, stearyl alcohol, behenyl alcohol, brassica alcohol; (d) a preservation system comprising: (i) from about 0.1% to less than 0.4% sodium benzoate, by weight of the composition; (ii) from about 0.3% to about 1.5% of a glycol selected from the group consisting of glycols can include butylene glycol, pentylene glycol, hexylene glycol, 1,2-hexanediol, caprylyl glycol, decylene glycol, and mixtures thereof; wherein the ratio of sodium benzoate to the glycol is less than 1:1; wherein the conditioner composition comprises a gel network.
While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter of the present invention, it is believed that the invention can be more readily understood from the following description taken in connection with the accompanying drawings, in which:
While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the present invention will be better understood from the following description.
Hair conditioners are used to improve the feel, appearance, and manageability of the hair. Hair conditioning compositions generally include a cationic surfactant, high melting point fatty compound(s) having a melting point of greater than 25° C. and in some examples from 40 to 85° C., and an aqueous carrier. Conditioning compositions also include a safe and effective preservation system to prevent the growth of microbes under regular storage and usage conditions. Common preservatives in conditioner products can include isothiazolinones (including methylisothiazolinone and a mixture of methylisothiazolinone and methylchloroisothiazolinone (commercially available as Kathon™ from Dow®), parabens (including Germaben®, methylparben, propylparaben, butylparaben, and phenoxyethanols, which are commercially available in Optiphen™ and Optiphen™ Plus from Ashland™), benzyl alcohol, and phenoxyethanol. Ethylenediaminetetraacetic acid (EDTA) and salts thereof including disodium EDTA, calcium disodium EDTA, and tetrasodium EDTA, are also frequently used in hair care compositions as a chelator that can also improve product performance and stability.
However, there is growing demand from some consumeres for a conditioner product and/or a preservation system that meets at least one, two, or all three of the following standards:
However, replacing traditional preservatives with preservatives that meet the standards, listed above, while maintaining antimicrobial effectiveness and product performance can be challenging. Table 1 and Table 2, below, include examples that have a sodium benzoate preservative, which meets the standards. However, if the conditioner composition had a smooth and creamy consistency, then the level of sodium benzoate was too low to effectively inhibit the growth of microbes. When the level of sodium benzoate was increased, the conditioner composition was too thin to easily apply with a user's hands, which can significantly impact product performance and the usage experience. As shown in Table 3 and described in accompanying text, a preservation system with sodium benzoate and a glycol, such as caprylyl glycol, or glyceryl esters, such as glyceryl caprylate/caprate and glyceryl caprylate (and) glyceryl undecylenate can be effective if the proper levels of each ingredient are added. It was found that a preservation system that contains sodium benzoate and a second composition selected from the group consisting of glycols, glyceryl esters, and combinations thereof contains all of the ingredients that have a EWG rating score of equal to or less than 3, can be EWG VERIFIED™, may not contain any of the ingredients that Whole Foods® Market lists as unacceptable, and can categorized as “risk-free” by the Yuka® Application, can maintain antimicrobial effectiveness, and can provide good conditioning performance. In some examples, the preservation system and/or the conditioner can also meet the COSMOS-standard (Jan. 1, 2019). The conditioner compositions containing this preservation system can have a uniform, smooth, creamy appearance and have an effective preservation system where the level of microbes (both bacteria and fungi) is undetectable (>99.99% reduction) as determined by the Bacterial and Fungal Microbial Susceptibility Test Methods, as described herein.
The second composition can contain a glycol and/or a glyceryl ester. Glycols and glyceryl esters both have two —OH groups on the molecule. Non-limiting examples of glycols can include butylene glycol, pentylene glycol, hexylene glycol, 1,2-hexanediol, caprylyl glycol, decylene glycol (1,2-decanedioi) and mixtures thereof. In one example, the glycol can be carpylyl Non-limiting examples of glycerol esters can include glyceryl caprylate, glyceryl caprate, glyceryl undecylenate and mixtures thereof.
The conditioner composition and/or preservation system can be free of or substantially free of certain preservatives, in particular preservatives that do not meet one or more of the standards, such as isothiazolinones including 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one (commercially available as Kathon™ CG from Dow®), benzyl alcohol, phenoxyethanol, cyclohexylglycerin, and/or parabens. The conditioner composition can be free of or substantially free of ethylenediaminetetraacetic acid (EDTA) and salts thereof. In addition to meeting the standards for a cationic surfactant and preservation system, some consumers prefer a conditioner composition that is free of or substantially free of the following: silicone, propellants, phthalates, parabens, isothiazolinones (e.g. Kathon™), phenoxyethanols, dyes, sulfates, and/or formaldehyde donors. The conditioner composition can also be vegan.
The conditioner composition can contain from about 0.2 wt % to about 1.5 wt % preservation system, alternatively from about 0.3 wt % to about 1.25 wt % preservation system, alternatively from about 0.4 wt % to about 1 wt % preservation system, alternatively from 0.5 wt % to about 0.8 wt % preservation system, and alternatively from about 0.6 wt % to about 0.8 wt % preservation system.
The conditioner composition can contain from about 0.05 wt % to about 0.8 wt % sodium benzoate, alternatively 0.1 wt % to about 0.5 wt % sodium benzoate, alternatively from about 0.2 wt % to about 0.4 wt % sodium benzoate. The conditioner composition can contain sodium benzoate and can contain less than 2% sodium benzoate, alternatively less than 1.5% sodium benzoate, alternatively less than 1% sodium benzoate, alternatively less than 0.8% sodium benzoate, alternatively less than 0.6 wt % sodium benzoate, and alternatively less than 0.5% sodium benzoate.
The preservation system can contain from about 20% to about 50% sodium benzoate, by weight of the preservation system, alternatively from about 25% to about 50% sodium benzoate, by weight of the preservation system, from about 30% to about 50% sodium benzoate, by weight of the preservation system, and from about 30% to about 40% sodium benzoate, by weight of the preservation system.
The conditioner composition can contain from about 0.3 wt % to about 1.5 wt % of a second composition, alternatively from about 0.32 wt % to about 1 wt %, alternatively from about 0.33 wt % to about 0.8 wt %, alternatively from about 0.34 wt % to about 0.6 wt %, alternatively from about 0.35 wt % to about 0.5 wt %, alternatively from about 0.37 wt % to about 0.45 wt %, and alternatively from about 0.38 wt % to about 0.43 wt %. If the conditioner composition contains too much glycol and/or glyceryl ester the gel network structure may be destroyed, and the conditioner will not have consumer acceptable rheology and/or performance.
The preservation system can contain from about 50% to about 80% of the second composition, by weight of the preservation system, alternatively from about 50% to about 75%, by weight of the preservation system, alternatively from about 50% to about 70%, by weight of the preservation system, and alternatively from about 50% to about 67%, by weight of the preservation system.
The weight ratio of sodium benzoate to the second composition can be from about 1:4 to about 1:1, alternatively from about 1:3 to about 1:1, alternatively from about 1:2 to about 1:1, and from about 1:1.7 to about 1:1.
The conditioner composition can have a shear stress from about 50 Pa to about 500 Pa, alternatively from about 75 Pa to about 450 Pa, from about 100 Pa to about 400 Pa, from about 125 Pa to about 375 Pa, from about 130 Pa, to about 350 Pa, and from about 135 Pa to about 325 Pa. The shear stress can be determined using the Shear Stress Test Method, described hereafter.
