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    • 专利摘要:
    oral compositions containing metal ions a composition for oral care containing a source of stannous ion, a source of zinc ion, a polyphosphate, and a thickening agent. The thickening agent contains polyvinylpyrrolidone, a polysaccharide gum and carboxymethylcellulose. the compositions have excellent rheological properties.
    公开号:BR112016028543B1
    申请号:R112016028543-3
    申请日:2014-06-20
    公开日:2020-12-15
    发明作者:Kavita VEMISHETTI；Linh Fruge；Michael Prencipe
    申请人:Colgate-Palmolive Company；
    IPC主号:
    专利说明:

    BACKGROUND
    Stellate ions, in particular stannous salts such as stannous fluoride, are known antimicrobial agents that are used in dentifrices as agents to prevent plaque. However, some disadvantages of tin salts include instability, a tendency to stain teeth, astringency and unpleasant taste for users.
    [002] Zinc ions, in particular zinc salts, are also known antimicrobial agents that are sometimes incorporated into toothpaste formulations. The use of various zinc salts is often limited by the solubility of zinc, undesirable astringency of the consumer when higher levels of zinc are used and the reactivity of zinc since zinc ions are available for reaction (ie, ions of zinc sometimes cause adverse reactions within the formulation).
    [003] Polyphosphates and ionic active ingredients have been used in toothpastes to promote oral health. Polyphosphates are known anti-tartar agents, which help to delay stone formation.
    [004] Although such ingredients have previously been used in toothpaste, for various reasons it has proved difficult to provide these ingredients together in a formulation with satisfactory chemical and physical stability.
    [005] An attempt to provide stable dentifrice compositions is to reduce the amount of water present in the composition. However, as described in the grounds of U.S. Patent Application Publication 2012-0207686, reducing the water level and optionally replacing some or all of the water removed with a humectant, creates problems in obtaining acceptable rheological and thickening properties in the composition.
    [006] When water, which is a highly polar solvent, is removed, some conventional thickening agents tend to gel improperly. Attempts to reduce the water content in dentifrice compositions include the dentifrices described in, for example, EP 0 638 307 Bl; Pat. US No. 4,647,451; and Pat. US No. 5,670,137. Such known formulations have been shown to exhibit progressive thickening over time, which prolongs the period of time or even prevents the toothpaste from reaching a rheological steady state. Ideally, toothpaste formulations need to reach a stable state for consumer acceptance within two weeks. If a formulation routinely increases viscosity over time, distribution of the formulation will become difficult, which is likely to result in consumer dissatisfaction.
    [007] US Patent Application Publication 2012/0207686 Al discloses toothpastes that may contain stony ions, zinc ions and certain polyphosphates comprising, in a single phase, an orally acceptable vehicle, including the vehicle a thickening agent comprising a system polymeric comprising, in combination, a cross-linked polyvinylpyrrolidone and a gum, wherein the toothpaste composition has a total water content of less than 10% based on the weight of the composition.
    [008] There is a need in the art to provide low-water single-phase toothpaste compositions that have an improved rheological profile and, in particular, have a stable rheology with an adequate viscosity that effectively reduces or eliminates the progressive thickening of the composition over time which, in turn, provides a composition that can be effectively distributed over the period of its useful life. BRIEF SUMMARY
    [009] The present invention relates to an oral care composition comprising: (a) a source of stannous ion; (b) a source of zinc ion; (c) polyphosphate; and (d) a thickening agent comprising: (1) 1 to 3.5% by weight of polyvinylpyrrolidone, (ii) 0.2 to 0.45% by weight of a polysaccharide gum, and (iii) 0.05 to 0.3% by weight of carboxymethylcellulose.
    [0010] In another aspect of the invention, the oral hygiene composition shows a viscosity increase of less than 70% in relation to the initial viscosity at a temperature of 25 ° C seven days after preparation of the composition. In another embodiment of the invention, the oral care composition exhibits an increase in viscosity of less than 60% over the initial viscosity at a temperature of 25 ° C seven days after preparation of the composition. In yet another embodiment of the invention, the oral care composition exhibits an increase in viscosity between 40% - 60% over the initial viscosity at a temperature of 25 ° C seven days after preparation of the composition (the viscosity measured in Viscosity is measured at 25 ° C using a Brookfield Model RVT viscometer, Spindle V74, at 1 RPM, the viscosity is in centipoise (cP)).
    [0011] Other areas of applicability of the present invention will become apparent from the detailed description provided below. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for illustrative purposes only and are not intended to limit the scope of the invention. DETAILED DESCRIPTION
    [0012] The following description of the preferred mode (s) is merely exemplary in nature and is in no way intended to limit the invention, its application or its uses.
