Oral care composition comprising a dicarboxylic acid

Abstract

Disclosed are oral care compositions comprising a dicarboxylic acid and being free of or having a low content of dental abrasives. The oral care compositions show the ability to remove stains from teeth, to prevent stains on the surface of the oral cavity and are thus suitable for tooth whitening.

Description

Technical Field

[0001] This invention relates to oral care compositions containing dicarboxylic acids that are free of dental abrasives or have a low content of dental abrasives and have the ability to remove dental stains. Background Technology

[0002] Oral care compositions (such as toothpaste and / or dental cleaning compositions) are applied to the oral cavity to clean and / or maintain the aesthetics and / or health of teeth, gums, and / or tongue. Additionally, many oral care compositions can be used to remove and / or prevent stains on oral surfaces. Whitening of hard tissue surfaces in oral care can be achieved through chemical or physical methods. Physical agents include combinations of brushes and abrasives. Chemical agents include oxidizing agents (e.g., peroxides), anti-tartar agents (e.g., polyphosphates), or other agents capable of removing surface stains through chemical action (e.g., bicarbonates).

[0003] Each reagent has its drawbacks. Oxidizing agents are difficult to avoid reacting with other components of the oral care composition throughout its lifespan. Additionally, they do not react with some surface stains, thus failing to achieve their primary purpose. Polyphosphate-based anti-tartar agents are very prone to hydrolysis, breaking down into ineffective orthophosphates. In the presence of soluble fluoride, this breakdown can be accelerated, producing insoluble fluoride. Furthermore, they can irritate the soft tissues of the mouth. Some other chemical reagents have characteristic tastes that are unpleasant to consumers. Bicarbonate-based toothpastes tend to taste like baking soda, and their unique experience is not enjoyed by most consumers. In short, formulating existing whitening agents is challenging due to the various reasons inherent in each reagent.

[0004] In addition to chemical whitening agents, toothpaste and / or dental cleaning compositions also contain abrasives to physically remove stains from hard tissue surfaces when applied in combination with a brush. Dental abrasives can damage teeth. Therefore, there is a need for a toothpaste composition that effectively removes stains while minimizing or eliminating abrasives.

[0005] Therefore, there is a need for a whitening toothpaste that can effectively remove stains with a low concentration of abrasives. Summary of the Invention

[0006] This invention discloses an oral care composition comprising: a) about 1.0% to about 10.0% by weight of the oral care composition of one or more dicarboxylic acids or their salts or combinations thereof, wherein the one or more dicarboxylic acids include oxalic acid, malic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, propanedioic acid, tartaric acid, D-tartaric acid, L-tartaric maleic acid or their salts or combinations thereof. b) one or more surfactants; and c) Less than 5% abrasive by weight of the oral care composition; The pH value of the oral care composition is in the range of about 2.0 to about 5.0.

[0007] This document also discloses an oral care composition comprising oxalic acid, malonic acid, or salts thereof, or combinations thereof, and one or more surfactants, wherein the pH of the composition is in the range of about 3.5 to about 4.5. Alternatively, the composition may further comprise up to about 5% dental abrasive by weight of the oral care composition.

[0008] In addition, oral care compositions exhibiting a cleaning power of at least about 25 film cleaning ratio (PCR) have been disclosed.

[0009] The present invention also relates to oral care compositions as disclosed herein for teeth whitening, removal of stains on teeth, prevention of stains on oral surfaces, or combinations thereof.

[0010] A method for whitening teeth by removing stains from teeth or preventing stains on the oral surface, or a combination thereof, is also disclosed, the method comprising: a) Depositing the oral care composition as disclosed herein onto a suitable application device, such as, for example, a toothbrush; b) Apply the oral care composition of step a) to the oral surface, for example, by brushing your teeth; c) Applying the oral care composition disclosed herein to the oral surface for a predetermined period of time, such as about 2 minutes or about 5 minutes; and d) Remove the oral care composition from the mouth by swallowing and optionally rinsing. Detailed Implementation

[0011] Embodiments of the present invention relate to oral care whitening compositions having dicarboxylic acids, such as oxalic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, propanedioic acid, maleic acid, malic acid, tartaric acid, D-tartaric acid, L-tartaric acid, or salts thereof, or combinations thereof, and providing unexpectedly high stain-removing benefits relative to other conventional chemical detergents within a specific pH range, but these compositions contain little or no abrasives. Tooth stains or discoloration are caused by cationic cross-linked proteins and extracellular polysaccharides, which then act as reservoirs of chromophores and organic and / or inorganic chromophores. Cross-linking can occur electrostatically via charge-charge, dipole-dipole, and / or dipole-charge interactions. Disruption of these electrostatic forces can promote stain removal. The compositions obtained according to embodiments of the present invention provide effective whitening benefits for oral hard tissues and have fewer disadvantages observed compared to other whitening agents. For example, the compositions of the present invention exhibit a film cleanliness ratio (PCR) of at least 25, or at least 30, or at least 40, or even at least 50.

[0012] Chemical whitening agents loosen the bonds of the colored matrix, thereby affecting its removal from the hard tissue surface of the oral cavity. While not wishing to be bound by theory, chemical agents containing effective solubilizing ligands for cationic crosslinking agents in the colored matrix on the hard tissue surface can be used to remove stains from the surface. Furthermore, the pH and ionic strength of the oral care composition can be used to further promote the solubilization of the cationic portion by the solubilizing ligands (i.e., the whitening agent) by reducing the electrostatic bond strength through protonation of the anionicly charged portion or by lowering the potential of the double layer.

[0013] The chelation effect assumes that complexes of polydentate ligands with metals are more stable than metal complexes of normalized monodentate ligands (e.g., 1 mole of bidentate ligands compared to 2 moles of similarly structured monodentate ligands) because the molar entropy of the bidentate chelate is reduced relative to the monodentate complex. Therefore, the unique properties of the dicarboxylate anion make it a highly effective stable ligand within a specific pH range. In this way, the dicarboxylate anion can dissolve and excise metal cations from stained oral enamel and dentin surfaces within a specific pH range, thereby allowing for easy removal of stained chromogens. While not wishing to be bound by theory, it is believed that the oral care compositions disclosed in this invention provide a surprisingly high whitening effect compared to conventional whitening agents such as pyrophosphates.

[0014] definition To more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition from IUPAC Compendium of Chemical Terminology, 2nd Edition (1997) may be applied, provided that the definition does not conflict with any other disclosure or definition applied herein, or render any claim to which the definition is applied uncertain or unenforceable.

[0015] As used herein, the term "oral care composition" includes products that are not intended for systemic administration of a particular therapeutic agent during ordinary use, but rather to remain in the oral cavity for a sufficient duration to contact the tooth surface or oral tissues. Examples of oral care compositions include dental floss, toothpaste, teething gel, subgingival gel, lotion, mouthwash, mousse, foam, oral spray, lozenges, chewing tablets, chewing gum, teeth whitening strips, dental floss and floss coatings, breath freshening soluble strips, unit-dose compositions, fiber compositions, or denture care or adhesive products. Oral care compositions may also be incorporated into strips or films for direct application or attachment to oral surfaces (such as teeth whitening strips). Examples of lotion compositions include the lotion composition of U.S. Patent No. 11,147,753, and clogging lotions, such as the clogging oil-in-water emulsion of U.S. Patent No. 11,096,874. Examples of unit-dose compositions include the unit-dose composition of U.S. Patent Application Publication No. 2019 / 0343732.

[0016] Unless otherwise specified, as used herein, the term "dental cleaning composition" includes dental or subgingival pastes, gels, or liquid formulations. A dental cleaning composition may be a monophasic composition or a combination of two or more individual dental cleaning compositions. A dental cleaning composition may be in any desired form, such as deep streaks, light streaks, multilayers, pastes surrounded by gels, or any combination thereof. In dental cleaning compositions comprising two or more individual dental cleaning compositions, each composition may be contained in a physically separate dispenser compartment and dispensed side-by-side.

[0017] The active ingredients and other ingredients used herein may be classified or described in accordance with their cosmetic and / or therapeutic benefits or their assumed modes of action or function. However, it should be understood that in some cases, the active substances and other ingredients used herein may provide more than one cosmetic and / or therapeutic benefit, or act or function via more than one mode of action. Therefore, the classification herein is for convenience only and is not intended to limit the ingredients to the specific functions or activities listed.

[0018] The term "orally acceptable carrier" includes one or more compatible solid or liquid excipients or diluents suitable for topical oral administration. As used herein, "compatible" means that the components of a composition are miscible but do not interact with each other, such interactions would significantly reduce the stability and / or efficacy of the composition. Carriers or excipients used in this invention may include common and conventional components of mouthwashes or mouthwashes. Mouthwash or mouthwash carrier materials generally include, but are not limited to, one or more of water, alcohols, humectants, surfactants, and acceptability improvers such as flavoring agents, sweeteners, coloring agents, and / or cooling agents.

[0019] As used herein, the term “substantially free” means that the composition contains no more than 0.05%, preferably no more than 0.01%, and more preferably no more than 0.001% of the specified material on a total weight basis.

[0020] As used herein, the term "substantially free of" means that the indicated material is not intentionally added to the composition, or preferably is not present at an analytically detectable level. This means a composition in which the indicated material is present only as an impurity among other intentionally added materials.

[0021] The term “oral hygiene program” or “program” can be used to describe the use of two or more separate and distinct steps of oral health care, such as toothpaste, mouthwash, dental floss, toothpicks, sprays, rinsing devices, and massagers.

[0022] As used herein, the term "total water content" refers to free water and water not bound to other components in the oral care composition.

[0023] For the purposes of this invention, the relevant molecular weight (MW) to be used is the relevant molecular weight of the material added during the preparation of the composition. For example, if the chelating agent is a citrate substance, it may be provided in the form of citric acid, sodium citrate, or virtually any other salt. The MW used is the MW of the specific salt or acid added to the composition, but any water of crystallization that may be present is ignored.

[0024] Although the compositions and methods described herein are “comprising” various components or steps, unless otherwise indicated, the compositions and methods may also consist “substantially” or “composed of” various components or steps.

[0025] As used in this article, the word "or" when used as a conjunction for two or more elements means including either the element alone or a combination of the elements; for example, X or Y means X or Y or both.

[0026] As used herein, the articles “an” and “a” are understood to refer to one or more materials protected or described in the claims, such as “oral care composition” or “bleaching agent”.

[0027] Unless otherwise specified, all measurements mentioned herein were performed at approximately 23°C (i.e., room temperature).

[0028] Generally, the numbering scheme shown in the version of the periodic table published in Chemical and Engineering News, 63(5), 27, 1985, is used to indicate element groups. In some cases, the common name assigned to the group may be used to indicate the element group; for example, for alkali metals in group 1, for alkaline earth metals in group 2, and so on.

[0029] Several types of scopes are disclosed in relation to this invention. When any type of scope is disclosed or protected by claims, the purpose is to disclose or protect by claims every possible value that such scope can reasonably cover, including the endpoints of the scope and any sub-scopes and combinations thereof covered therein.

[0030] The dental cleaning compositions of the present invention may be in any suitable form, such as solid, liquid, powder, paste, or combinations thereof. Oral care compositions may be dental cleaning agents, teething gels, subgingival gels, mouthwashes, mousses, foams, oral sprays, tablets, chewing tablets, chewing gum, teeth whitening strips, dental floss and floss coatings, breath freshening soluble strips, or denture care or adhesive products. Components of the dental cleaning composition may be incorporated into film, strip, foam, or fiber-based dental cleaning compositions.

[0031] The oral care compositions described herein contain dicarboxylic acids, one or more surfactants, and contain little or no abrasives. Furthermore, the oral care compositions of the present invention may contain a variety of active and inactive ingredients as described below, such as, but not limited to, hop extracts, dicarboxylic acids, tin ion sources, calcium ion sources, water, fluoride ion sources, zinc ion sources, one or more polyphosphates, humectants, surfactants, other ingredients, and any combination thereof, as described below. The following section headings are provided only for organization and convenience. In some cases, compounds may fall within one or more portions. For example, stannous fluoride may be a tin compound and / or a fluoride compound. Additionally, oxalic acid or a salt thereof may be a dicarboxylic acid, a polydentate ligand, and / or a whitening agent.