The conditioner composition can have a pH of less than 5. Alternatively, the conditioner composition can have a pH from about 2.5 to about 5, alternatively from about 3.5 to about 4.5. The pH can be determined using the pH Test Method, described hereafter.
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, the terms “include,” “includes,” and “including,” are meant to be non-limiting and are understood to mean “comprise,” “comprises,” and “comprising,” respectively.
As used herein, the term “free of” means that 0% of an ingredient was intentionally added to the conditioner composition, or the conditioner composition comprises 0% of an ingredient by total weight of the composition, thus no detectable amount of the stated ingredient.
The term “substantially free of” as used herein means less than 0.5%, less than 0.3%, less than 0.1%, less than 0.05%, less than 0.01%, or less than an immaterial amount of a stated ingredient by total weight of the composition.
As used herein, “mixtures” is meant to include a simple combination of materials and any compounds that may result from their combination.
All percentages, parts and ratios are based upon the total weight of the compositions of the present invention, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active 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.
Cationic Surfactant
The compositions of the present invention can comprise a cationic surfactant. The cationic surfactant can be included in the composition at a level of from about 0.1%, alternatively from about 0.5%, alternatively from about 0.8%, alternatively from about 1.0%, and to about 20%, alternatively to about 10%, alternatively to about 8.0%, alternatively to about 6.0% by weight of the composition, in view of providing the benefits of the present invention.
The surfactant can be water-insoluble. In the present invention, “water-insoluble surfactants” means that the surfactants have a solubility in water at 25° C. of alternatively below 0.5 g/100 g (excluding 0.5 g/100 g) water, alternatively 0.3 g/100 g water or less.
Cationic surfactant can be one cationic surfactant or a mixture of two or more cationic surfactants. Alternatively, the cationic surfactant is selected from: a mono-long alkyl amine; a di-long alkyl quaternized ammonium salt; a mono-long alkyl cationic neutralized amino acid esters; a combination of a mono-long alkyl amine and a di-long alkyl quaternized ammonium salt; and a combination of a mono-long alkyl amine and a mono-long alkyl cationic neutralized amino acid esters.
In some examples, the conditioner composition can be substantially free of or free of cationic surfactants that have a quaternized ammonium salt.
Mono-Long Alkyl Amine
Mono-long alkyl amine can include those having one long alkyl chain of alternatively from 19 to 30 carbon atoms, alternatively from 19 to 24 carbon atoms, alternatively from 20 to 24 carbon atoms, alternatively from 20 to 22 alkyl group. Mono-long alkyl amines can include mono-long alkyl amidoamines Primary, secondary, and tertiary fatty amines can be used.
Tertiary amido amines having an alkyl group of from about 19 to about 22 carbons. Exemplary tertiary amido amines include: behenamidopropyldimethylamine, behenamidopropyldiethylamine, behenamidoethyldiethylamine, behenamidoethyldimethylamine, brassicamidopropyldimethylamine, brassicamidopropyldiethylamine, brassicamidoethyldiethylamine, brassicamidoethyldimethylamine Amines in the present invention are disclosed in U.S. Pat. No. 4,275,055, Nachtigal, et al.
In some examples, the conditioner composition can be substantially free of or free of stearamidopropyldimethylamine, stearamidopropyldiethylamine, stearamidoethyldiethylamine, stearamidoethyldimethylamine, palmitamidopropyldimethyl amine, palmitamidopropyldiethylamine, palmitamidoethyldiethylamine, palmitamidoethyldimethylamine, arachidamidopropyldimethylamine, arachidamidopropyldiethyl amine, arachidamidoethyldiethylamine, arachidamidoethyldimethylamine, and/or diethylaminoethylstearamide.
These amines are used in combination with acids such as 1-glutamic acid, lactic acid, hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid, tartaric acid, citric acid, 1-glutamic hydrochloride, maleic acid, and mixtures thereof; alternatively 1-glutamic acid, lactic acid, citric acid, at a molar ratio of the amine to the acid of from about 1:0.3 to about 1:2, alternatively from about 1:0.4 to about 1:1.
In some examples, the conditioner composition can be free of mono long alkyl quaternized ammonium salts.
Di-Long Alkyl Quaternized Ammonium Salts
When used, di-long alkyl quaternized ammonium salts are alternatively combined with a mono-long alkyl quaternized ammonium salt and/or mono-long alkyl amine salt, at the weight ratio of from 1:1 to 1:5, alternatively from 1:1.2 to 1:5, alternatively from 1:1.5 to 1:4, in view of stability in rheology and conditioning benefits.
Di-long alkyl quaternized ammonium salts can have two long alkyl chains of from 12 to 30 carbon atoms, alternatively from 16 to 24 carbon atoms, alternatively from 18 to 22 carbon atoms. Such di-long alkyl quaternized ammonium salts can have the formula (I):
wherein two of R71, R72, R73 and R74 are selected from an aliphatic group of from 12 to 30 carbon atoms, alternatively from 16 to 24 carbon atoms, alternatively from 18 to 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 30 carbon atoms; the remainder of R71, R72, R73 and R74 are independently selected from an aliphatic group of from 1 to about 8 carbon atoms, alternatively from 1 to 3 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 8 carbon atoms; and X− is a salt-forming anion selected from the group consisting of halides such as chloride and bromide, C1-C4 alkyl sulfate such as methosulfate and ethosulfate, and mixtures thereof. The aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. The longer chain aliphatic groups, e.g., those of about 16 carbons, or higher, can be saturated or unsaturated. Alternatively, two of R71, R72, R73 and R74 are selected from an alkyl group of from 12 to 30 carbon atoms, alternatively from 16 to 24 carbon atoms, alternatively from 18 to 22 carbon atoms; and the remainder of R71, R72, R73 and R74 are independently selected from CH3, C2H5, C2H4OH, CH2C6H5, and mixtures thereof.
Di-long alkyl cationic surfactants can include, for example, dialkyl (14-18) dimethyl ammonium chloride, ditallow alkyl dimethyl ammonium chloride, dihydrogenated tallow alkyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, and dicetyl dimethyl ammonium chloride.
High Melting Point Fatty Compound
The composition of the present invention comprises a high melting point fatty compound. The high melting point fatty compound can be included in the composition at a level of from about 1.0%, alternatively from about 1.5%, alternatively from about 2.0%, alternatively from about 2.5%, even alternatively from about 3%, and to about 30%, alternatively to about 15%, alternatively to about 8.0%, alternatively to about 7% by weight of the composition, in view of providing the benefits of the present invention.
The high melting point fatty compound can have a melting point of 25° C. or higher, alternatively 40° C. or higher, alternatively 45° C. or higher, alternatively 47° C. or higher, alternatively 49° C. or higher, in view of stability of the emulsion especially the gel network. Alternatively, such melting point is up to about 90° C., alternatively up to about 80° C., alternatively up to about 75° C., even alternatively up to about 71° C., in view of easier manufacturing and easier emulsification. In the present invention, the high melting point fatty compound can be used as a single compound or as a blend or mixture of at least two high melting point fatty compounds. When used as such blend or mixture, the above melting point means the melting point of the blend or mixture.
The high melting point fatty compound can be selected from the group consisting of fatty alcohols, fatty acids, and mixtures thereof. Further, it is understood by the artisan that, depending on the number and position of double bonds, and length and position of the branches, certain compounds having certain required carbon atoms may have a melting point of less than the above preferred in the present invention. Such compounds of low melting point are not intended to be included in this section. Nonlimiting examples of the high melting point compounds are found in International Cosmetic Ingredient Dictionary, Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992.