    [0013] As used throughout, ranges are used as abbreviations to describe each value that is within the range. Any value within the range can be selected as the end of the range. In addition, all references cited herein are hereby incorporated by reference in their entirety. In the event of a conflict in a definition in this description and that of a cited reference, this disclosure controls.
    [0014] Unless otherwise specified, all percentages and quantities expressed here and elsewhere in the specification are to be understood as referring to weight percentages. The quantities given are based on the active weight of the material,
    [0015] The oral care compositions of the various modalities are preferably in the form of a toothpaste. The term "dentifrice" as used throughout this description, denotes a paste or gel formulation. A dentifrice composition is a product that, in the normal course of administration, is not intentionally swallowed for the purpose of systemic administration of particular therapeutic agents, but is well retained in the oral cavity for a time sufficient to contact substantially all dental surfaces and / or oral tissues for the purpose of oral activity. The toothpaste can be in any desired shape, such as deep striped, striped to the surface, multi-layered, having a gel surrounding the paste, or any combination of them,
    [0016] The composition of the invention includes a zinc compound which provides a source of zinc ions. Zinc ions have been found to help reduce gingivitis, plaque, sensitivity and improved breathing benefits. The zinc compound can be a soluble or sparingly soluble zinc compound with inorganic or organic counterions. Examples include fluoride, chloride, chlorofluoride, acetate, hexafluorozirconate, sulfate, tartrate, gluconate, citrate, lactate, malate, glycinate, pyrophosphate, metaphosphate, oxalate, phosphate, carbonate salts, zinc oxides and other salts listed in Pat. US No. 4,022,880. Preferably, the zinc compound is zinc oxide.
    [0017] Zinc ions are derived from the zinc compound, that is, source of zinc ion, present in the toothpaste composition in an effective amount. An effective amount of zinc ions is defined from at least 1000 ppm of zinc ion, preferably from 2,000 ppm to 15,000 ppm. More preferably, the zinc ions are present in an amount between 3,000 ppm and 13,000 ppm and even more preferably between 4,000 ppm and 10,000 ppm. This is the total amount of zinc ions that is present in the compositions for release on the tooth surface. The amount of zinc compound (source of zinc) used in the oral composition of the invention can vary from 0.5 to 5.0% by weight, based on the total weight of the composition, typically from 1 to 4% by weight, based on in the total weight of the oral care composition.
    [0018] The compositions also include a stannous compound that provides a stony ion source. Suitable stony ion compounds or sources include, without limitation, stannous fluoride, other stannous halides such as stannous chloride dihydrate, stannous pyrophosphate, organic stannous carboxylate salts such as stannous format, acetate, gluconate, lactate, tartrate, oxalate, malonate and citrate, and the like. One or more sources of stannous ions are optional and illustratively present in an amount of total weight from 0.01% to 10%, for example, 0.1% to 3%, 0.3% to 0.7% and 0, 4% to 0.6%.
    [0019] The combined metal ion sources (tin and zinc) will be present in an amount of 0.25% to 11%, by weight of the final composition. Preferably, the metal ion sources are present in an amount of 0.4 to 7%, more preferably 1% to 5%, or 2% to 3.25%.
    [0020] The toothpaste composition includes a thickening agent that provides the toothpaste with the required rheological properties, so that the toothpaste can be stored in a dispensing container over a period of time and then reliably dispensed to from it by the user. The toothpaste should preferably have the correct viscosity not only to be dispensed, but also to exhibit an acceptable consistency inside the mouth during tooth brushing. The present inventors have found that the use of a thickening agent containing at least three components provides improved rheological properties to the composition. The three components are polyvinylpyrrolidone (PVP), a polysaccharide and carboxymethyl cellulose (CMC) gum.
    [0021] PVP can be cross-linked and can comprise a homopolymer of N-vinyl-2-pyrrolidone. Polyvinylpyrrolidone can comprise from 1 to 3.5% by weight of the composition, in a form of 2.75% to 3.25% by weight of the composition, and in another form of 1% - 1.5%.