[0032] Dicarboxylic acid Oral care compositions contain dicarboxylic acids. Dicarboxylic acids include compounds having two carboxylic acid functional groups. Dicarboxylic acids may include compounds defined by formula VIII-A, formula VIII-B, and / or formula VIII-C, or salts thereof.

[0033] Formula VIII_A. dicarboxylic acid R can be empty, alkyl, alkenyl, allyl, phenyl, benzyl, acetyl, aliphatic, aromatic, polyethylene glycol, polymer, O, N, P, or combinations thereof. R can also be further functionalized with one or more functional groups such as -OH, -NH2 and / or alkyl, alkenyl, aromatic, or combinations thereof.

[0034] Formula VIII-B. dicarboxylic acid R can be empty, alkyl, alkenyl, allyl, phenyl, benzyl, acetyl, aliphatic, aromatic, polyethylene glycol, polymer, O, N, P, or combinations thereof. R can also be further functionalized with one or more functional groups such as -OH, -NH2 and / or alkyl, alkenyl, aromatic, or combinations thereof.

[0035] X1 and X2 can be independently H, an alkali metal, an alkaline earth metal, a transition metal, or a combination thereof. Suitable alkali metals include lithium, sodium, potassium, or a combination thereof. Suitable alkaline earth metals include magnesium, calcium, barium, or a combination thereof. Suitable transition metals include titanium, chromium, iron, nickel, copper, zinc, tin, gold, silver, or a combination thereof.

[0036] Formula VIII-C. dicarboxylic acid R1 can be empty, alkyl, alkenyl, allyl, phenyl, benzyl, acetyl, aliphatic, aromatic, polyethylene glycol, polymer, O, N, P, or combinations thereof. R can also be further functionalized with one or more functional groups such as -OH, -NH2 and / or alkyl, alkenyl, aromatic, or combinations thereof.

[0037] X1 and X2 can be independently H, an alkali metal, an alkaline earth metal, a transition metal, or a combination thereof. Suitable alkali metals include lithium, sodium, potassium, or a combination thereof. Suitable alkaline earth metals include magnesium, calcium, barium, or a combination thereof. Suitable transition metals include titanium, chromium, iron, nickel, copper, zinc, tin, gold, silver, or a combination thereof.

[0038] Dicarboxylic acids can be added to formulations as neutral acids (as shown in Formula VIII-A) or as monosalts of dicarboxylic acids (where one of the carboxylic acid functional groups is a salt and the other is neutral), disalts of dicarboxylic acids (where both carboxylic acid functional groups are salts), or combinations thereof. Furthermore, as is well known to those skilled in the art, whether one or both carboxylic acid functional groups of a dicarboxylic acid are neutral or charged in solution can be affected by the pH of the solution. For example, a neutral dicarboxylic acid can be added to an aqueous solution, and if the pH is below the pKa of the carboxylic acid functional groups, one or both protons from the two carboxylic acid functional groups can be removed, as shown in Formula VIII-D below.

[0039] Acid-base properties of formula VIII-D. dicarboxylic acids, where M is any metal.

[0040] Dicarboxylic acids may include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, hexadecanoic acid, jasminoides, eurythic acid, malic acid, maleic acid, tartaric acid, D-tartaric acid, L-tartaric acid, phthalic acid, methylmalonic acid, dimethylmalonic acid, propanedioic acid, mesooxalic acid, dihydroxymalonic acid, fumaric acid, terephthalic acid, glutaric acid, their salts, or combinations thereof. Dicarboxylic acids may include suitable salts of dicarboxylic acids, such as, when a dicarboxylic acid includes a salt of oxalic acid: monoalkali metal oxalates, dialkali metal oxalates, monopotassium monohydrooxalate, dipotassium oxalate, monosodium monohydrooxalate, disodium oxalate, titanium oxalate, and / or other metal salts of oxalate. Dicarboxylic acids may also include hydrates of dicarboxylic acids and / or hydrates of salts of dicarboxylic acids.

[0041] Suitable dicarboxylic acid compounds for use in this invention include malonic acid, methylmalonic acid, propanedioic acid, tartaric acid, D-tartaric acid, L-tartaric acid, malic acid, dimethylmalonic acid, oxalic acid, dihydroxymalonic acid, oxalic acid, their salts, or combinations thereof, wherein oxalic acid, malonic acid, methylmalonic acid, D-tartaric acid, their salts, or combinations thereof appear to be highly effective. These dicarboxylic acid compounds are particularly suitable because they have shown surprisingly high whitening benefits. While not wishing to be bound by theory, it is believed that certain dicarboxylic acid compounds have a surprisingly high affinity for certain cationic crosslinking agents in the colored matrix commonly present on the surface of oral hard tissues, thereby leading to the removal of stains from the surface.

[0042] Suitable dicarboxylic acid compounds include dicarboxylic acids described by formula VIII-A, wherein R is a methylene or ethylene group that is absent or includes one or two substituents, and / or an acetyl group.

[0043] Unbound by theory, we assume that the whitening effect of dicarboxylic acid and its corresponding anion is driven by the ability of dicarboxylic acid to reach and remove chromophores and tooth surfaces, as well as the cation bridges between chromophores and epidermal proteins.

[0044] The oral care composition may contain about 0.01% to about 10%, or about 1.0% to about 10%, or about 1.5% to about 7.5%, or about 2.0% to about 5.0% or about 2.8% to about 3.6% of dicarboxylic acid by weight of the oral care composition.

[0045] surfactants Oral care compositions may contain one or more surfactants. Surfactants can be used to make the composition more cosmetically acceptable and can help disperse dicarboxylic acids. Surfactants are preferably detergency agents that impart detergency and foaming properties to the composition. Suitable surfactants are anionic, cationic, nonionic, amphoteric, amphoteric, and betaine surfactants in safe and effective amounts.

[0046] Suitable anionic surfactants include, for example, water-soluble salts of alkyl sulfates having 8 to 20 carbon atoms in the alkyl group and water-soluble salts of sulfonated monoglycerides of fatty acids having 8 to 20 carbon atoms. Examples of such anionic surfactants suitable for use in this invention are sodium lauryl sulfate (SLS) and sodium coconut monoglyceride sulfonate. Other suitable anionic surfactants include sarcosine salts (such as sodium lauroyl sarcosine), taurine salts, sodium lauryl sulfoacetate, sodium lauroyl hydroxyethyl sulfonate, sodium lauryl polyoxyethylene ether carboxylate, and sodium dodecylbenzene sulfonate. Combinations of anionic surfactants may also be used.

[0047] Another suitable class of anionic surfactants are alkyl phosphates. These surface-active organophosphate reagents exhibit strong affinity for enamel surfaces and a strong tendency to surface-bind, thereby desorbing surface proteins and maintaining their attachment to the enamel surface. Suitable examples of organophosphate compounds include monoesters, diesters, and trimers represented by the following general formulas: Z1, Z2, or Z3 may be the same or different, and at least one of them is an organic moiety. Z1, Z2, or Z3 may be selected from straight-chain or branched alkyl or alkenyl groups of 1 to 22 carbon atoms, optionally substituted with: one or more phosphate groups; alkoxylated alkyl or alkenyl groups, (poly)saccharide groups, polyol groups, or polyether groups. Some other reagents include alkyl phosphates or alkenyl phosphates represented by the following structures: Wherein R1 represents a straight-chain or branched alkyl or alkenyl group having 6 to 22 carbon atoms, optionally substituted with one or more phosphate groups; n and m are individually and respectively 2 to 4, and a and b are individually and respectively 0 to 20; Z and Z may be the same or different, each representing hydrogen, alkali metal, ammonium, protonated alkylamine or protonated functionalized alkylamine, such as alkanolamine or R-(OCH2)(OCH)- group. Examples of suitable reagents include alkyl phosphates and alkyl (poly)alkoxy phosphates, such as lauryl phosphate; PPGS cetearyl polyoxyethylene ether-10 phosphate; lauryl polyoxyethylene ether-1 phosphate; lauryl polyoxyethylene ether-3 phosphate; lauryl polyoxyethylene ether-9 phosphate; trilauryl polyoxyethylene ether-4 phosphate; C 12-18PEG 9 phosphate ester: and dilauryl polyoxyethylene ether-10 sodium phosphate. Alkyl phosphates may be polymers. Examples of polymeric alkyl phosphate esters include those containing repeating alkoxy groups as polymeric moieties, specifically those containing three or more ethoxy, propoxy, isopropoxy, or butoxy groups.

[0048] Other suitable anionic surfactants are sarcosinates, hydroxyethyl sulfonates, and taurines, especially their alkali metal or ammonium salts. Examples include lauroyl sarcosinate, myristoyl sarcosinate, palmitoyl sarcosinate, stearoyl sarcosinate, oleoyl sarcosinate, or combinations thereof.

[0049] Other suitable anionic surfactants include sodium or potassium alkyl sulfates, such as sodium lauryl sulfate, acyl hydroxyethyl sulfonate, acyl methyl hydroxyethyl sulfonate, alkyl ether carboxylates, acyl alanine salts, acyl glutamate salts, acyl glycinate salts, acyl sarcosine salts, sodium methyl acyl taurate, sodium lauryl ether sulfosuccinate, α-olefin sulfonate, alkylbenzene sulfonate, sodium lauroyl lactate, sodium lauryl glucoside hydroxypropyl sulfonate, and / or combinations thereof.

[0050] Suitable taurine surfactants are represented by formula (I): Wherein R1 is a saturated or unsaturated straight-chain or branched alkyl chain having 6 to 18 carbon atoms; R2 is H or methyl, and M is H, sodium, or potassium. Preferably, R1 is a saturated or unsaturated straight-chain or branched alkyl chain having 8 to 18 carbon atoms. Optionally, but preferably, the taurine surfactant comprises one or more of the following: potassium cocoyl taurate, potassium methyl cocoyl taurate, sodium hexanoyl methyl taurate, sodium cocoyl taurate, sodium lauroyl taurate, sodium methyl cocoyl taurate, sodium methyl lauroyl taurate, sodium methyl myristoyl taurate, sodium methyl oleoyl taurate, and combinations thereof.

[0051] The zwitterionic surfactants or amphoteric surfactants that can be used herein include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, wherein the aliphatic group can be straight-chain or branched, and one of the aliphatic substituents contains 8 to 18 carbon atoms, and one of the aliphatic substituents contains an anionic water-solubilizing group, such as a carboxyl, sulfonate, sulfate, phosphate, or phosphonate group. Suitable betaine surfactants are disclosed in U.S. Patent No. 5,180,577. Typical alkyl dimethyl betaines include decyl betaine or 2-(N-decyl-N,N-dimethylamine) acetate, cocoyl betaine or 2-(N-cocoyl-N,N-dimethylamine) acetate, tetradecyl betaine, palmityl betaine, lauryl betaine, hexadecyl betaine, hexadecyl betaine, stearyl betaine, etc. Amide betaines can be exemplified by cocamidoethyl betaine, cocamidopropyl betaine (CADB), and lauramidopropyl betaine. Other suitable amphoteric surfactants include betaine, sulfobetaine, sodium lauryl amphoteric acetate, alkyl amphoteric diacetates, and / or combinations thereof.

[0052] Suitable cationic surfactants include, for example, quaternary ammonium compound derivatives having a long alkyl chain containing 8 to 18 carbon atoms, such as lauryltrimethylammonium chloride; cetylpyridinium chloride; hexadecyltrimethylammonium bromide; hexadecylpyridinium fluoride or combinations thereof.