Among a variety of high melting point fatty compounds, fatty alcohols are alternatively used in the composition of the present invention. The fatty alcohols can have from about 14 to about 30 carbon atoms, alternatively from about 16 to about 22 carbon atoms. These fatty alcohols are saturated and can be straight or branched chain alcohols.
Fatty alcohols can include, for example, cetyl alcohol (having a melting point of about 56° C.), stearyl alcohol (having a melting point of about 58-59° C.), behenyl alcohol (having a melting point of about 71° C.), and mixtures thereof. These compounds are known to have the above melting point. However, they often have lower melting points when supplied, since such supplied products are often mixtures of fatty alcohols having alkyl chain length distribution in which the main alkyl chain is cetyl, stearyl, brassica or behenyl group.
The fatty alcohol can be a mixture of cetyl alcohol and stearyl alcohol.
Generally, in the mixture, the weight ratio of cetyl alcohol to stearyl alcohol is alternatively from about 1:9 to 9:1, alternatively from about 1:4 to about 4:1, alternatively from about 1:2.3 to about 1.5:1.
When using higher level of total cationic surfactant and high melting point fatty compounds, the mixture has the weight ratio of cetyl alcohol to stearyl alcohol of alternatively from about 1:1 to about 4:1, alternatively from about 1:1 to about 2:1, alternatively from about 1.2:1 to about 2:1, in view of avoiding to get too thick for spreadability. It may also provide more conditioning on damaged part of the hair.
Aqueous Carrier
The composition of the present invention can include an aqueous carrier. The level and species of the carrier can be selected according to the compatibility with other components, and other desired characteristic of the product.
The carrier can include water and water solutions of lower alkyl alcohols. The lower alkyl alcohols can be monohydric alcohols having 1 to 6 carbons, alternatively ethanol and isopropanol.
Alternatively, the aqueous carrier is substantially water. Deionized water is alternatively used. Water from natural sources including mineral cations can also be used, depending on the desired characteristic of the product. Generally, the compositions of the present invention comprise from about 40% to about 99%, alternatively from about 50% to about 95%, and alternatively from about 70% to about 93%, and alternatively from about 80% to about 92% water.
Gel Network
The gel network composition can be included in conditioner compositions to provide conditioning benefits, including improved wet feel of the hair after rinsing the conditioner. As used herein, the term “gel network” refers to a lamellar or vesicular solid crystalline phase which comprises at least one high melting point fatty compound, such as a fatty alcohol, as specified below, at least one surfactant, in particular a cationic surfactant, as specified below, and water or other suitable solvents. The lamellar or vesicular phase comprises bi-layers made up of a first layer comprising the high melting point fatty compound and the surfactant and alternating with a second layer comprising the water or other suitable solvent. Gel networks, generally, are further described by G. M. Eccleston, “Functions of Mixed Emulsifiers and Emulsifying Waxes in Dermatological Lotions and Creams”, Colloids and Surfaces A: Physiochem. and Eng. Aspects 123-124 (1997) 169-182; and by G. M Eccleston, “The Microstructure of Semisolid Creams”, Pharmacy International, Vol. 7, 63-70 (1986).
A gel network can be formed by the cationic surfactant, the high melting point fatty compound, and an aqueous carrier. The gel network is suitable for providing various conditioning benefits, such as slippery feel during the application to wet hair and softness and moisturized feel on dry hair.
Alternatively, when the gel network is formed, the cationic surfactant and the high melting point fatty compound are contained at a level such that the weight ratio of the cationic surfactant to the high melting point fatty compound is in the range of, alternatively from about 1:1 to about 1:10, alternatively from about 1:1.5 to about 1:7, alternatively from about 1:2 to about 1:6, in view of providing improved wet conditioning benefits.
Alternatively, especially when the gel network is formed, the composition of the present invention is substantially free of anionic surfactants, in view of stability of the gel network. In the present invention, “the composition being substantially free of anionic surfactants” means that: the composition is free of anionic surfactants; or, if the composition contains anionic surfactants, the level of such anionic surfactants is very low. In the present invention, a total level of such anionic surfactants, if included, alternatively 1% or less, alternatively 0.5% or less, alternatively 0.1% or less by weight of the composition. Most alternatively, the total level of such anionic surfactants is 0% by weight of the composition.
Additional Components
The composition of the present invention may include other additional components, which may be selected by the artisan according to the desired characteristics of the final product and which are suitable for rendering the composition more cosmetically or aesthetically acceptable or to provide them with additional usage benefits. Such other additional components generally are used individually at levels of from about 0.001% to about 10%, alternatively up to about 5% by weight of the composition.
A wide variety of other additional components can be formulated into the present compositions. These include: other conditioning agents such as aloe vera gel; aloe barbadensis leaf juice; Ecklonia radiata extract; natural oils and waxes with shea butter, safflower oil, cocoa butter, orange peel wax, olive oil, macadamia seed oil, Oenothera biennis oil, Crambe abyssinica see oil, argon oil, camelina oil, sunflower oil, almond oil, argania spinosa kernel oil, grape see oil, jojoba oil, coconut oil, meadowfoam seed oil, neem oil, linseed oil, castor oil, soybean oil, sesame oil, beeswax, sunflower wax, candelilla wax, rice bran wax, carnauba wax, bayberry wax and soy wax; essential oils such as lime peel oil, lavender oil, peppermint oil, cedarwood oil, tea tree oil, ylang-ylang oil and coensage oil which can be used in fragrance; hydrolyzed collagen with tradename Peptein 2000 available from Hormel, vitamin E with tradename Emix-d available from Eisai, panthenol available from Roche, panthenyl ethyl ether available from Roche, hydrolyzed keratin, proteins, plant extracts, and nutrients; pH adjusting agents, such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts, in general, such as potassium acetate and sodium chloride; coloring agents, such as any of the FD&C or D&C dyes; perfumes; and sequestering agents, such as disodium ethylenediamine tetra-acetate; and ultraviolet and infrared screening and absorbing agents such as octyl salicylate; antioxidants include: rosemary, tocopherol, vitamin E, vitamin A, tea extracts, and hydroxyacetophenone (available as Symsave® H from Symrise®); amino acids include histidine, 1-arginine and others.
Bacterial Microbial Susceptibility Testing Method
Bacterial microbial susceptibility testing is used to assess the anti-bacterial effectiveness of the preservation system in cosmetic rinse-off conditioner.
A bacterial pool (mixture in equal volumes) of challenge organisms used in the test is comprised of standardized solutions of the bacterial strains Escherichia coli (ATCC#8739), Staphylococcus aureus (ATCC#6538), Pseudomonas aeruginosa (ATCC#9027), Burkholderia cepacia (ATCC#25416), as well as Klebsiella pneumoniae, Enterobacter gergoviae and Serratia marcescens strains isolated from cosmetic products. The bacterial pool is prepared to have a concentration of approximately 6-8 log cfu/ml. To start the test, 0.1 ml of the bacterial pool is added into 10.0 g of a test conditioner. The test conditioner is then incubated for 2 days at 20-25° C. After incubation, a 1.0 g aliquot of product is neutralized using Modified Letheen Broth containing 1.5% polysorbate 80 (commercially available as Tween® 80 from Croda™) and 1% Lecithin to aid in microbial recovery/enumeration. Then, multiple diluted concentrations of this sample are transferred into petri dishes containing Modified Letheen Agar with 1.5% Tween® 80, and the agar plates are incubated at least 2 days at 30-35° C. Bacterial colony forming units (cfus) are then enumerated, and a bacterial log reduction from the starting log cfu/g challenge level is reported.