    [0022] The toothpaste compositions of the invention have an effective viscosity and elastic limit to provide the toothpaste with the required rheological properties, so that the toothpaste can be stored in a dispensing container over a period of time and thereafter reliably dispensed from there by the user. The toothpaste should preferably have the correct viscosity not only to be dispensed but also to exhibit an acceptable consistency inside the mouth during tooth brushing. The compositions have a stable rheology that effectively reduces or eliminates the progressive thickening of the composition over time, which, in turn, provides a composition that can be effectively distributed over the period of its useful life. Viscosity and elastic limit are substantially constant over time, for example, two weeks, 6 weeks, 6 months, one year, etc. in one embodiment, the dentifrice compositions reach a stable state for acceptance by the consumer within two weeks. If a formulation routinely increases viscosity over time, distribution of the formulation will become difficult, which is likely to result in consumer dissatisfaction. As used herein, "elastic limit" is the amount of stress at which a material deforms after 7 days. The compositions of the invention have an elastic limit measured by a Brookfield viscometer at 25 ° C from 15 pascal (Pa) to 70 Pa, in a 20 Pa to 50 Pa modality. The compositions of the invention typically have a maximum Brookfield viscosity A 25 ° C after 7 days of 150000 centipoise (cP) (150000 mPa.s) at 1000000 cP (1000000 mPa.s), in another modality 200000 cP (200000 mPa.s) at 700000 cP (700000 mPa.s).
    [0023] Both CMC and polysaccharide gums contain carboxylate groups along their backbones. Although both materials are loaded polysaccharides, the density of the carboxylate groups charged along the structure is different and typically much higher for CMC than for many polysaccharide gums. For example, a commercially available CMC, CMC 2000S (available from CPKelco) has a degree of substitution of 0.9 carboxylate groups for sugar residue. Other CMCs have a degree of substitution of 0.7, 1.0 or 1.2 carboxylate groups for sugar residue. A preferred polysaccharide gum, xanthan gum, in comparison, has a degree of substitution of <0.4 carboxylate groups for sugar residue. The amount of CMC and polysaccharide gum, together, is typically 0.5%, or less by weight of the composition.
    [0024] In certain embodiments, the polysaccharide gum thickening agent has a maximum of 0.5 groups loaded per unit of sugar residue along the polysaccharide structure. For more information, see PCT Order No. PCT / US2009 / 039268, filed on April 2, 2009, which is incorporated herein by reference.
    [0025] Examples of polysaccharide gums include xanthan gum, gum arabic, guar gum, locust bean gum, tragacanth gum, gellan gum and tare gum. Polysaccharide gum, for example, xanthan gum, is present in an amount of 0.2 to 0.45% by weight based on the weight of the composition, in a form of 0.35 to 0.45% by weight of the composition and, in another embodiment, from 0.2 to 0.3% by weight of the composition.
    [0026] In addition to the three components described herein, the thickening agent may optionally contain minor amounts of additional thickeners, for example, carrageenan, starch, hydroxyethropropylcellulose, hydroxybutylmethylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose and colloidal silica. Poloxamers can also be used. Poloxamer is a synthetic block copolymer of ethylene oxide and propylene oxide. It is available in several types. Here, poloxamer 407 is preferable. It can be partially dissolved in water. When the temperature is above 65 ° C, it can dissolve in glycerin. POLOXAMER 407® is available, for example, from BASF CORPORATION, New Jersey, USA. Carbomers can also be used. The thickening agent may further comprise additional inorganic thickening agents such as colloidal magnesium aluminum silicate or finely divided silica to further improve the texture.
    [0027] In one embodiment, the total amount of thickening agent ranges from 1% by weight to 5% by weight based on the weight of the composition. In another embodiment, the amount of thickening agent is 1.5 wt% to 3.75 wt% based on the weight of the composition.
    [0028] Oral compositions also contain a polyphosphate. Polyphosphates are known to help delay stone formation. It is understood that a polyphosphate consists of two or more phosphate molecules arranged mainly in a linear configuration, although some cyclic derivatives may be present. Suitable polyphosphates are inorganic polyphosphate salts, which are preferably alkali metal salts. In some embodiments polyphosphates have an average chain length of 4, or less, or 3, or less. Typical examples include a tripolyphosphate or a pyrophosphate.
    [0029] In one embodiment, polyphosphate is an alkali metal salt of a pyrophosphate. Examples of polyphosphates include tetrasodium pyrophosphate (TSPP) and sodium tripolyphosphate (STPP) and sodium acid pyrophosphate (SAPP). Mixtures of one or more polyphosphates can be used.
    [0030] An effective amount of a polyphosphate can be 0.1% to 30%, or 2% to 20%, or 1% to 10%, or 3% to 7% by weight of the total toothpaste composition .