[0053] Suitable nonionic surfactants include, for example, compounds prepared by the condensation of an alkylene group (which is inherently hydrophilic) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. Examples of suitable nonionic surfactants may include Pluronics. ® (i.e., poloxamer), alkylphenol polyoxyethylene condensates, products derived from the condensation of ethylene oxide with propylene oxide and ethylenediamine, fatty alcohol ethylene oxide condensates, long-chain tertiary amine oxides, long-chain tertiary phosphine oxides, long-chain dialkyl sulfoxides, and combinations thereof. Other suitable nonionic surfactants include alkyl glucosamides, alkyl glucosides, and / or combinations thereof.

[0054] One or more surfactants may also include one or more natural and / or naturally derived surfactants. Natural surfactants may include surfactants derived from natural products and / or minimally processed or unprocessed surfactants. Natural surfactants may include: hydrogenated, non-hydrogenated or partially hydrogenated vegetable oils, vegetable oils, passion fruit oil, candelilla wax, cocoyl caprylate, caprylate, dioctyl ether, lauryl alcohol, tetradecyl myristate, dioctyl ether, caprylic acid, octyl ester, octyl caprylate, octyl caprylate, undecane, tridecane, decyl oleate, decyl oleate, hexadecyl palmitate, stearic acid, palmitic acid, glyceryl stearate, hydrogenated, non-hydrogenated or partially hydrogenated vegetable glycerides, polyglycerol-2 dihydroxystearate, hexadecyl alcohol / octadecanol, sucrose polystearate, glycerin, octadecyl alcohol, hydrolyzed, partially hydrolyzed Hydrolyzed or unhydrolyzed plant proteins, hydrolyzed, partially hydrolyzed or unhydrolyzed wheat protein hydrolysates, polyglycerol-3 diisostearate, glyceryl oleate, myristyl alcohol, hexadecyl alcohol, sodium hexadecylstearyl sulfate, hexadecylstearyl alcohol, glyceryl laurate, triglycerides caprylate, cocoglyceryl esters, lecithin, dioctyl ether, xanthan gum, sodium cocosulfate, ammonium lauryl sulfate, sodium cocosulfate, sodium cocoglutamate, polyalkyl glucosides (such as decyl glucoside, hexadecylstearyl glucoside), hexadecylstearyl polyglucoside, cocoglycoside and lauryl glucoside and / or combinations thereof. Natural surfactants may include any of the natural ingredients sold by BASF, such as, for example, CegeSoft. ® Cetiol ® Cutina ® Dehymuls ® Emulgade ® Emulgin ® Eutanol ® Gluadin ® Lameform ® LameSoft ® Lanette ® Monomuls ® Myritol ® Plantacare ® Plantaquat ® Platasil ® Rheocare ® Sulfopon ® Texapon ® and / or combinations thereof.

[0055] Other specific examples of surfactants include sodium lauryl sulfate, sodium lauryl hydroxyethyl sulfonate, sodium lauroyl methyl hydroxyethyl sulfonate, sodium cocoyl glutamate, sodium dodecylbenzene sulfonate, alkali metal or ammonium salts of lauroyl sarcosine, myristoyl sarcosine, palmitoyl sarcosine, stearoyl sarcosine, and oleoyl sarcosine; polyoxyethylene sorbitan monostearate, isostearate, and laurate; sodium lauryl sulfoacetate; sodium, potassium, and ethanolamine salts of N-lauroyl sarcosine, N-lauroyl, N-myristoyl, or N-palmitoyl sarcosine; polyoxyethylene condensates of alkylphenols; cocamidopropyl betaine, lauroamideopropyl betaine, palmitoyl betaine, sodium cocoyl glutamate, etc. Additional surfactants desired include fatty acid salts of glutamate, alkyl glucosides, taurine, betaine, caprylate, and / or mixtures thereof. Oral care compositions may also be sulfate-free.

[0056] Oral care compositions may contain one or more surfactants, each surfactant in a content of about 0.01% to about 15%, about 0.3% to about 10%, about 0.3% to about 2.5% by weight of the oral care composition, or a total content of about 3% to about 10%, about 4% to about 7.5%, or about 4.5% to about 6%. Furthermore, the total amount of surfactant may be suitable for the type of composition. For example, compositions in the form of dental cleaning agents, pastes, or gels contain at least about 1% surfactant by weight of the composition. As another example, compositions in the form of mouthwash or mouthwash contain at most 0.5% surfactant by weight of the oral care composition.

[0057] friction agent The oral care compositions of the present invention may include an abrasive. The abrasive may be added to the oral care formulation to further aid in the removal of surface stains on teeth by dicarboxylic acid. The oral care formulation may include calcium abrasives and / or non-calcium abrasives, such as silica abrasives.

[0058] Oral care compositions may contain calcium abrasives. The calcium abrasive may be any suitable abrasive compound that, when applied to the oral cavity, provides and / or delivers calcium ions into the oral cavity. Oral care compositions may contain about 5% to about 70%, about 10% to about 60%, about 20% to about 50%, about 25% to about 40%, or about 1% to about 50% of calcium abrasives. The calcium abrasive may contain one or more calcium abrasive compounds, such as calcium carbonate, precipitated calcium carbonate (PCC), ground calcium carbonate (GCC), chalk, dicalcium phosphate, calcium pyrophosphate, and / or mixtures thereof.

[0059] Oral care compositions may contain non-calcium abrasives, such as bentonite, silica gel (alone and of any structure), precipitated silica, amorphous precipitated silica (alone and also of any structure), silica hydrate, perlite, titanium dioxide, calcium pyrophosphate, calcium hydrogen phosphate dihydrate, alumina, alumina hydrate, calcined alumina, aluminum silicate, insoluble sodium metaphosphate, insoluble potassium metaphosphate, insoluble magnesium carbonate, zirconium silicate, particulate thermosetting resins, and other suitable abrasive materials. Such materials may be incorporated into oral care compositions to tailor the polishing properties of the targeted dental cleaning formulation. Oral care compositions may contain approximately 5% to approximately 70%, approximately 10% to approximately 50%, approximately 10% to approximately 60%, approximately 20% to approximately 50%, approximately 25% to approximately 40%, or approximately 1% to approximately 50% of the non-calcium abrasives by weight of the oral care composition.

[0060] Alternatively, the oral care composition may be substantially free of, substantially free of, substantially free of, or free of silica, alumina, or any other non-calcium abrasive. The oral care composition may contain less than about 5%, less than about 1%, less than about 0.5%, less than about 0.1%, or 0% of non-calcium abrasives, such as silica and / or alumina.

[0061] Oral care compositions may also contain silica abrasives, such as silica gel (in its own form or of any structure), precipitated silica, amorphous precipitated silica (in its own form or of any structure), silica hydrates, and / or combinations thereof. Oral care compositions may contain about 5% to about 70%, about 10% to about 60%, about 10% to about 50%, about 20% to about 50%, about 25% to about 40%, or about 1% to about 50% of silica abrasives.

[0062] When an oral care composition contains dicarboxylic acid, the composition may include a low amount of abrasive or contain no abrasive, because dicarboxylic acid can provide sufficiently high whitening benefits without the need for abrasive.

[0063] While mouthwash compositions typically do not contain abrasives, dental cleaning compositions typically do. However, the dental cleaning compositions and / or toothpaste compositions of embodiments of the present invention may contain low amounts of abrasives or none at all, because small amounts of abrasives can support the whitening and stain-removing effects of the oral care composition. Therefore, the oral care composition or dental cleaning composition may contain less than about 5%, less than 4%, less than 3%, less than 2.5%, about 0.5% to about 2%, or less than about 2% of abrasives by weight of the composition. The oral care composition or dental cleaning composition may also be substantially free of, substantially free of, or contain no abrasives.

[0064] pH value The pH of the oral care compositions described herein may be from about 2.0 to about 5.0, from about 2.5 to about 5.0, from about 3.5 to about 5.0, from about 3.0 to about 4.5, or from about 3.5 to about 4.5. The pH of the mouthwash aqueous solution may be determined as the pH of the pure solution. The pH of the dental cleaning composition may be determined as the paste pH, which is the pH of a mixture of the dental cleaning composition and water (such as a 1:4, 1:3, or 1:2 mixture of the dental cleaning composition and water).

[0065] The oral care compositions described herein have a preferred pH of below about 5.5 or below about 5.0 to ensure the effectiveness of dicarboxylic acids. While not wishing to be bound by theory, it is believed that dicarboxylic acids exhibit unique properties at pH values ​​below about 5.5 or below about 5.0, producing anti-fouling and stain-removing effects, but surfaces in the oral cavity may also be sensitive to low pH. However, surprisingly, it has been found that whitening effects are optimal at low pH values ​​below about 4.5. Additionally, at pH values ​​above about 7, metal ion sources, if present, will react with water and / or hydroxide ions to form insoluble metal oxides and / or metal hydroxides. The formation of these insoluble compounds can limit the ability of dicarboxylic acids to stabilize metal ions in the oral care compositions and / or can limit the interaction of dicarboxylic acids with target metal ions in the oral cavity. As described herein, the pH of an oral care composition can be measured immediately after mixing, or after aging the composition by placing it under ambient temperature or accelerated temperature and humidity conditions, such as measuring pH for approximately 28 days or longer prior to measurement at temperatures of 25°C, 30°C and / or 40°C and relative humidity of 30%, 60% and / or 75%.

[0066] buffer Oral care compositions may contain one or more buffers. As used herein, a buffer is a reagent that can be used to adjust the pH of the slurry in an oral care composition. These buffers include alkali metal hydroxides, carbonates, sesquicarbonates, borates, silicates, phosphates, imidazoles, and mixtures thereof. Specific buffers include monosodium phosphate, trisodium phosphate, sodium hydroxide, potassium hydroxide, alkali metal carbonates, sodium carbonate, imidazoles, pyrophosphates, citric acid, and sodium citrate. Oral care compositions may contain one or more buffers, each in an amount of about 0.1% to about 30%, about 1% to about 10%, or about 1.5% to about 3% by weight of the composition of the invention.

[0067] Fluorides Oral care compositions may contain fluoride, which may be provided by a fluoride ion source. The fluoride ion source may contain one or more fluoride-containing compounds, such as stannous fluoride, sodium fluoride, potassium fluoride, titanium fluoride, calcium fluoride, calcium phosphate silicate fluoride, amine fluoride, sodium monofluorophosphate, zinc fluoride, and / or mixtures thereof.

[0068] If applicable, the fluoride ion source and the tin ion source can be the same compound, such as, for example, stannous fluoride, which can generate tin ions and fluoride ions. Alternatively, if applicable, the fluoride ion source and the tin ion source can be separate compounds, such as when the tin ion source is stannous chloride and the fluoride ion source is sodium monofluorophosphate or sodium fluoride.

[0069] If applicable, the fluoride ion source and the zinc ion source can be the same compound, such as, for example, zinc fluoride, which generates both zinc and fluoride ions. Alternatively, the fluoride ion source and the zinc ion source can be separate compounds, such as when the zinc ion source is zinc phosphate and the fluoride ion source is stannous fluoride.

[0070] The fluoride ion source may be substantially free of stannous fluoride or contain no stannous fluoride. Therefore, oral care compositions may contain sodium fluoride, potassium fluoride, amine fluoride, sodium monofluorophosphate, zinc fluoride, and / or mixtures thereof.

[0071] The oral care composition may contain a fluoride ion source capable of providing about 50 ppm to about 5000 ppm, and preferably about 500 ppm to about 3000 ppm, of free fluoride ions. To deliver the desired amount of fluoride ions, the fluoride ion source may be present in the oral care composition in an amount of about 0.0025% to about 5%, about 0.01% to about 10%, about 0.2% to about 1%, about 0.5% to about 1.5%, or about 0.3% to about 0.6% by weight of the oral care composition. Alternatively, the oral care composition may contain less than 0.1%, less than 0.01%, substantially no, substantially no, or no fluoride ion source.