A 1 log cfu/g reduction equates to ˜a 90% bacterial reduction. A 2 log cfu/g reduction equates to ˜a 99% bacterial reduction. A 3 log cfu/g reduction equates to ˜a 99.9% bacterial reduction. A 4 log cfu/g reduction equates to ˜a 99.99% bacterial reduction. Greater log cfu/g reduction values indicate greater antimicrobial robustness from the preservation system.
Fungal Microbial Susceptibility Testing Method:
Fungal microbial susceptibility testing is used to assess the anti-fungal effectiveness of the preservation system in cosmetic rinse-off conditioner.
Standardized ATCC strains of the yeast Candida albicans (ATCC#10231) and mold Aspergillus brasiliensis (frm. niger) (ATCC#16404) are mixed in 1:1 (v:v) ratio, and this fungal pool is used as inoculum in the test. The concentration of the fungal pool is approximately 6-8 log cfu/ml. To start the test, 0.1 ml of the fungal pool is added into 10.0 g of a testing conditioner. After the inoculated sample is incubated for 2 days at 20-25° C., a 1.0 g aliquot of product is neutralized using Modified Letheen Broth containing 1.5% Tween® 80 and 1% Lecithin to aid in microbial recovery/enumeration. Then, multiple diluted concentrations of this sample are transferred into petri dishes containing Modified Letheen Agar with 1.5% Tween 80, and the agar plates are incubated for at least 5 days at 20-25° C., at which time fungal colony forming units (cfus) are then enumerated, and a fungal log reduction from the starting log cfu/g challenge level is calculated.
A 1 log cfu/g reduction equates to ˜a 90% fungal reduction. A 2 log cfu/g reduction equates to ˜a 99% fungal reduction. A 3 log cfu/g reduction equates to ˜a 99.9% fungal reduction. A 4 log cfu/g reduction equates to ˜a 99.99% fungal reduction. Greater log cfu/g reduction values indicate greater anti-fungal robustness from the preservation system.
Shear Stress
Shear stress is measured by shear rate sweep condition with a rheometer available from TA Instruments with a mode name of ARG2. Geometry has 40 mm diameter, 2° C. cone angle, and gap of 49 μm. Shear rate is logarithmically increased from 0 to 1200/s for 1 min, and temperature is kept at 26.7° C. Share stress at a high shear rate of 950/s is measured and defined above.
pH Method
First, calibrate the Mettler Toledo Seven Compact pH meter. Do this by turning on the pH meter and waiting for 30 seconds. Then take the electrode out of the storage solution, rinse the electrode with distilled water, and carefully wipe the electrode with a scientific cleaning wipe, such as a Kimiwipe®. Submerse the electrode in the pH 4 buffer and press the calibrate button. Wait until the pH icon stops flashing and press the calibrate button a second time. Rinse the electrode with distilled water and carefully wipe the electrode with a scientific cleaning wipe. Then submerse the electrode into the pH 7 buffer and press the calibrate button a second time. Wait until the pH icon stops flashing and press the calibrate button a third time. Rinse the electrode with distilled water and carefully wipe the electrode with a scientific cleaning wipe. Then submerse the electrode into the pH 10 buffer and press the calibrate button a third time. Wait until the pH icon stops flashing and press the measure button. Rinse the electrode with distilled water and carefully wipe with a scientific cleaning wipe.
Submerse the electrode into the testing sample and press the read button. Wait until the pH icon stops flashing and record the value.
The following are non-limiting examples of the conditioner compositions described herein. It will be appreciated that other modifications of the present invention within the skill of those in the 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 amount stated reflects the weight percent of the added material, unless otherwise specified.
The examples in Tables 1-3 were made as follows. Sodium benzoate and L-glutamic were dissolved in the water. The mixture was heated to 80° C. Then, the cationic surfactant and fatty alcohols were added to the mixture. Next, the mixture was cooled while the cationic surfactant and fatty alcohols continue to dissolve. Then, glycols or glyceryl esters were added, followed by oils and perfume when the temperature was below 45° C. The composition was cooled to room temperature to make the conditioner composition.
In Tables 1-3, below, the Micro˜Bacteria @ 2 days and the Micro-Fungi @ 2 days is determined by the Bacterial and Fungal Microbial Susceptibility Test Methods, described herein. In order for the preservation system to be effective, the level of microbes (bacteria and fungi) needs to be undetectable, which means that there is a greater than 99.99% reduction in microbes at two days as determined by the Bacterial and Fungal Microbial Susceptibility Test Methods. In Table 2, below, N/A indicates that the test was not performed.
Comparative Example 1 is the control and does not contain a preservation system. Comparative Example 1 does not provide enough microbe reduction at 2 days for bacteria and fungi.
Comparative Examples 2, 3, and 4 contain 0.20 wt %, 0.25 wt %, and 0.40 wt % sodium benzoate and these examples have an undetectable level (>99.99% reduction) of bacteria at two days. However, a preservation system that contains only sodium benzoate at these levels does not provide enough fungi reduction at two days, as these examples only have a ˜90% reduction.
Comparative Examples 5 and 6 include a preservation system that has both sodium benzoate and caprylyl glycol. These examples have an undetectable level (>99.99% reduction) of bacteria at two days. The combination of sodium benzoate and caprylyl glycol improves the reduction of fungi at 2 days, as compared to Comparative Examples 2, 3, and 4. However, there is still a detectable level of fungi and therefore the preservation system in these examples is not considered effective.
Comparative Example 7 has a preservation system with 0.20 wt % sodium benzoate and 0.40 wt % glyceryl caprylate/caprate (a glyceryl ester) and this example has an undetectable level (>99.99% reduction) of bacteria at two days. However, it has a >90% reduction in fungi at two days and is ineffective.
Similar to Comparative Example 7, Comparative Example 8 has a preservation system with 0.20 wt % sodium benzoate and 0.40 wt % glyceryl caprylate (and) glyceryl undeylenate and this example has an undetectable level (>99.99% reduction) of bacteria at two days. However, it has a >90% reduction in fungi at two days and is ineffective.
Comparative Example 9 contains 0.20% sodium benzoate and behentrimonium chloride (cationic surfactant) and this example has an undetectable level (>99.99% reduction) of bacteria at two days. However, it has a detectable level of fungi (>99% reduction) at two days and is therefore ineffective.
Comparative Example 10 contains 1 wt % sodium benzoate. As shown in
Comparative Example 11 contains 2 wt % caprylyl glycol. As shown in
1Sodium Benzoate, available from Kalama ®
2Caprylyl Glycol, available from Procter and Gamble ®
3Glyceryl Caprylate/Caprate (STEPAN-MILD ® GCC), available from Stepan ®
4Glyceryl Caprylate (and) Glyceryl Undecylenate (Lexgard ® Natural), available from Index ®
5Behentrimonium Chloride/IPA (Genamin KDMP), available from Clariant ™ at 80% active level
6Behenamidopropyl Dimethylamine (BAPDMA) (Incromine ™ BD), available from Croda ®
7L-Glutamic Acid, available from Ajinomoto ®
8Cetyl alcohol, 95% active level available from Procter & Gamble ®
9Stearyl alcohol, 97% active level, available from Procter & Gamble ®
All of the Examples in Table 3 have preservation systems that are effective (i.e. bacteria and fungi are not detectable (>99.99% reduction) at 2 days) and a creamy and smooth appearance that is consumer preferred.
All of the Examples in Table 3 have a creamy and smooth appearance that can be consumer preferred.
Combinations:
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 and any patent application or patent to which this application claims priority or benefit thereof, 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 |
---|---|---|---|
2356168 | Mabley | Aug 1944 | A |
2396278 | Otto | Mar 1946 | A |
2438091 | Lynch | Mar 1948 | A |
2486921 | Byerly | Nov 1949 | A |
2486922 | Bruce | Nov 1949 | A |
2528378 | Mannheimer | Oct 1950 | A |
2613185 | Marshall | Oct 1952 | A |
2658072 | Milton | Nov 1953 | A |
2694668 | Fricke | Nov 1954 | A |
2809971 | Jack et al. | Oct 1957 | A |
3152046 | Maria | Oct 1964 | A |
3236733 | Karsten et al. | Feb 1966 | A |
3321425 | Karl-ludwig et al. | May 1967 | A |
3332880 | Adriaan et al. | Jul 1967 | A |
3426440 | Shen et al. | Feb 1969 | A |
3463308 | Deneke | Aug 1969 | A |
3489688 | Pospischil | Jan 1970 | A |
3653383 | Wise | Apr 1972 | A |
3695989 | Albert | Oct 1972 | A |
3753196 | Kurtz et al. | Aug 1973 | A |
3761418 | Parran | Sep 1973 | A |
3929678 | Laughlin | Dec 1975 | A |
3967921 | Haberli et al. | Jul 1976 | A |
4020156 | Murray et al. | Apr 1977 | A |
4051081 | Jabs et al. | Sep 1977 | A |
4089945 | Brinkman et al. | May 1978 | A |
4149551 | Benjamin et al. | Apr 1979 | A |
4196190 | Gehman et al. | Apr 1980 | A |
4197865 | Jacquet et al. | Apr 1980 | A |
4206196 | Davis | Jun 1980 | A |
4217914 | Jacquet et al. | Aug 1980 | A |
4272511 | Papantoniou et al. | Jun 1981 | A |
4323683 | Bolich, Jr. et al. | Apr 1982 | A |
4345080 | Bolich, Jr. | Aug 1982 | A |
D266829 | Yoshizawa et al. | Nov 1982 | S |
4379753 | Bolich, Jr. | Apr 1983 | A |
4381919 | Jacquet et al. | May 1983 | A |
4422853 | Jacquet et al. | Dec 1983 | A |
4470982 | Winkler | Sep 1984 | A |
4507280 | Pohl et al. | Mar 1985 | A |
4529586 | De Marco et al. | Jul 1985 | A |
4536361 | Torobin | Aug 1985 | A |
4565647 | Llenado | Jan 1986 | A |
D286450 | Tovey | Oct 1986 | S |
4663158 | Wolfram et al. | May 1987 | A |
4710374 | Grollier et al. | Dec 1987 | A |
4822613 | Rodero | Apr 1989 | A |
4885107 | Wetzel | Dec 1989 | A |
4976953 | Orr et al. | Dec 1990 | A |
4990280 | Thorengaard | Feb 1991 | A |
5055384 | Kuehnert | Oct 1991 | A |
5061481 | Suzuki et al. | Oct 1991 | A |
5062889 | Hoehl et al. | Nov 1991 | A |
5062994 | Imperatori | Nov 1991 | A |
5094853 | Hagarty | Mar 1992 | A |
5098636 | Balk | Mar 1992 | A |
5100657 | Ansher-jackson et al. | Mar 1992 | A |
5100658 | Bolich, Jr. et al. | Mar 1992 | A |
5104646 | Bolich, Jr. | Apr 1992 | A |
5106609 | Bolich, Jr. | Apr 1992 | A |
5166276 | Hayama et al. | Nov 1992 | A |
D334420 | Copeland et al. | Mar 1993 | S |
5220033 | Kamei et al. | Jun 1993 | A |
5261426 | Kellett et al. | Nov 1993 | A |
5280079 | Allen et al. | Jan 1994 | A |
RE34584 | Grote et al. | Apr 1994 | E |
5391368 | Gerstein | Feb 1995 | A |
D357115 | Ashley et al. | Apr 1995 | S |
5409703 | Mcanalley et al. | Apr 1995 | A |
D358025 | Martin et al. | May 1995 | S |
5415810 | Lee | May 1995 | A |
5429628 | Trinh et al. | Jul 1995 | A |
5455114 | Ohmory | Oct 1995 | A |
5457895 | Thompson et al. | Oct 1995 | A |
5476597 | Sakata et al. | Dec 1995 | A |
5501238 | Borstel et al. | Mar 1996 | A |
5580481 | Sakata et al. | Dec 1996 | A |
5582786 | Brunskill et al. | Dec 1996 | A |
D378180 | Hayes | Feb 1997 | S |
5660845 | Trinh et al. | Aug 1997 | A |
5672576 | Behrens et al. | Sep 1997 | A |
5673576 | Chen et al. | Oct 1997 | A |
5674478 | Dodd | Oct 1997 | A |
5750122 | Evans | May 1998 | A |
5780047 | Kamiya et al. | Jul 1998 | A |
D398847 | Wyslotsky | Sep 1998 | S |
5885561 | Flemming et al. | Mar 1999 | A |
D407640 | Crapser et al. | Apr 1999 | S |
D408223 | Henry | Apr 1999 | S |
5911224 | Berger | Jun 1999 | A |
5925603 | D'Angelo | Jul 1999 | A |
5955419 | Barket, Jr. et al. | Sep 1999 | A |
5976454 | Sterzel et al. | Nov 1999 | A |
D418415 | Hayes | Jan 2000 | S |
D418750 | Blin | Jan 2000 | S |
6010719 | Remon et al. | Jan 2000 | A |
6029808 | Peck et al. | Feb 2000 | A |
6034043 | Fujiwara | Mar 2000 | A |
D427902 | Hayes | Jul 2000 | S |
6106849 | Malkan et al. | Aug 2000 | A |
6177391 | Zafar | Jan 2001 | B1 |
6200949 | Reijmer et al. | Mar 2001 | B1 |
D442739 | Friesenhahn | May 2001 | S |
D443389 | Friesenhahn | Jun 2001 | S |
D449881 | Mock, Sr. | Oct 2001 | S |
D450378 | Minakuchi et al. | Nov 2001 | S |
6365142 | Tamura | Apr 2002 | B1 |
D462900 | Yamada et al. | Sep 2002 | S |
6458754 | Velazquez et al. | Oct 2002 | B1 |
D465303 | Friesenhahn | Nov 2002 | S |
6503521 | Atis et al. | Jan 2003 | B1 |
6525034 | Dalrymple et al. | Feb 2003 | B2 |
D484749 | Garraway | Jan 2004 | S |
6790814 | Marin | Sep 2004 | B1 |
6800295 | Fox | Oct 2004 | B2 |
6808375 | Kloetzer | Oct 2004 | B2 |
6825161 | Shefer et al. | Nov 2004 | B2 |
6831046 | Carew et al. | Dec 2004 | B2 |
6846784 | Engel et al. | Jan 2005 | B2 |
6878368 | Ohta et al. | Apr 2005 | B2 |
6943200 | Corrand et al. | Sep 2005 | B1 |
D515915 | Karim | Feb 2006 | S |
7015181 | Lambino | Mar 2006 | B2 |
7208460 | Shefer et al. | Apr 2007 | B2 |
D549051 | Nordwall | Aug 2007 | S |
7285520 | Krzysik | Oct 2007 | B2 |
7387787 | Fox | Jun 2008 | B2 |