[0072] Metal Oral care compositions as described herein may contain a metal, which may be provided by a metal ion source comprising one or more metal ions. Suitable metal ion sources include compounds having metal ions, such as, but not limited to, Sn, Zn, K, Cu, Mn, Mg, Sr, Ti, Fe, Mo, B, Ba, Ce, Al, In, and / or mixtures thereof. The metal ion source may be any compound having a suitable metal and any accompanying ligands and / or anions. Suitable ligands and / or anions that may pair with a metal ion source include, but are not limited to, acetate, ammonium sulfate, benzoate, bromide, borate, carbonate, chloride, citrate, gluconate, glycerophosphate, hydroxide, iodide, oxalate, oxides, propionate, D-lactate, DL-lactate, orthophosphate, pyrophosphate, sulfate, nitrate, tartrate, and / or mixtures thereof.

[0073] The oral care composition may contain about 0.01% to about 10%, about 1% to about 5%, or about 0.5% to about 15% of a metal and / or metal ion source by weight of the oral care composition.

[0074] tin The oral care composition of the present invention may contain tin, which may be provided by a tin ion source. The tin ion source may be any suitable compound that, when the oral care composition is applied to the oral cavity, provides tin ions in the oral care composition and / or delivers tin ions to the oral cavity. The tin ion source may contain one or more tin-containing compounds, such as stannous fluoride, stannous chloride, stannous bromide, stannous iodide, stannous oxide, stannous oxalate, stannous sulfate, stannous sulfide, tin fluoride, stannous chloride, stannous bromide, stannous iodide, stannous sulfide, and / or mixtures thereof. The tin ion source may contain stannous fluoride, stannous chloride, and / or mixtures thereof. The tin ion source may also be a fluorine-free tin ion source, such as stannous chloride.

[0075] The oral care composition may contain about 0.0025% to about 5%, about 0.01% to about 10%, about 0.2% to about 1%, about 0.4% to about 1%, or about 0.3% to about 0.6% of tin and / or a tin ion source by weight of the oral care composition. Alternatively, the oral care composition may be substantially free of, substantially free of, or free of tin.

[0076] Zinc Oral care compositions may contain zinc, which may be provided by a zinc ion source. The zinc ion source may include one or more zinc-containing compounds, such as zinc fluoride, zinc lactate, zinc oxide, zinc phosphate, zinc chloride, zinc acetate, zinc hexafluorozirconate, zinc sulfate, zinc tartrate, zinc gluconate, zinc citrate, zinc malate, zinc glycinate, zinc pyrophosphate, zinc metaphosphate, zinc oxalate, and / or zinc carbonate. The zinc ion source may also be a fluoride-free zinc ion source, such as zinc phosphate, zinc oxide, and / or zinc citrate.

[0077] Zinc and / or a zinc ion source may be present in the total oral care composition in amounts of about 0.01% to about 10%, about 0.2% to about 1%, about 0.4% to about 1%, or about 0.3% to about 0.6% by weight of the oral care composition. Alternatively, the oral care composition may be substantially free of, substantially free of, or free of zinc.

[0078] Potassium Oral care compositions may contain potassium, which may be provided by a potassium ion source. The potassium ion source may include one or more potassium-containing compounds, such as potassium nitrate, potassium fluoride, potassium chloride, or combinations thereof.

[0079] The oral care composition may contain about 0.01% to about 10%, about 0.2% to about 1%, about 0.4% to about 1%, or about 0.3% to about 0.6% of potassium and / or a potassium ion source by weight of the oral care composition. Alternatively, the oral care composition may be substantially free of, substantially free of, or free of potassium.

[0080] Antibacterial agents Oral care compositions may contain one or more antimicrobial agents. Suitable antimicrobial agents include any molecule that provides antimicrobial activity in the oral cavity. Suitable antimicrobial agents include hop acid, tin ion source, benzyl alcohol, sodium benzoate, menthyl acetate, menthyl lactate, L-menthol, o-menthol, copper chlorophyllin complexes, phenol, hydroxyquinoline, and / or combinations thereof.

[0081] Oral care compositions may contain about 0.01% to about 10%, about 1% to about 5%, or about 0.5% to about 15% of an antimicrobial agent.

[0082] Bioactive substances Oral care compositions may also contain bioactive substances suitable for tooth remineralization. Suitable bioactive substances include bioactive glass and Novamin. ™ Recaldent ™Hydroxyapatite, one or more amino acids (e.g., arginine, citrulline, glycine, lysine, or histidine), or combinations thereof. Suitable examples of compositions containing arginine can be found in U.S. Patent Nos. 4,154,813 and 5,762,911, the entire contents of which are incorporated herein by reference. Other suitable bioactive substances include any calcium phosphate compound. Other suitable bioactive substances include compounds comprising both a calcium source and a phosphate source.

[0083] Amino acids are organic compounds containing an amine functional group, a carboxyl functional group, and a side chain unique to each amino acid. Suitable amino acids include, for example, amino acids with positive or negative side chains, amino acids with acidic or basic side chains, amino acids with polar, uncharged side chains, amino acids with hydrophobic side chains, and / or combinations thereof. Suitable amino acids also include, for example, arginine, histidine, lysine, aspartic acid, glutamic acid, serine, threonine, asparagine, glutamine, cysteine, selenocysteine, glycine, proline, alanine, valine, isoleucine, leucine, methionine, phenylalanine, tyrosine, tryptophan, citrulline, ornithine, creatine, diaminobutyric acid, diaminopropionic acid, their salts, and / or combinations thereof.

[0084] Bioactive glasses contain calcium and / or phosphate, which may be present in proportions similar to hydroxyapatite. These glasses are tissue-adhesive and biocompatible. Bioactive glasses may contain phosphopeptides, calcium sources, phosphate sources, silica sources, sodium sources, and / or combinations thereof.

[0085] The oral care composition may contain about 0.01% to about 20%, about 0.1% to about 10%, or about 1% to about 10% of a bioactive substance based on the weight of the oral care composition.

[0086] Quaternary ammonium compounds Oral care compositions may contain quaternary ammonium compounds. Quaternary ammonium compounds in compositions of embodiments of the present invention may include those in which one or two substituents on the quaternary nitrogen have a carbon chain length (typically an alkyl group) of about 8 to about 20, typically about 10 to 18 carbon atoms, while the remaining substituents (typically alkyl or benzyl groups) have a lower number of carbon atoms, such as about 1 to about 7, typically those of methyl or ethyl groups. Cetylpyridinium chloride, hexadecyl fluorinated pyridinium, tetradecyl pyridinium chloride, N-tetradecyl-4-ethyl pyridinium chloride, domethacin, benzalkonium chloride, benzyl chloride, methylbenzyl chloride, dodecyltrimethylammonium bromide, dodecyl dimethyl (2-phenoxyethyl)ammonium bromide, benzyl dimethoxystearyl ammonium chloride, quaternized 5-amino-1,3-bis(2-ethylhexyl)-5-methylhexahydropyrimidine, lauryltrimethylammonium chloride, cocoyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, diisobutylphenoxyethyl dimethylbenzylammonium chloride, and dodecyltrimethylammonium bromide are typical examples of quaternary ammonium antimicrobial agents. Other compounds are bis[4-(R-amino)-1-pyridinium]alkanes, as disclosed in U.S. Patent No. 4,206,215 to Bailey. Pyridinium compounds are preferred quaternary ammonium compounds, particularly hexadecylpyridinium or tetradecylpyridinium halide salts (i.e., chlorides, bromides, fluorides, and iodides). Hexadecylpyridinium fluoride salts are particularly preferred.

[0087] The oral care composition may contain at least about 0.025%, at least about 0.035%, at least about 0.045% to about 1.0%, about 0.025% to about 1%, or about 0.01% to about 10% of a quaternary ammonium compound by weight of the composition. Alternatively, the oral care composition may be substantially free of, substantially free of, or contain no quaternary ammonium compound.

[0088] Isoprene-modified flavonoids Oral care compositions may contain isoprene-modified flavonoids. Flavonoids are a group of natural substances widely found in fruits, vegetables, grains, bark, roots, stems, flowers, tea, and wine. Flavonoids can have a variety of beneficial effects on health, such as antioxidant, anti-inflammatory, antimutagenic, anticancer, and antibacterial effects. Isoprene-modified flavonoids are flavonoids that include at least one isoprene functional group (3-methylbut-2-en-1-yl, as shown in Formula IX), which has previously been identified as promoting binding to cell membranes. Therefore, while not wishing to be bound by theory, it is believed that the addition of an isoprene group (i.e., isoprene modification) to flavonoids can enhance the activity of the original flavonoid by increasing the lipophilicity of the parent molecule and improving the permeability of the isoprene molecule to bacterial cell membranes. Increasing lipophilicity to increase permeability to cell membranes may be a double-edged sword, as isoprene-modified flavonoids tend to be insoluble at high Log P values ​​(high lipophilicity). Log P can be an important indicator of antibacterial efficacy.

[0089] Therefore, the term isoprene flavonoids may include naturally occurring flavonoids having one or more isoprene functional groups, flavonoids having synthetically added isoprene functional groups, and / or isoprene flavonoids having synthetically added additional isoprene functional groups.

[0090] Formula IX. Isoprene functional group, where R represents other parts of the molecule. Other suitable functional groups of the parent molecule that improve the structure-activity relationship (e.g., structure-MIC relationship) of the isoprene molecule include additional heterocycles containing nitrogen or oxygen, alkyl amino chains, or alkyl chains substituted to one or more aromatic rings of the parent flavonoid.

[0091] Flavonoids may have a 15-carbon backbone having at least two benzene rings and at least one heterocycle. Some suitable flavonoid backbones may be shown in formula X (flavonoid backbone), formula XI (isoflavone backbone), and / or formula XII (neoflavonoid backbone).

[0092] Formula X. Flavonoid backbone Formula XI. Isoflavone backbone Formula XII. New flavonoid backbone Other suitable flavonoid subgroups include anthocyanins, flavonoids, flavanones, flavanols, flavans, isoflavones, chalcones, and / or combinations thereof.

[0093] Isoprene flavonoids may include naturally isolated isoprene flavonoids or naturally isolated flavonoids, which are synthetically modified by a variety of synthetic methods known to those skilled in the art of synthetic organic chemistry to add one or more isoprene functional groups.

[0094] Other suitable isoprene-based flavonoids may include psoralen chalcone, psoralen dihydroflavonoid, methyl psoralen chalcone, Corylifol A, icariin A, icariin A1, icariin B, icariin C, icariin, icariin I, icariin II, icariin, isopsoralen chalcone, isoflavone, neopsoralen isoflavone, 6-isoprene naringenin, 8-isoprene naringenin, sophoranone G, (-)-stigmocarpin, flavol, quercetin, myristoyl phenol, sophora flavescens chalcone, sophoraecin, morinone G, morinone C, panduratin A, 6-geranyl naringenin, Australone A, 6,8-diisoprene sennaol, dorsmanin C, dorsmanin F, 8-isoprene kaempferol, 7-O-methyl lupin isoflavone, lupin isoflavone, 6-isoprene genistein, isowighteone, yellow lupin veneterone and / or combinations thereof.

[0095] Preferably, isoprene flavonoids are highly likely to have a MIC of less than about 25 ppm against Staphylococcus aureus (a Gram-positive bacterium). Suitable isoprene flavonoids include psoralen dihydroflavonoids, methyl psoralen, Corylifol A, icariin, isoflavone, neopsoralen isoflavone, 6-isoprene naringenin, 8-isoprene naringenin, sophoranone G, (-)-stigmosiderin, matrine, morinone C, pandanatin A and / or combinations thereof.

[0096] Preferably, isoprene flavonoids are highly likely to have a MIC of less than about 25 ppm against *Escherichia coli* (a Gram-negative bacterium). Suitable isoprene flavonoids include methyl psoralen, isoxoflavone, 8-isoprene naringenin, sophoranone G, matrine, pandanatin A, and / or combinations thereof.

[0097] Approximately 1000 isoprene flavonoids have been identified from plants. Based on previously reported numbers of isoprene flavonoids, isoprene flavonoids are the most common subclass, while isoprene flavanols are the rarest. Although naturally occurring isoprene flavonoids have been detected with diverse structural characteristics, their distribution in plants is narrow, unlike their parent flavonoid counterparts which are present in almost all plants. Most isoprene flavonoids are found in the following families: Guttiferae, Leguminosae, Moraceae, Rutaceae, and Umbelliferae. Leguminosae and Moraceae, due to their consumption as fruits and vegetables, are the most frequently studied families, and many novel isoprene flavonoids have been explored. Hops contain 8-isoprene naringenin and isoxalohumol, which may play a role in the health benefits of beer.

[0098] Isoprene flavonoids can be incorporated into hop extract, added to a standalone extract, or added as a standalone component of the oral care compositions disclosed herein.

[0099] Suitable isoprene-modified flavonoids can possess specific octanol-water partition coefficients. Octanol-water partition coefficients can be used to predict the lipophilicity of compounds. Without wishing to be bound by theory, compounds falling within the scope described herein are believed to be able to enter and / or disrupt the major hydrophobic phospholipid bilayer that constitutes the microbial cell membrane. Therefore, octanol-water partition coefficients can be correlated with the antibacterial activity of isoprene-modified flavonoids. Suitable isoprene-modified flavonoids may have log P values ​​of at least about 2, at least about 4, about 2 to about 10, about 4 to about 10, about 4 to about 7, or about 4 to about 7.

[0100] The oral care composition may contain at least about 0.001%, about 0.001% to about 5%, about 0.01% to about 2%, about 0.0001% to about 2%, or at least about 0.05% of isoprene flavonoids.

[0101] amino acids Oral care compositions may contain amino acids. As described herein, amino acids may include one or more amino acids, peptides, and / or polypeptides.

[0102] As shown in Formula XIII, an amino acid is an organic compound containing an amine functional group, a carboxyl functional group, and a side chain (R in Formula XIII) specific to each amino acid. Suitable amino acids include, for example, amino acids with positive or negative side chains, amino acids with acidic or basic side chains, amino acids with polar, uncharged side chains, amino acids with hydrophobic side chains, and / or combinations thereof. Suitable amino acids also include, for example, arginine, histidine, lysine, aspartic acid, glutamic acid, serine, threonine, asparagine, glutamine, cysteine, selenocysteine, glycine, proline, alanine, valine, isoleucine, leucine, methionine, phenylalanine, tyrosine, tryptophan, citrulline, ornithine, creatine, diaminobutyric acid, diaminopropionic acid, their salts, and / or combinations thereof.

[0103] Suitable amino acids include compounds of formula XIII, naturally occurring or synthetically derived compounds. Based on the R group and the environment, amino acids can be zwitterionic, neutral, positively charged, or negatively charged. The charge of amino acids and whether specific functional groups can interact with tin under specific pH conditions are well known to those skilled in the art.

[0104] Formula XIII. Amino acids. R is any suitable functional group. Suitable amino acids include one or more basic amino acids, one or more acidic amino acids, one or more neutral amino acids, or combinations thereof.

[0105] The oral care composition may contain about 0.01% to about 20%, about 0.1% to about 10%, about 0.5% to about 6%, or about 1% to about 10% of amino acids by weight of the oral care composition.

[0106] As used herein, the term "neutral amino acid" includes not only naturally occurring neutral amino acids such as alanine, asparagine, cysteine, glutamine, glycine, isoleucine, leucine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine, but also biologically acceptable amino acids with an isoelectric point in the pH range of 5.0 to 7.0. Biologically preferred acceptable neutral amino acids have a single amino group and a carboxyl group in the molecule or its functional derivatives, such as functional derivatives with modified side chains, although having similar or substantially similar physicochemical properties. In another embodiment, the amino acid will be at least partially water-soluble and provide a pH of less than 7 in an aqueous solution of 1 g / 1000 ml at 25°C.

[0107] Therefore, the neutral amino acids suitable for embodiments of the present invention include, but are not limited to, alanine, GABA, asparagine, cysteine, cystine, glutamine, glycine, hydroxyproline, isoleucine, leucine, methionine, phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine, valine, their salts, or mixtures thereof. Preferably, the neutral amino acids used in embodiments of the present invention may include asparagine, glutamine, glycine, their salts, or mixtures thereof. Neutral amino acids may have an isoelectric point of 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, or 7.0 in an aqueous solution at 25°C. Preferably, the neutral amino acid is selected from proline, glutamine, or glycine, more preferably in its free form (i.e., uncoordinated). If the neutral amino acid is in its salt form, suitable salts include those known in the art as pharmaceutically acceptable and considered physiologically acceptable at the provided amounts and concentrations. Preferably, the neutral amino acid is present in amounts from about 0.0001% to about 10%, preferably about 0.05% to about 5%, preferably about 0.1% to about 3%, preferably about 0.5% to about 3%, and preferably about 1% to about 3% by weight of the composition. In one aspect, the neutral amino acid is glutamine (or a salt thereof). In another aspect, the neutral amino acid is proline (or a salt thereof). In yet another aspect, the neutral amino acid is glycine (or a salt thereof).

[0108] The oral care composition may contain about 0.0001% to about 20%, about 0.1% to about 10%, about 0.5% to about 6%, or about 1% to about 10% of neutral amino acids by weight of the oral care composition.

[0109] Hops The oral care composition of the present invention may comprise hops. The hops may comprise at least one hop compound of Formula I and / or Formula IV. The compounds of Formula I and / or Formula IV may be provided from any suitable source, such as extracts from hops or hops (Humulus lupulus), hops themselves, their synthetic derivatives and / or salts, prodrugs, or other similar substances. The hop extract may comprise one or more hop α-acids, one or more hop iso-α-acids, one or more hop β-acids, one or more hop oils, one or more flavonoids, one or more solvents, and / or water. Suitable hop α-acids (generally represented by Formula I) may include humulone (Formula II), polyhumulone, humulone-like humulone, post-humulone, pro-humulone, and / or mixtures thereof. Suitable hop iso-α-acids may include cis-isohumulone and / or trans-isohumulone. The isomerization of humulone to trans-isohumulone may be represented by Formula III.

[0110] Formula I. Hops α-acid. A is an acidic hydroxyl functional group at the α-position, B is an acidic hydroxyl functional group at the β-position, and R is an alkyl functional group.

[0111] Formula II. Humulin Formula III. Humulone is isomerized to isohylocourne.

[0112] Suitable hop β-acids may include humulone, humulone-like compounds, polyhumulone, and / or mixtures thereof. Suitable hop β-acids may include compounds described in formulas IV, V, VI, and / or VII.

[0113] Formula IV. Hops β-acid. B is an acidic hydroxyl functional group at the β-position, and R is an alkyl functional group.

[0114] Formula V. Humulone Formula VI. Polyhumulone Formula VII. Humulone While hop alpha acids exhibit some antibacterial activity, they also possess a bitter taste. The bitterness provided by hop alpha acids is suitable for beer, but not for oral care compositions. In contrast, hop β acids can be associated with higher antibacterial and / or anti-caries activity, but are less bitter. Therefore, hop extracts with a higher ratio of β to alpha acids than typically found in nature could be suitable for use in oral care compositions as antibacterial and / or anti-caries agents.

[0115] Depending on the type of hops, natural hop sources may contain about 2% to about 12% hop β-acid by weight of the hop source. Hop extracts used in other applications, such as in beer brewing, may contain about 15% to about 35% hop β-acid by weight of the extract. The hop extracts desired herein may contain at least about 35%, at least about 40%, at least about 45%, about 35% to about 95%, about 40% to about 90%, or about 45% to about 99% hop β-acid. Hop β-acid may be in acidic form (i.e., having hydrogen atoms attached to hydroxyl functional groups) or in salt form.

[0116] Suitable hop extracts are described in detail in U.S. Patent No. 7,910,140, ​​the entire contents of which are incorporated herein by reference. The desired hop β-acids may be non-hydrogenated, partially hydrogenated by a non-naturally occurring chemical reaction, or hydrogenated by a non-naturally occurring chemical reaction. Hop β-acids may be substantially free of or substantially free of hydrogenated hop β-acids and / or hop acids. Non-naturally occurring chemical reactions are those involving compounds not present in hops, such as chemical hydrogenation reactions carried out at high temperatures and / or with metal catalysts that are not typically experienced in wild hops.

[0117] Natural hop sources may contain about 2% to about 12% hop alpha acid by weight of the hop source. Hop extracts used in other applications, such as in beer brewing, may contain about 15% to about 35% hop alpha acid by weight of the extract. The hop extracts used herein may contain less than about 10%, less than about 5%, less than about 1%, or less than about 0.5% hop alpha acid by weight of the extract.

[0118] Hop oil may contain terpenes such as myrcene, humulene, caryophyllene, and / or mixtures thereof. The hop extract desired herein may contain less than 5%, less than 2.5%, or less than 2% by weight of the extract of one or more hop oils.

[0119] Flavonoids present in hop extracts may include xanthohumol, 8-isoprene naringenin, isoxanthohumol, and / or mixtures thereof. Hop extracts may be substantially free of, substantially free of, contain no, or have less than 250 ppm, less than 150 ppm, and / or less than 100 ppm of one or more flavonoids.

[0120] As described in U.S. Patent No. 5,370,863, hop acid has previously been added to oral care compositions. However, the oral care composition taught in U.S. Patent No. 5,370,863 contains only up to 0.01% by weight of the oral care composition. While not wishing to be bound by theory, it is believed that only small amounts of hop acid can be incorporated into U.S. Patent No. 5,370,863 because hop alpha acid has a bitter taste. Hop extracts with low levels of hop alpha acid do not have this problem.

[0121] Hop compounds can be combined with extracts from another plant, such as species of the genus Magnolia, or without extracts from another plant. Hop compounds can be combined with triclosan or without triclosan.

[0122] Oral care compositions may contain about 0.01% to about 10%, greater than 0.01% to about 10%, about 0.05%, about 10%, about 0.1% to about 10%, about 0.2% to about 10%, about 0.2% to about 10%, about 0.2% to about 5%, about 0.25% to about 2%, about 0.05% to about 2%, or greater than 0.25% to about 2% of hops, such as hop β-acid, as described herein. Hop, such as hop β-acid, may be provided from suitable hop extracts, the hop plant itself, or synthetic derivatives. Hop, such as hop β-acid, may be provided as a neutral, acidic compound and / or as a salt having a suitable counterion such as sodium, potassium, ammonia, or any other suitable counterion.

[0123] Hops may be provided by hop extracts, such as extracts derived from hops, having at least 35% hop β-acid and less than 1% hop α-acid by weight of the extract. Oral care compositions may contain 0.01% to about 10%, greater than 0.01% to about 10%, about 0.05%, about 10%, about 0.1% to about 10%, about 0.2% to about 10%, about 0.2% to about 10%, about 0.2% to about 5%, about 0.25% to about 2%, about 0.05% to about 2%, or greater than 0.25% to about 2%, as described herein.

[0124] Polyphosphate Oral care compositions may contain polyphosphates, which may be provided by a polyphosphate source. A polyphosphate source may contain one or more polyphosphate molecules. Polyphosphates are a class of substances obtained by the dehydration and condensation of orthophosphates to form linear and cyclic polyphosphates of varying chain lengths. Therefore, polyphosphate molecules are typically identified by the average number (n) of polyphosphate molecules, as described below. Although some cyclic derivatives may exist, polyphosphates are generally considered to consist of two or more phosphate molecules arranged primarily in a linear configuration.