D578881 | Friedland | Oct 2008 | S |
D588332 | Phelan | Mar 2009 | S |
7832552 | Newman | Nov 2010 | B2 |
7846462 | Spadini et al. | Dec 2010 | B2 |
7892992 | Kamada et al. | Feb 2011 | B2 |
7901696 | Eknoian et al. | Mar 2011 | B2 |
D640921 | Caldwell | Jul 2011 | S |
D651096 | Nakagiri | Dec 2011 | S |
D655154 | Amos | Mar 2012 | S |
8197830 | Helfman et al. | Jun 2012 | B2 |
8268764 | Glenn, Jr. et al. | Sep 2012 | B2 |
8273333 | Glenn, Jr. | Sep 2012 | B2 |
8288332 | Fossum et al. | Oct 2012 | B2 |
8309505 | Fossum et al. | Nov 2012 | B2 |
8349341 | Glenn, Jr. et al. | Jan 2013 | B2 |
8349786 | Glenn, Jr. et al. | Jan 2013 | B2 |
8349787 | Glenn, Jr. et al. | Jan 2013 | B2 |
8357728 | Butler et al. | Jan 2013 | B2 |
D680882 | Logue | Apr 2013 | S |
8415287 | Glenn, Jr. et al. | Apr 2013 | B2 |
D682622 | Keys | May 2013 | S |
8461090 | Glenn, Jr. et al. | Jun 2013 | B2 |
8461091 | Glenn, Jr. | Jun 2013 | B2 |
8466099 | Glenn, Jr. et al. | Jun 2013 | B2 |
D685436 | Menting | Jul 2013 | S |
8476211 | Glenn, Jr. et al. | Jul 2013 | B2 |
8546640 | Popovsky et al. | Oct 2013 | B2 |
D694621 | Mccarthy | Dec 2013 | S |
8723333 | Park et al. | May 2014 | B2 |
8765170 | Glenn, Jr. | Jul 2014 | B2 |
D739227 | Mitchell et al. | Sep 2015 | S |
D740928 | Bruining et al. | Oct 2015 | S |
9198838 | Glenn, Jr. | Dec 2015 | B2 |
D769522 | Venet | Oct 2016 | S |
9539444 | Kinoshita et al. | Jan 2017 | B2 |
D793025 | Slusarczyk et al. | Aug 2017 | S |
D797551 | Chatterton | Sep 2017 | S |
D798143 | Chatterton | Sep 2017 | S |
D808583 | Zietek | Jan 2018 | S |
10226404 | Takahashi et al. | Mar 2019 | B2 |
10278915 | Kawa | May 2019 | B1 |
10294586 | Sivik et al. | May 2019 | B2 |
D851344 | Carlson et al. | Jun 2019 | S |
D857156 | Hani | Aug 2019 | S |
10391046 | Hartnett et al. | Aug 2019 | B2 |
10413496 | Pistorio et al. | Sep 2019 | B2 |
D862020 | Gorrell et al. | Oct 2019 | S |
10449131 | Li et al. | Oct 2019 | B2 |
D866893 | Hunt et al. | Nov 2019 | S |
D867717 | Chavez | Nov 2019 | S |
D868953 | Mckendree | Dec 2019 | S |
10569286 | Anderson et al. | Feb 2020 | B2 |
10694917 | Dreher et al. | Jun 2020 | B2 |
D910434 | Tan et al. | Feb 2021 | S |
D910457 | Lee | Feb 2021 | S |
20020077264 | Roberts et al. | Jun 2002 | A1 |
20020081930 | Jackson et al. | Jun 2002 | A1 |
20020098994 | Zafar | Jul 2002 | A1 |
20020099109 | Dufton et al. | Jul 2002 | A1 |
20020177621 | Hanada et al. | Nov 2002 | A1 |
20020187181 | Godbey et al. | Dec 2002 | A1 |
20030018242 | Hursh et al. | Jan 2003 | A1 |
20030032573 | Tanner et al. | Feb 2003 | A1 |
20030045441 | Hsu et al. | Mar 2003 | A1 |
20030069154 | Hsu et al. | Apr 2003 | A1 |
20030080150 | Cowan | May 2003 | A1 |
20030082129 | Buckingham et al. | May 2003 | A1 |
20030099691 | Lydzinski et al. | May 2003 | A1 |
20030099692 | Lydzinski et al. | May 2003 | A1 |
20030180242 | Eccard et al. | Sep 2003 | A1 |
20030186826 | Eccard et al. | Oct 2003 | A1 |
20030194416 | Shefer | Oct 2003 | A1 |
20030199412 | Gupta | Oct 2003 | A1 |
20030209166 | Vanmaele et al. | Nov 2003 | A1 |
20030215522 | Johnson et al. | Nov 2003 | A1 |
20030232183 | Dufton | Dec 2003 | A1 |
20040029762 | Hensley | Feb 2004 | A1 |
20040032859 | Miao | Feb 2004 | A1 |
20040048759 | Ribble et al. | Mar 2004 | A1 |
20040048771 | Mcdermott | Mar 2004 | A1 |
20040053808 | Raehse et al. | Mar 2004 | A1 |
20040059055 | Inada | Mar 2004 | A1 |
20040071742 | Popplewell | Apr 2004 | A1 |
20040071755 | Fox | Apr 2004 | A1 |
20040108615 | Foley | Jun 2004 | A1 |
20040110656 | Casey et al. | Jun 2004 | A1 |
20040115155 | Salvador et al. | Jun 2004 | A1 |
20040126585 | Kerins et al. | Jul 2004 | A1 |
20040175404 | Shefer | Sep 2004 | A1 |
20040180597 | Kamada | Sep 2004 | A1 |
20040202632 | Gott et al. | Oct 2004 | A1 |
20040206270 | Vanmaele et al. | Oct 2004 | A1 |
20040242097 | Hasenoehrl | Dec 2004 | A1 |
20040242772 | Huth et al. | Dec 2004 | A1 |
20050069575 | Fox | Mar 2005 | A1 |
20050136780 | Clark et al. | Jun 2005 | A1 |
20050137272 | Gaserod | Jun 2005 | A1 |
20050159730 | Kathrani et al. | Jul 2005 | A1 |
20050202992 | Grandio et al. | Sep 2005 | A1 |
20050220745 | Lu | Oct 2005 | A1 |
20050232954 | Yoshinari et al. | Oct 2005 | A1 |
20050272836 | Yaginuma et al. | Dec 2005 | A1 |
20050287106 | Legendre | Dec 2005 | A1 |
20060002880 | Peffly et al. | Jan 2006 | A1 |
20060013869 | Ignatious | Jan 2006 | A1 |
20060024256 | Wells et al. | Feb 2006 | A1 |
20060052263 | Roreger et al. | Mar 2006 | A1 |
20060064510 | Low et al. | Mar 2006 | A1 |
20060078528 | Yang et al. | Apr 2006 | A1 |
20060078529 | Uchida et al. | Apr 2006 | A1 |
20060128592 | Ross | Jun 2006 | A1 |
20060159730 | Simon | Jul 2006 | A1 |
20060228319 | Vona, Jr. et al. | Oct 2006 | A1 |
20060269501 | Johnson | Nov 2006 | A1 |
20060274263 | Yacktman et al. | Dec 2006 | A1 |
20070028939 | Mareri et al. | Feb 2007 | A1 |
20070031369 | Verboom et al. | Feb 2007 | A1 |
20070099813 | Luizzi | May 2007 | A1 |
20070110792 | Simon | May 2007 | A9 |
20070135528 | Butler et al. | Jun 2007 | A1 |
20070149435 | Koenig et al. | Jun 2007 | A1 |
20070190005 | Rozsa | Aug 2007 | A1 |
20070225388 | Cooper et al. | Sep 2007 | A1 |
20070237736 | Burgo et al. | Oct 2007 | A1 |
20080035174 | Aubrun-sonneville | Feb 2008 | A1 |
20080083420 | Glenn et al. | Apr 2008 | A1 |
20080090939 | Netravali et al. | Apr 2008 | A1 |
20080131695 | Aquad et al. | Jun 2008 | A1 |
20080138492 | Cingotti | Jun 2008 | A1 |
20080139672 | Rozsa et al. | Jun 2008 | A1 |
20080152894 | Beihoffer et al. | Jun 2008 | A1 |
20080153730 | Tsaur | Jun 2008 | A1 |
20080187507 | Johnson | Aug 2008 | A1 |
20080215023 | Scavone et al. | Sep 2008 | A1 |
20080292669 | Deng et al. | Nov 2008 | A1 |
20080293839 | Stobby | Nov 2008 | A1 |
20090197787 | Venet et al. | Aug 2009 | A1 |
20090232873 | Glenn, Jr. et al. | Sep 2009 | A1 |
20090263342 | Glenn, Jr. | Oct 2009 | A1 |
20100018641 | Branham | Jan 2010 | A1 |
20100150858 | Runglertkriangkrai | Jun 2010 | A1 |
20100150976 | Schnitzler | Jun 2010 | A1 |
20100167971 | Glenn, Jr. et al. | Jul 2010 | A1 |
20100173817 | Glenn, Jr. et al. | Jul 2010 | A1 |
20100286011 | Glenn, Jr. et al. | Nov 2010 | A1 |
20100291165 | Glenn, Jr. et al. | Nov 2010 | A1 |
20110023240 | Fossum | Feb 2011 | A1 |
20110027328 | Baig et al. | Feb 2011 | A1 |
20110028374 | Fossum et al. | Feb 2011 | A1 |
20110033509 | Simon | Feb 2011 | A1 |
20110165110 | Kinoshita et al. | Jul 2011 | A1 |
20110182956 | Glenn, Jr. et al. | Jul 2011 | A1 |
20110189247 | Glenn, Jr. | Aug 2011 | A1 |
20110195098 | Glenn, Jr. | Aug 2011 | A1 |
20110250256 | Hyun-oh et al. | Oct 2011 | A1 |
20110287687 | Kramer et al. | Nov 2011 | A1 |
20120021026 | Glenn, Jr. | Jan 2012 | A1 |
20120052036 | Glenn, Jr. | Mar 2012 | A1 |
20120052037 | Sivik et al. | Mar 2012 | A1 |
20120107534 | Wnuk et al. | May 2012 | A1 |
20120237576 | Gordon | Sep 2012 | A1 |
20120270029 | Glenn, Jr. et al. | Oct 2012 | A1 |
20120294823 | Aramwit | Nov 2012 | A1 |
20120321580 | Glenn, Jr. | Dec 2012 | A1 |
20130236520 | Popovsky et al. | Sep 2013 | A1 |
20130280193 | Carter et al. | Oct 2013 | A1 |
20130303419 | Glenn, Jr. et al. | Nov 2013 | A1 |
20140105942 | Pistorio et al. | Apr 2014 | A1 |
20140329428 | Glenn, Jr. | Nov 2014 | A1 |
20140356307 | Yang | Dec 2014 | A1 |
20150017218 | Pettigrew et al. | Jan 2015 | A1 |
20150250701 | Hamersky et al. | Sep 2015 | A1 |
20150290109 | Simonnet et al. | Oct 2015 | A1 |
20150297494 | Mao | Oct 2015 | A1 |
20150313803 | Lynch et al. | Nov 2015 | A1 |
20150313804 | Lynch et al. | Nov 2015 | A1 |
20150313805 | Lynch et al. | Nov 2015 | A1 |
20150313806 | Lynch et al. | Nov 2015 | A1 |
20150313807 | Lynch et al. | Nov 2015 | A1 |
20150313808 | Lynch et al. | Nov 2015 | A1 |
20150313809 | Lynch et al. | Nov 2015 | A1 |
20150313823 | Lockett et al. | Nov 2015 | A1 |
20150315350 | Mao et al. | Nov 2015 | A1 |
20160089314 | Marsh | Mar 2016 | A1 |
20160101026 | Pratt | Apr 2016 | A1 |
20160101204 | Lynch | Apr 2016 | A1 |
20160143825 | Pesaro et al. | May 2016 | A1 |
20160143827 | Castan Barberan et al. | May 2016 | A1 |
20160158134 | Disalvo | Jun 2016 | A1 |
20160206533 | Callens | Jul 2016 | A1 |
20160243007 | Constantine et al. | Aug 2016 | A1 |
20160250109 | Dreher et al. | Sep 2016 | A1 |
20160361242 | Durtschi et al. | Dec 2016 | A1 |
20160367104 | Dreher et al. | Dec 2016 | A1 |
20170056300 | Constantine et al. | Mar 2017 | A1 |
20170056301 | Constantine et al. | Mar 2017 | A1 |
20170105917 | Iwata | Apr 2017 | A1 |
20170121641 | Smith | May 2017 | A1 |
20170202760 | Callens | Jul 2017 | A1 |
20170335080 | Mao et al. | Nov 2017 | A1 |
20180028435 | Punsch et al. | Feb 2018 | A1 |
20180071193 | Fields | Mar 2018 | A1 |
20180311135 | Chang et al. | Nov 2018 | A1 |
20180311137 | McKiernan | Nov 2018 | A1 |
20180333339 | Hamersky | Nov 2018 | A1 |
20180333494 | Lane et al. | Nov 2018 | A1 |
20180334644 | Hamersky et al. | Nov 2018 | A1 |
20180360702 | Demarcq et al. | Dec 2018 | A1 |
20190282457 | Pratt | Sep 2019 | A1 |
20190282461 | Glassmeyer | Sep 2019 | A1 |
20190350819 | Hamersky et al. | Nov 2019 | A1 |
20200093710 | Hamersky | Mar 2020 | A1 |
20200108003 | Iwata et al. | Apr 2020 | A1 |
20200197272 | Hertenstein et al. | Jun 2020 | A1 |
20200214946 | Chan et al. | Jul 2020 | A1 |
20200308360 | Mao et al. | Oct 2020 | A1 |
20200405587 | Song | Dec 2020 | A1 |
20210000733 | Hilvert | Jan 2021 | A1 |
20210094744 | Benson et al. | Apr 2021 | A1 |
20210107263 | Bartolucci et al. | Apr 2021 | A1 |
20210147763 | Tan et al. | May 2021 | A1 |
20210161784 | Zhao et al. | Jun 2021 | A1 |
20220168200 | Zhao et al. | Jun 2022 | A1 |
Number | Date | Country |
---|---|---|
1138091 | Dec 1996 | CN |
1219388 | Jun 1999 | CN |
1268558 | Oct 2000 | CN |
1357613 | Jul 2002 | CN |
1530431 | Sep 2004 | CN |
1583991 | Feb 2005 | CN |
106726634 | May 2017 | CN |
106728634 | May 2017 | CN |
109589279 | Mar 2020 | CN |
19607851 | Sep 1997 | DE |
10331767 | Feb 2005 | DE |
102010002863 | Sep 2011 | DE |
102010026747 | Jan 2012 | DE |
DM100932 | Apr 2018 | DE |
DM100938 | Apr 2018 | DE |
DM101063 | May 2018 | DE |
DM101100 | May 2018 | DE |
DM101101 | May 2018 | DE |
609808 | Aug 1994 | EP |
0858828 | Aug 1998 | EP |
1206933 | May 2002 | EP |
1217987 | Dec 2004 | EP |
1160311 | Mar 2006 | EP |