[0125] Preferred polyphosphates are those having an average of two or more phosphate groups, so that sufficient unbound phosphate functional groups are generated for effective surface adsorption, which enhances the anionic surface charge and the surface's hydrophilic properties. Preferred polyphosphates include straight-chain polyphosphates having the following formula: XO(XPO3). n X, where X is sodium, potassium, ammonium, or any other alkali metal cation, and n on average is from about 2 to about 21. Alkaline earth metal cations (such as calcium) are not preferred because they tend to form insoluble fluoride salts from aqueous solutions containing fluoride ions and alkaline earth metal cations. Therefore, the oral care compositions disclosed herein may be free of, substantially free of, or substantially free of calcium pyrophosphate.

[0126] Some examples of suitable polyphosphate molecules include, for example, pyrophosphate (n=2), tripolyphosphate (n=3), tetrapolyphosphate (n=4), sodium polyphosphate (n=6), hexapolyphosphate (n=13), benzene polyphosphate (n=14), and hexametaphosphate (n=21), which is also known as Glass H. Polyphosphates may include those polyphosphate compounds produced by FMC Corporation, ICL Performance Products, and / or Astaris.

[0127] The oral care composition may contain about 0.01% to about 15%, about 0.1% to about 10%, about 0.5% to about 5%, about 1% to about 20%, or about 10% or less of a polyphosphate source based on the weight of the oral care composition. Alternatively, the oral care composition may be substantially free of, substantially free of, or free of polyphosphates.

[0128] Whitening agent The oral care composition may contain a whitening agent in amounts of about 0.1% to about 10%, about 0.2% to about 5%, about 1% to about 5%, or about 1% to about 15% by weight of the oral care composition. The whitening agent may be a compound suitable for whitening at least one tooth in the oral cavity. The whitening agent may include peroxides, metal chlorites, perborates, percarbonates, peroxy acids, persulfates, dicarboxylic acids, and combinations thereof. Suitable peroxides include solid peroxides, hydrogen peroxide, urea peroxide, calcium peroxide, benzoyl peroxide, sodium peroxide, barium peroxide, inorganic peroxides, hydroperoxides, organic peroxides, and mixtures thereof. Suitable metal chlorites include calcium chlorite, barium chlorite, magnesium chlorite, lithium chlorite, sodium chlorite, and potassium chlorite. Other suitable whitening agents include sodium persulfate, potassium persulfate, peroxydone complex (polyvinylpyrrolidone and hydrogen peroxide), 6-phthaliminoperoxyhexanoic acid, phthaliminoperoxyhexanoic acid, or mixtures thereof.

[0129] Monodentate ligands Oral care compositions may contain a monodentate ligand having a molecular weight (MW) of less than 1000 g / mol. The monodentate ligand has a single functional group capable of interacting with a central atom such as a tin ion. The monodentate ligand must be suitable for use in the oral care composition and may be included in the oral care composition listed on the FDA's Generally Recognized As Safe (GRAS) list or other suitable lists within the jurisdiction of concern.

[0130] As described herein, monodentate ligands may contain a single functional group capable of chelating, associating, and / or bonding with tin. Suitable functional groups capable of chelating, associating, and / or bonding with tin include carbonyl, amine, and other functional groups known to those skilled in the art. Suitable carbonyl functional groups may include carboxylic acids, esters, amides, or ketones.

[0131] Monodentate ligands may contain a single carboxylic acid functional group. Suitable monodentate ligands containing carboxylic acids may include compounds having the formula R-COOH, where R is any organic structure. Suitable monodentate ligands containing carboxylic acids may also include aliphatic carboxylic acids, aromatic carboxylic acids, sugar acids, their salts, and / or combinations thereof.

[0132] Aliphatic carboxylic acids may contain a carboxylic acid functional group attached to a straight-chain hydrocarbon chain, a branched hydrocarbon chain, and / or a cyclic hydrocarbon molecule. Aliphatic carboxylic acids may be fully saturated or unsaturated and have one or more alkene and / or alkyne functional groups. Other functional groups may be present and bonded to the hydrocarbon chain, including halogenated variants of the hydrocarbon chain. Aliphatic carboxylic acids may also include hydroxy acids, which are organic compounds having an alcohol functional group at the α, β, or γ position relative to the carboxylic acid functional group. Suitable α-hydroxy acids include lactic acid and / or its salts.

[0133] Aromatic carboxylic acids may contain a carboxylic acid functional group attached to at least one aromatic functional group. Suitable aromatic carboxylic acid groups may include benzoic acid, salicylic acid, and / or combinations thereof.

[0134] Carboxylic acids may include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, ascorbic acid, benzoic acid, octanoic acid, cholic acid, glycine, alanine, valine, isoleucine, leucine, phenylalanine, linoleic acid, nicotinic acid, oleic acid, propionic acid, sorbic acid, stearic acid, gluconic acid, lactic acid, carbonic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, their salts and / or combinations thereof.

[0135] Oral care compositions may contain about 0.01% to about 10%, about 0.1% to about 15%, about 1% to about 5%, or about 0.0001% to about 25% of monodental ligands by weight of the composition.

[0136] Multidentate ligands Oral care compositions may contain polydentate ligands with a molecular weight (MW) of less than 1000 g / mol or less than 2500 g / mol. The polydentate ligands have at least two functional groups capable of interacting with a central atom such as a tin ion. Additionally, the polydentate ligands must be suitable for use in oral care compositions and may be included in the oral care composition listed on the FDA's Generally Recognized As Safe (GRAS) list or another suitable list within the jurisdiction of concern.

[0137] As described herein, polydentate ligands may contain at least two functional groups that can chelate, associate, and / or bond with tin. Polydentate ligands may include dipentate ligands (i.e., having two functional groups), tripentate ligands (i.e., having three functional groups), tetradentate ligands (i.e., having four functional groups), etc.

[0138] Suitable functional groups that can chelate, associate, and / or bond with tin include carbonyl, phosphate, nitrate, amine, and other functional groups known to those skilled in the art. Suitable carbonyl functional groups may include carboxylic acids, esters, amides, or ketones.

[0139] Polydentate ligands can contain two or more carboxylic acid functional groups. Suitable polydentate ligands containing carboxylic acids can include compounds having the formula HOOC-R-COOH, where R is any organic structure. Suitable polydentate ligands containing two or more carboxylic acids can also include dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, etc.

[0140] Other suitable polydentate ligands include compounds containing at least two phosphate functional groups. Therefore, as described herein, polydentate ligands can include polyphosphates.

[0141] Other suitable polydentate ligands include hop β-acids, such as humulone, humulone-like compounds, polyhumulone, and / or combinations thereof. Hop β-acids can be synthetically derived and / or extracted from natural sources.

[0142] Polydentate ligands may also include phosphate groups as functional groups to interact with tin. Suitable phosphate compounds include phosphates, organophosphates, or combinations thereof. Suitable phosphates include orthophosphates, hydrogen phosphates, dihydrogen phosphates, alkylated phosphates, and combinations thereof. Polydentate ligands may include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, hexadecanoic acid, jasminoides, styracidin, equisetic acid, maleic acid, malic acid, tartaric acid, D-tartaric acid, L-tartaric acid, phthalic acid, citric acid, phytic acid, pyrophosphate, tripolyphosphate, tetrapolyphosphate, hexametaphosphate, their salts, and / or combinations thereof.

[0143] The oral care composition may contain about 0.01% to about 10%, about 0.1% to about 15%, about 1% to about 5%, or about 0.0001% to about 25% of a multidentate ligand by weight of the composition.

[0144] Oral acceptable carrier Oral care compositions may also include an orally acceptable carrier that contains other compounds intended for the oral care composition. For example, oral care compositions disclosed herein may also include humectants, thickeners, polymers, water, buffers, alcohols, and acceptability improvers (such as sweeteners, flavorings, colorings), or combinations thereof.

[0145] wetting agent Oral care compositions may contain one or more humectants, have low levels of humectants, or contain no humectants. Humectants are used to increase the consistency or "texture" of the oral care composition or dental cleaning and to prevent the dental cleaning from drying out. Suitable humectants include polyethylene glycol (having a variety of different molecular weights), propylene glycol, glycerin, erythritol, xylitol, sorbitol, mannitol, butylene glycol, lactitol, hydrogenated starch hydrolysate, and / or mixtures thereof. Oral care compositions may contain one or more humectants, each in an amount of 0% to about 80%, about 40% to about 80%, about 50% to about 75%, or about 60% to about 70% by weight of the oral care composition.

[0146] water The oral care composition of the present invention may be an anhydrous dental cleaning composition, a low-water formulation, or a high-water formulation. Generally, the oral care composition may contain 0% to about 99%, about 20% or more, about 30% or more, about 50% or more, up to about 45%, or up to about 75% of water by weight of the composition.

[0147] In high-water-content dental floss formulations, the dental floss composition comprises about 45% to about 80% water by weight of the composition. The high-water-content dental floss composition may comprise about 50% to about 75%, about 50% to about 65%, about 50% to about 65%, or about 60% to about 70% water by weight of the composition. Water may be added to the high-water-content dental floss formulation, and / or water may enter the composition due to the inclusion of other ingredients.

[0148] In low-water dental cleaning formulations, the dental cleaning composition contains about 10% to about 45% water by weight of the composition. The low-water dental cleaning composition may contain about 10% to about 35%, about 15% to about 25%, or about 20% to about 25% water by weight of the composition. Water may be added to the low-water dental cleaning formulation, and / or water may enter the composition due to the inclusion of other ingredients.

[0149] In anhydrous dental cleaning formulations, the dental cleaning composition contains less than about 10% water by weight of the composition. Anhydrous dental cleaning compositions contain less than about 5%, less than about 1%, or 0% water by weight of the composition. Water may be added to the anhydrous formulation, and / or water may be incorporated into the dental cleaning composition due to the presence of other ingredients.

[0150] Oral care compositions may also be mouthwash formulations. Mouthwash formulations may contain about 75% to about 99%, about 75% to about 95%, or about 80% to about 95% water.

[0151] Thickener Oral care compositions may contain one or more thickeners. Thickeners may be used in oral care compositions to provide a gel-like structure that stabilizes the toothpaste and prevents phase separation. Suitable thickeners include polysaccharides, polymers, and / or silica thickeners. Some non-limiting examples of polysaccharides include starch; starch glycerin; gums such as carrageenan gum, tragacanth gum, gum arabic, solanum, xanthan gum, guar gum, and cellulose gum; magnesium aluminum silicate (colloidal magnesium aluminum silicate); carrageenan; sodium alginate; agar; pectin; gelatin; cellulose compounds such as cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, hydroxymethyl carboxypropyl cellulose, methyl cellulose, ethyl cellulose, and sulfated cellulose; natural and synthetic clays, such as lithium montmorillonite clay; and mixtures thereof.

[0152] Thickeners may include polysaccharides. Polysaccharides suitable for use herein include carrageenan, gellan gum, locust bean gum, xanthan gum, carbomer, poloxamer, modified cellulose, and mixtures thereof. Carrageenan is a polysaccharide derived from seaweed. Several types of carrageenan exist, which can be distinguished by their seaweed origin and / or by their degree and position of sulfation. Thickeners may include κ-carrageenan, modified κ-carrageenan, ι-carrageenan, modified ι-carrageenan, λ-carrageenan, and mixtures thereof. Carrageenan suitable for use herein includes those commercially available under the series name "Viscarin" from FMC Company, including but not limited to Viscarin TP 329, Viscarin TP388, and Viscarin TP 389.

[0153] Thickeners may comprise one or more polymers. Polymers may be polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyacrylic acid, polymers derived from at least one acrylic acid monomer, copolymers of maleic anhydride and methyl vinyl ether, or crosslinked polyacrylic acid polymers having various weight percentages and ranges of average molecular weights in the oral care composition. Polymers may include polyacrylate crosslinked polymers, such as polyacrylate crosslinked polymer-6. Suitable sources of polyacrylate crosslinked polymer-6 may include Sepimach Zen, commercially available from Seppic. ™ .

[0154] Thickeners may include inorganic thickeners. Some non-limiting examples of suitable inorganic thickeners include colloidal magnesium aluminum silicate and silica thickeners. Non-limiting examples of silica thickeners that may be used include, for example, amorphous precipitated silica, such as ZEODENT. ® 165% silica. Other non-limiting silica thickeners include ZEODENT. ® 153, 163, and 167, and ZEOFREE ® 177 and 265 silica products (both purchased from Evonik Corporation) and AEROSIL ® Pyrolytic silica. Oral care compositions may contain 0.01% to about 15%, 0.1% to about 10%, about 0.2% to about 5%, or about 0.5% to about 2% of one or more thickeners. Furthermore, the total amount of thickener may be suitable for the type of composition. For example, compositions in the form of dental cleaning agents, pastes, or gels contain at least about 0.5% surfactant by weight of the composition. Similarly, compositions in the form of mouthwash or mouthwash contain up to 0.1% surfactant by weight of the oral care composition.

[0155] Other ingredients Oral care compositions may contain a variety of other ingredients, such as flavoring agents, sweeteners, coloring agents, preservatives, buffers, or other ingredients suitable for use in oral care compositions, as described below.

[0156] Flavoring agents can also be added to oral care compositions. Suitable flavoring agents include wintergreen oil, peppermint oil, spearmint oil, clove bud oil, menthol, p-propenyl anisole, methyl salicylate, eucalyptol, cinnamon, 1-menthol acetate, sage, eugenol, parsley oil, hydroxyphenyl ethyl ketone, α-ionone, oregano, lemon, orange, propenyl ethyl guaiacol, cinnamon, vanillin, ethyl vanillin, heliotrope, 4-cis-heptenal, dimethyl butyl ketone, methyl p-tert-butylphenylacetate, and mixtures thereof. Cooling agents can also be part of the flavoring agent system. Preferred cooling agents in the compositions of the present invention are p-menthanecarbamoyl reagents, such as N-ethyl-p-menthane-3-carboxamide (commercially known as "WS-3") or N-(ethoxycarbonylmethyl)-3-p-menthanecarboxamide (commercially known as "WS-5"), and mixtures thereof. Flavoring agents are typically used in compositions at a concentration of about 0.001% to about 5% by weight of the oral care composition. The amount may be appropriate for the type of composition. For example, compositions in the form of dental cleaning agents, pastes, or gels contain about 0.3% to about 2%, about 0.5% to about 1.5%, or about 0.5% to about 1% by weight of the oral care composition. Similarly, compositions in the form of mouthwashes or mouthwashes contain about 0.05% to about 0.5%, about 0.1% to about 0.4%, or about 0.2% to about 0.3% by weight of the oral care composition. These flavoring agents typically comprise aldehydes, ketones, esters, phenols, acids, and mixtures of aliphatic, aromatic, and other alcohols.

[0157] Sweeteners can be added to oral care compositions to give the product a pleasant taste. Suitable sweeteners include saccharin (such as sodium saccharin, potassium saccharin, or calcium saccharin), cyclosulfonates (such as sodium, potassium, or calcium salts), acesulfame K, arbutin, neohesperidin dihydrochalcone, aminoglycoside, dextrose, levulose, sucrose, mannose, sucralose, stevia, and glucose.

[0158] Colorants are added to improve the aesthetic appearance of products. Suitable colorants include, but are not limited to, those approved by the relevant regulatory agencies such as the FDA and those listed in the European Food and Drug Directive, and include pigments such as TiO2, as well as colors such as FD&C and D&C dyes.

[0159] Preservatives can also be added to oral care compositions to prevent bacterial growth. Suitable preservatives approved for use in oral compositions, such as methylparaben, propylparaben, benzoic acid, and sodium benzoate, can be added in safe and effective amounts.

[0160] Titanium dioxide may also be added to the compositions of the present invention. Titanium dioxide is a white powder that increases the opacity of the composition. Titanium dioxide typically comprises about 0.25% to about 5% by weight of the oral care composition.

[0161] Other ingredients may be used in oral care compositions, such as desensitizers, rehabilitative agents, other caries prevention agents, chelating agents / polyvalent chelating agents, vitamins, amino acids, proteins, other anti-plaque / anti-tartar agents, light-blocking agents, antibiotics, anti-enzymes, enzymes, pH control agents, oxidants, antioxidants, etc.

[0162] Oral care composition form Suitable compositions for delivering dicarboxylic acids include emulsion compositions such as those in U.S. Patent No. 11,147,753 (the entire contents of which are incorporated herein by reference), unit-dose compositions such as those in U.S. Patent Application Publication No. 2019 / 0343732 (the entire contents of which are incorporated herein by reference), no-rinse oral care compositions, clogging emulsions such as those in U.S. Patent No. 11,096,874 (the entire contents of which are incorporated herein by reference), dental cleaning compositions, mouthwash compositions, mouthwash compositions, teeth whitening gels, subgingival gels, mouthwashes, mousses, foams, oral sprays, tablets, chewing tablets, chewing gum, teeth whitening strips, dental floss and floss coatings, breath freshening soluble strips, denture care products, denture adhesive products, or combinations thereof.

[0163] method The oral care compositions described herein can produce beneficial effects on oral health, such as treating, reducing, and / or preventing tooth decay, cavities, gingivitis, and / or combinations thereof, and / or whitening teeth, removing stains from teeth, and / or preventing stain buildup when applied to the oral cavity. For example, a user may dispense at least one inch of a suitable oral care composition strip as described herein (containing, for example, less than 3 ml) into an oral care appliance such as a toothbrush, applicator, and / or mouth tray and apply it to the oral cavity and / or teeth.

[0164] It can instruct users to brush their teeth thoroughly for at least 30 seconds, at least one minute, at least 90 seconds, or at least two minutes, at least once, at least twice, or at least three times a day. It can also instruct users to spit out the oral care composition after brushing.

[0165] Users may also be instructed to rinse with a mouthwash composition containing dicarboxylic acid after brushing or in lieu of brushing. The appropriate amount of mouthwash or mouthwash composition to be used is about or more than 10 ml. Users may be instructed to rinse thoroughly with the oral care composition for at least 30 seconds, at least one minute, at least 90 seconds, or at least two minutes, at least once, at least twice, or at least three times daily. Users may also be instructed to spit out the oral care composition after the process is complete.

[0166] Oral care compositions according to embodiments of the present invention can be used to treat, reduce, and / or prevent dental caries, cavities, gingivitis, and / or combinations thereof. Oral care compositions according to embodiments of the present invention can be used to provide beneficial whitening effects, such as whitening teeth, removing stains from teeth, and / or preventing stain buildup on teeth. Oral care compositions usable in this method contain a dicarboxylic acid as described above and contain little or no abrasive.

[0167] Oral care compositions may include primary packaging, such as tubes, bottles, and / or drums. The primary packaging may be placed within secondary packaging, such as cartons, shrink wrap, etc. Instructions for use of the oral care composition may be printed on the primary and / or secondary packaging. The scope of this method is intended to include instructions provided by the manufacturer, distributor, and / or producer of the oral care composition.

[0168] If the oral care composition is toothpaste, the user may be instructed to dispense toothpaste from the tube. The user may be instructed to apply a portion of toothpaste to the toothbrush. This portion of toothpaste may be any suitable shape, such as a strip, a pea-sized amount, or various other shapes that will fit onto any mechanical and / or manual brush head. The user may be instructed to apply a strip of toothpaste at least about 1 inch, at least about 0.5 inches, at least 1 inch, and / or at least 0.5 inches to the bristles of a toothbrush (such as a soft-bristled toothbrush). The user may be instructed to apply a pea-sized or rice-grain-sized portion of toothpaste to the bristles of the toothbrush, such as in cases where the toothbrush is used by a child under 6 years of age and / or under 2 years of age. The user may be instructed to brush for at least about 30 seconds, at least about 1 minute, at least about 90 seconds, at least about 2 minutes, at least 30 seconds, at least 1 minute, at least 90 seconds, and / or at least 2 minutes. The user may be instructed to brush thoroughly and / or as directed by a doctor and / or dentist. The user may be instructed to brush after each meal. Users can be instructed to brush their teeth at least once, at least twice, and / or at least three times a day. Users can also be instructed to brush no more than three times a day, for reasons such as preventing Sn staining. Users can be instructed to brush their teeth in the morning and / or before bedtime.

[0169] Because it contains ingredients that are not intended to produce the desired effect, the user can be instructed not to swallow the toothpaste composition. The user can be instructed to spit out (or cough up) the toothpaste composition after stopping the brushing cycle.

[0170] If the oral care composition is a mouthwash, the user may be instructed to dispense the mouthwash from the bottle containing the mouthwash. The user may be instructed to use the mouthwash at least once daily, at least twice daily, and / or at least three times daily. The user may be instructed to use the mouthwash composition after using toothpaste and / or dental floss. The user may be instructed to rinse in the mouth for a period of time, such as between the teeth. The user may be instructed to rinse vigorously with a portion of the mouthwash. The user may be instructed to use approximately 5 mL to approximately 50 mL, approximately 10 mL to approximately 40 mL, 10 mL, 20 mL, 25 mL, 30 mL, 40 mL, 2 teaspoons, and / or 4 teaspoons of mouthwash. The user may be instructed to rinse with the mouthwash for at least approximately 30 seconds, at least approximately 1 minute, at least approximately 90 seconds, at least approximately 2 minutes, at least 30 seconds, at least 1 minute, at least 90 seconds, and / or at least 2 minutes. Due to the presence of ingredients unsuitable for ingestion, such as fluoride, the user may be instructed not to swallow the mouthwash composition. The user can be instructed to spit out (or cough up) the mouthwash composition after the rinsing cycle has stopped.

[0171] Instructions for use of oral care compositions such as toothpaste compositions and / or mouthwashes may vary based on age. For example, one set of instructions may be provided for adults and children aged at least 6 years or at least 2 years, while a second set of instructions may be provided for children aged 6 years or less.

[0172] Example The following embodiments further illustrate the invention, and these embodiments should not be construed in any way as limiting the scope of the invention. After reading this specification, various other aspects, modifications, and equivalents thereof may be proposed to those skilled in the art without departing from the spirit of the invention or the scope of the appended claims.

[0173] Membrane cleanliness ratio (PCR) The film cleaning ratio (PCR) method is a well-known industry approach used to study the extrinsic detergency properties of oral care compositions or toothpastes containing abrasives as a means of estimating their clinical detergency potential. This method was initially disclosed by Stookey et al. (1982) and later improved by Schemehorn et al. (2011) to produce deeper, stronger stains. The method of Schemehorn et al. was used here to evaluate the ability of dicarboxylate-containing formulations to remove stain mimics. Their detergency was determined as PCR values, which are the relative amount of cleaning produced by the test formulation relative to a control suspension of calcium pyrophosphate in a thickening slurry, again described in detail by Stookey et al. and Schemehorn et al. The PCR values ​​obtained in this paper are reported in Table 4. Statistical groupings were determined using the JMP statistical software package with a difference test at α = 0.05. Treatments with different letter codes were statistically significant (p < 0.05).

[0174] The oral care compositions in Table 1 are commercially available.

[0175] Table 1. Oral Care Compositions To determine the cleaning efficacy of the chemical whitening agent in an oral care composition by using the supernatant of toothpaste to exclude the contribution of physical abrasives, 35g of toothpaste was vigorously mixed with 65g of water under ventilated conditions until homogeneous. The resulting slurry was centrifuged at 10,000 RPM to separate the abrasive from the chemical whitening agent. The supernatant was decanted from the compacted abrasive and used to determine the detergency of the chemical whitening agent without abrasive in a PCR method. Sufficient toothpaste was mixed with water to ensure at least 65g of supernatant was obtained for PCR.