1808157 | Jul 2007 | EP |
1958532 | Aug 2008 | EP |
2085434 | Aug 2009 | EP |
1317916 | Oct 2010 | EP |
2606725 | Jun 2013 | EP |
2871685 | Dec 2005 | FR |
2886845 | Dec 2006 | FR |
2992217 | Dec 2013 | FR |
2235204 | Feb 1991 | GB |
2355008 | Apr 2001 | GB |
58021608 | Feb 1983 | JP |
S58216109 | Dec 1983 | JP |
S6272609 | Apr 1987 | JP |
S6272610 | Apr 1987 | JP |
S6281432 | Apr 1987 | JP |
H01172319 | Jul 1989 | JP |
H01313418 | Dec 1989 | JP |
H0275650 | Mar 1990 | JP |
H05344873 | Dec 1993 | JP |
H0617083 | Jan 1994 | JP |
0753349 | Feb 1995 | JP |
H0789852 | Apr 1995 | JP |
H08325133 | Dec 1996 | JP |
H09216909 | Aug 1997 | JP |
H10251371 | Sep 1998 | JP |
H11322591 | Nov 1999 | JP |
2000053998 | Feb 2000 | JP |
2003073700 | Mar 2003 | JP |
2003082397 | Mar 2003 | JP |
2003113032 | Apr 2003 | JP |
2004256799 | Sep 2004 | JP |
2004345983 | Dec 2004 | JP |
2005171063 | Jun 2005 | JP |
2006097010 | Apr 2006 | JP |
2007091954 | Apr 2007 | JP |
2007197540 | Aug 2007 | JP |
20020003442 | Jan 2002 | KR |
20150049027 | May 2015 | KR |
8301943 | Jun 1983 | WO |
9514495 | Jun 1995 | WO |
0112134 | Feb 2001 | WO |
0119948 | Mar 2001 | WO |
0125393 | Apr 2001 | WO |
200125322 | Apr 2001 | WO |
2001024770 | Apr 2001 | WO |
2001054667 | Aug 2001 | WO |
2004032859 | Apr 2004 | WO |
2004041991 | May 2004 | WO |
2005003423 | Jan 2005 | WO |
2005070374 | Aug 2005 | WO |
2005075547 | Aug 2005 | WO |
2007033598 | Mar 2007 | WO |
2007093558 | Aug 2007 | WO |
2009016555 | Feb 2009 | WO |
2009019571 | Feb 2009 | WO |
2009095891 | Aug 2009 | WO |
2010077627 | Jul 2010 | WO |
2010085569 | Jul 2010 | WO |
2011113501 | Sep 2011 | WO |
2012120199 | Sep 2012 | WO |
2012172207 | Dec 2012 | WO |
2013150044 | Oct 2013 | WO |
2014124070 | Aug 2014 | WO |
2015053281 | Apr 2015 | WO |
2018023180 | Feb 2018 | WO |
2018098542 | Jun 2018 | WO |
2019001940 | Jan 2019 | WO |
2019014868 | Jan 2019 | WO |
2019090098 | May 2019 | WO |
2019142194 | Jul 2019 | WO |
Entry |
---|
VegeCide. https://web.archive.org/web/20120824144807/http://www.ingredientstodiefor.com/item/VegeCide/925/. Published: Aug. 24, 2012. |
PCT Search Report and Written Opinion for PCT/US2020/062656 dated Mar. 12, 2021. |
All Office Actions, U.S. Appl. No. 16/953,975. |
All Office Actions, U.S. Appl. No. 17/108,081. |
All Office Actions, U.S. Appl. No. 17/209,292. |
Anonymous “P8136 Poly(vinyl alcohol)” Internet article, [Online] XP002538935 retrieved from the Internet: URL:hllp/20NWW.sigmaaldrich.com/catalog/ProductDetail.do?D7=0%N25-SEARCH_ CONCAT PNOIDBRAND KEY%N4=P8136%7SCIAL%N25=0%QS=ON%F=SPEC retrieved on Jul. 28, 2009. |
Briscoe et al. “The effects of hydrogen bonding upon the viscosity of aqueous poly( vinyl alcohol) solutions,” from Polymer, 41 (2000), pp. 3851-3860. |
Guerrini et al. “Thermal and Structural Characterization of Nanofibers of Poly( vinyl alcohol) Produced by Electrospinning”, Journal of Applied Polymer Science, vol. 112, Feb. 9, 2009, pp. 1680-1687. |
Hildebrand, T., et al. “Quantification of bone microarchitecture with the structure mode index”, Computer Methods in Biomechanics and Biomedical Engineering, vol. 1, Jan. 14, 1997, pp. 15-23. |
How Gemz work?, Gemz Hair Care, published on Oct. 1, 2018, retrieved on Apr. 27, 2021, retrieved from the Internet URL: https:// www.youtube.com/watch?v=ts1waYk43g4. |
https ://www.craftcuts.com/hexagon-craft-shape. htmlHexagon wood cutouts, www.craftcuts.com, 1 page, reviewed as early as May 2018 (Year: 2018). |
Okasaka et al., “Evaluation Of Anionic Surfactants Effects On The Skin Barrier Function Based On Skin Permeability”, Pharmaceutical Development and Technology, vol. 24, No. 1, Jan. 23, 2018, pp. 99-104. |
Product Review: Gemz Solid Shampoo, Travel As Much, published on Mar. 19, 2019, retrieved on Apr. 27, 2021, retrieved from the Internet URL: https://travelasmuch.com/gemz-solid-shampoo-review/. |
Unpublished U.S. Appl. No. 17/209,292, filed Mar. 23, 2021, to Jennifer Mary Marsh et. al. |
Vaughan, C.D. “Solubility, Effects in Product, Package, Penetration and Preservation”, Cosmetics and Toiletries, vol. 103, Oct. 1988. |
Veslerby, A.: “Star Volume in Bone Research: A Histomorphometric Analysis Of Trabecular Bone Structure UsingVertical Sections”, Anal Rec: Feb. 1993, 232(2), pp. 325-334. |
Zhang et al. “Study on Morphology of Electrospun Poly( vinyl alcohol) Mats,” European Polymer Journal 41 (2005), pp. 423-432. |
All Office Actions; U.S. Appl. No. 17/398,024, filed Aug. 10, 2021. |
All Office Actions; U.S. Appl. No. 17/398,025, filed Aug. 10, 2021. |
All Office Actions; U.S. Appl. No. 17/398,020, filed Aug. 10, 2021. |
Unpublished U.S. Appl. No. 17/398,020, filed Aug. 10, 2021, to Jean Jianqun Zhao et. al. |
Unpublished U.S. Appl. No. 17/398,024, filed Aug. 10, 2021, to Jean Jianqun Zhao et. al. |
Unpublished U.S. Appl. No. 17/398,025, filed Aug. 10, 2021, to Jean Jianqun Zhao et. al. |
All Office Actions; U.S. Appl. No. 17/537,549, filed Nov. 30, 2021. |
Number | Date | Country | |
---|---|---|---|
20210161780 A1 | Jun 2021 | US |
Number | Date | Country | |
---|---|---|---|
62942209 | Dec 2019 | US | |
62942208 | Dec 2019 | US |