[0176] To obtain the oral care compositions in Tables 2 and 3, a volume of water was added to a beaker, and oxalic acid (Sigma Aldrich (Burlington, MA, USA)) or malonic acid (Sigma Aldrich (Burlington, MA, USA)) was added to the beaker and completely dissolved using a stirring rod and magnetic mixer. After the dicarboxylic acid was completely dissolved, a volume of sodium lauryl sulfate solution was added and completely mixed using a stirring rod. A calibrated pH probe was then inserted, and the pH was adjusted dropwise with 1N NaOH (Sigma Aldrich (Burlington, MA, USA)) until the target pH was reached. 25 g of the composition was then diluted in 40 g of water to determine the detergency of the resulting solution according to a PCR method. Furthermore, the compositions in Table 3 containing low amounts of abrasives were diluted with carboxymethyl cellulose, glycerin, or an aqueous diluent specified in the PCR method described by Schemehorn et al. (2011) instead of water alone.

[0177] Table 2. Oral Care Compositions Table 3. Oral Care Compositions The silica-free toothpaste examples in Table 4 were prepared by mixing one or more humectants, water, sweeteners, and salts, buffers, dyes, and / or stabilizers to produce a liquid mixture. The liquid mixture was homogenized at 25°C until homogeneous and completely dissolved. Next, sodium hydroxide (50% solution) was added to the liquid mixture, and the liquid mixture was homogenized at 25°C until homogeneous and completely dissolved. Separate powder mixtures were prepared by mixing abrasive silica, thickening silica, and opacifiers with any thickener such as xanthan gum, carrageenan, and / or sodium carboxymethyl cellulose. The powder mixture was then mixed with the liquid mixture and completely homogenized. Next, surfactants (such as sodium lauryl sulfate) and flavoring agents were added to the mixture. The contents were homogenized at 25°C until homogeneous, and entrained air was removed by vacuum.

[0178] Table 4. Oral Care Compositions Table A. Thin Film Cleaning Ratio The results in Table A show the effect of chemical composition on stain removal when using only the toothpaste supernatant in PCR, compared to the effect of chemical composition and abrasive combination when using the entire toothpaste composition. All four full toothpaste compositions had PCR scores above 75, significantly different from all five supernatant compositions. As the low PCR results indicate, using only chemical components in regular toothpaste does not produce a significant stain removal effect in this technique; for example, the PCR scores for all supernatants were less than 15 units. Colgate Cavity Protection and Crest Cavity Protection are not whitening toothpastes and do not contain special whitening agents other than toothpaste abrasives, yet they removed sufficient stains, achieving PCR scores of 76.5 and 84.5 units, respectively. This is significantly higher than what could be achieved with any of the chemical compositions in the toothpaste supernatants considered. Even more stains could be removed when enhanced cleaning abrasives and chemical whitening agents are added to regular toothpaste. This is evidenced by the significantly higher PCR scores of Crest3D White Glamorous White and Brilliance toothpaste compared to Crest Cavity Protection and Colgate Cavity Protection.

[0179] Table B. Membrane Cleaning Ratio The PCR method was used again, but the results in Table B were obtained using the examples from Table 2. The complete toothpaste compositions of CrestCavity Protection and Colgate Cavity Protection were used. Both toothpastes were considered baseline compositions to control the accumulation of foreign stains on the tooth surface with minimal stain removal. With malonic acid alone, the compositions at pH 5.5 (Example 1) and pH 4.5 (Example 2) were not as effective at removing stains from the tooth surface as the baseline toothpaste. However, the composition at pH 3.5 (Example 3) showed no difference from Colgate Cavity Protection, indicating that a practically effective amount of stain was removed during the PCR evaluation. With oxalic acid alone, the composition at pH 5.5 (Example 4) was not as effective at removing stains from the tooth surface as the baseline toothpaste. However, the compositions at pH 4.5 (Example 5) and pH 3.5 (Example 6) effectively removed stains from the tooth surface. In Example 6, the stain removal amount was significantly greater than that of Colgate Cavity Protection, indicating that a substantial amount of stains was effectively removed during the PCR evaluation using only chemical whitening agents without abrasives. This is an unexpected result compared to the results in Table A regarding the effect of conventional chemical whitening agents on stain removal obtained by PCR. Finally, in the case of the combination of malonic acid and oxalic acid, the composition at pH 5.5 (Example 7) was not effective at removing tooth stains from the tooth surface compared to the benchmark toothpaste. However, the compositions at pH 4.5 (Example 8) and pH 3.5 (Example 9) effectively removed tooth stains from the tooth surface. In Example 9, this composition was significantly more effective than both Crest Cavity Protection and Colgate Cavity Protection, indicating that a significantly larger amount of effective tooth stains were removed using only chemical whitening agents without abrasives. This is an unexpected result compared to the results in Table A regarding the effect of conventional chemical whitening agents on stain removal obtained by PCR.

[0180] Table C. Thin Film Cleaning Ratio The PCR method was used again, but the results in Table C were obtained using the example compositions from Table 3. In this experiment, the effect of silica content at three different pH values ​​was considered. In Example 10, it was a repeat composition of Example 5 previously described. Importantly, a smaller amount of dental silica further enhanced detergency compared to Example 10. Examples 11-15 showed no difference from the baseline compositions containing significantly less dental abrasive. Crest Cavity Protection contained 16% dental abrasive, while Colgate Cavity Protection contained more than 15% dental abrasive. The compositions containing a low pH (4.5) chemical whitening agent (oxalate) and a very small amount of dental abrasive (less than 2% dental silica) removed stains from the tooth surface as effectively as the baseline compositions. This was an unexpected result compared to the results in Table A regarding the effect of conventional chemical whitening agents on detergency obtained by the PCR method.

[0181] Table D. Thin Film Cleaning Ratio PCR was used again, but the results in Table D were obtained using the examples from Table 4. In this experiment, the effect of dicarboxylic acid content at a single pH value was considered. The dicarboxylic acid content was equimolar in the 3% oxalic acid (Example 16) and 3.44% malonic acid (Example 17) samples, as were the dicarboxylic acid contents of the 1.5% oxalic acid (Example 18) and 1.77% malonic acid (Example 19) samples. The performance of the samples was consistent with the previous examples at pH 4.5 and with zero silica content. However, these samples were buffered with citric acid in a fully formulated toothpaste composition, rather than with independent pH control as in the previous experiments. Here, the citric acid / sodium citrate content varied with the specified oxalic acid and malonic acid concentrations to control the pH upon water dilution. Different citrate buffer systems were used because oxalate and malonic acid have different pKa values. Importantly, increasing the amount of dicarboxylic acid anions improved cleaning performance. The increased detergency compared to the supernatant of conventional stain-removing toothpaste is evident; however, it reaches a practically effective threshold (i.e., a PCR value of approximately 25) when the dicarboxylic acid anion concentration is reduced to approximately 1.5% molar equivalent of oxalate anion. Based on these results and not wanting to be bound by theory, we estimate that cleaning at approximately pH 4.5 requires at least approximately 1.0% molar equivalent of oxalate anion to achieve a PCR fraction of at least approximately 25 units. A PCR fraction of at least approximately 25 units removes more stains than conventional whitening chemicals alone.

[0182] As may be used herein, the terms “substantially,” “about,” and “approximately” indicate the inherent degree of uncertainty that may belong to any quantitative comparison, value, measure, or other representation. These terms also indicate the extent to which a quantitative representation may differ from the stated reference value without causing a change in the essential function of the subject matter under discussion. Furthermore, the dimensions and values ​​disclosed herein are not intended to be construed as strictly limited to the stated precise numerical values. Rather, unless otherwise specified, each such dimension is intended to represent the stated value and the range surrounding its functional equivalent. For example, a dimension disclosed as “40 mm” is intended to represent “about 40 mm.”

[0183] Unless expressly excluded or otherwise limited, every reference cited herein, including any cross-references or related patents or patent applications, and any patent application or patent claiming priority to or benefiting from it, is incorporated herein by reference in its entirety. Reference to any reference is not an endorsement of it as prior art to any disclosed or protected art herein, nor is it an endorsement of any such invention, either on its own or in combination with any one or more references. Furthermore, where any meaning or definition of a term in this invention conflicts with any meaning or definition of the same term in referenced documents, the meaning or definition given to that term in this invention shall prevail.

[0184] While specific embodiments of the invention have been illustrated and described by way of example, it will be apparent 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. Therefore, it is intended that all such changes and modifications falling within the scope of the invention be covered by the appended claims.

Claims

1. An oral care composition, said oral care composition comprising a) about 1.0% to about 10.0% by weight of the oral care composition of one or more dicarboxylic acids or their salts or combinations thereof, wherein the one or more dicarboxylic acids include oxalic acid, malic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, propanedioic acid, tartaric acid, D-tartaric acid, L-tartaric acid, maleic acid or their salts or combinations thereof. b) one or more surfactants; and c) Less than 5% abrasive by weight of the oral care composition; The pH value of the composition is in the range of about 2.0 to about 5.

0.

2. The oral care composition according to the preceding claim, wherein the one or more dicarboxylic acids comprise oxalic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, malonic acid, D-tartaric acid, L-tartaric acid, maleic acid, or salts thereof or combinations thereof, preferably wherein the one or more dicarboxylic acids comprise oxalic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, malonic acid, D-tartaric acid, maleic acid, or salts thereof or combinations thereof, more preferably wherein the one or more dicarboxylic acids comprise oxalic acid, malonic acid, or salts thereof or combinations thereof, and even more preferably wherein the one or more dicarboxylic acids comprise oxalic acid or its salts thereof or combinations thereof.

3. The oral care composition according to any one of the preceding claims, wherein the oral care composition comprises about 1.5% to about 7.5%, preferably about 2.0% to about 5.0%, more preferably about 2.5% to about 4.0%, and more preferably about 2.8% to about 3.6% of the oral care composition by weight.

4. The oral care composition according to any one of the preceding claims, wherein the pH value of the oral care composition is in the range of about 2.5 to about 5.0, preferably in the range of about 3.5 to about 5.0, and more preferably in the range of about 3.5 to about 4.

5.

5. The oral care composition according to any one of the preceding claims, wherein the oral care composition comprises less than 4%, preferably less than 3%, more preferably less than 2.5% of an abrasive by weight of the composition.

6. The oral care composition according to any one of claims 1 to 5, wherein the oral care composition is substantially free of abrasives, preferably substantially free of abrasives, and more preferably free of abrasives.

7. The oral care composition according to any one of the preceding claims, wherein the abrasive comprises a silica abrasive, a calcium abrasive, a phosphate abrasive, or a combination thereof.

8. The oral care composition according to any one of the preceding claims, wherein the one or more surfactants comprises anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, betaine surfactants or combinations thereof, preferably anionic surfactants, betaine surfactants or combinations thereof, more preferably wherein the anionic surfactant comprises sodium lauryl sulfate and / or the betaine surfactant comprises cocamidopropyl betaine.

9. The oral care composition according to any one of the preceding claims, wherein the oral care composition comprises about 3.0% to about 10.0%, preferably about 4.0% to about 7.5%, more preferably about 4.5% to about 6.0% of the one or more surfactants by weight of the oral care composition.

10. The oral care composition according to any one of the preceding claims, wherein the oral care composition further comprises a humectant, a thickener, water, a buffer, a sweetener, a flavoring agent, or a combination thereof.

11. The oral care composition according to the preceding claim, wherein the thickener comprises polysaccharides, polymers, silica thickeners, or combinations thereof.

12. The oral care composition according to any one of the preceding claims, wherein the oral care composition comprises about 60% to about 95%, preferably about 70% to about 95%, more preferably at least about 80% to about 90% of water by weight of the oral care composition.

13. The oral care composition according to any one of claims 1 to 11, wherein the oral care composition comprises about 40% to about 80%, preferably about 50% to about 75%, more preferably at least about 60% to about 70% of a humectant by weight of the oral care composition.

14. The oral care composition according to any one of the preceding claims, wherein the oral care composition exhibits a film cleaning ratio (PCR) of at least 25, preferably at least 30, more preferably at least 40, and even more preferably at least 50.

15. The oral care composition according to any one of the preceding claims, wherein the oral care composition is used for teeth whitening, removing stains on teeth, preventing stains on oral surfaces, or a combination thereof.

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