    [0031] The compositions of the invention contain an orally acceptable carrier. The terms "vehicle" or "aqueous vehicle", as used throughout this description, designate any safe and effective materials for use in this document, other than the source of stannous ions, the source of zinc ions, the source of polyphosphate and of the thickening agent. Such materials include, for example, water, humectants, ionic active ingredients, buffering agents, anti-calculating agents, abrasive polishing materials, peroxide sources, alkali metal bicarbonate salts, surfactants, titanium dioxide, coloring agents, flavor systems, sweetening agents, antimicrobial agents, herbal agents, desensitizing agents, stain reducing agents and mixtures thereof. Such materials are well known in the art and are easily chosen by a person skilled in the art based on the desired physical and aesthetic properties for the compositions being prepared. The carriers typically comprise 40% to 99%, preferably 70% to 98%, and more preferably 90% to 95%, by weight of the toothpaste composition.
    [0032] The composition may comprise at least one humectant. The humectant serves to keep toothpaste compositions from being hardened by exposure to air and certain humectants can also impart desirable sweetness of flavor to toothpaste compositions. Humectants suitable for use in the invention include glycerin, sorbitol, polyethylene glycol, propylene glycol, xylitol and other edible polyhydric alcohols. Glycerin, polyethylene glycol, polypropylene glycol and their mixtures, especially their mixtures, are preferred. The humectant generally comprises from 0.1% to 70%, preferably from 1% to 60%, and more preferably from 15% to 55%, by weight of the composition.
    [0033] The compositions described herein may also contain a buffering agent. The buffer system is preferably adapted to chelate the tin ions in the composition. Buffering agents, as used herein, refer to agents that can be used to adjust the pH of the compositions to a range of pH 3.0 to pH 10, in some embodiments a pH of 4 to 7 or 4.5 to 6 or from 5 to 5.5.
    [0034] Buffering agents include alkali metal hydroxides, ammonium hydroxide, organic ammonium compounds, carbonates, sesquicarbonates, borates, silicates, phosphates, imidazole and mixtures thereof. Specific buffering agents include monosodium phosphate, trisodium phosphate, sodium benzoate, benzoic acid, sodium hydroxide, potassium hydroxide, alkali metal carbonate salts, sodium carbonate, imidazole, pyrophosphate, citric acid and sodium citrate. In some embodiments, the buffer system may comprise at least one of an organic acid or an alkali metal salt thereof, the organic acid being, preferably, citric acid. The buffer system may comprise a mixture of citric acid and trisodium citrate. Buffering agents are used at a level of 0.1% to 30%, in a mode of 0.1% to 10%, and in another mode of 1% to 5%, and in another mode of 0.3% to 3 % by weight of the present composition.
    [0035] The compositions may contain a source of fluoride ion. The fluoride ion source here is a fluoride source capable of providing free fluoride ions and is typically soluble. Sources of fluoride ion include stannous fluoride, sodium fluoride, potassium fluoride, indium fluoride, zinc fluoride, sodium monofluorophosphate, sodium fluorosilicate, ammonium fluorosilicate, amine fluoride (for example, N'-octadecyltrimethylenethine N'-octadylamine) , N, N'-tris (2-ethanol) - dihydrofluoride), ammonium fluoride, titanium fluoride, hexafluorosulfate and their combinations;
    [0036] Sodium fluoride and stannous fluoride are the preferred sources of soluble ion fluoride. Norris et al., Pat. US No. 2,947,725, and Pat. US No. 3,678,154, and Pat. US No. 6,190,644 disclose such fluoride ion sources as well as others.
    [0037] The present compositions may contain a source of soluble fluoride ion capable of providing from 50 ppm to 3500 ppm, and preferably from 500 ppm to 3000 ppm of free fluoride ions. To provide the desired amount of fluoride ions, the fluoride ion source can be present in the total toothpaste composition in an amount of 0.1% to 5%, preferably 0.2% to 1%, and most preferably 0 , 3 to 0.6%, by weight of the total toothpaste composition.
    [0038] Correspondingly, the present invention also provides a method for the manufacture of a toothpaste composition, the method comprising providing a source of stannous ions, mixing the source of stannous ions with an aqueous buffer system adapted to chelate stony ions in a premixing and combining the premix with at least one active component and an orally acceptable vehicle of the toothpaste composition.
    [0039] The compositions of the invention may contain water. The water used in the preparation of commercially suitable oral compositions should preferably be low in ions and free from organic impurities. In the dentifrice composition, water will generally comprise less than 15%, in a modality less than 10%, in another modality of 0.1% to 10%, and in another modality of 0% to 6%, by weight of the composition here displayed. The amounts of water include free water that is added plus that introduced with other materials, such as silica, surfactant solutions and / or color solutions.
    [0040] The compositions can also employ synthetic anionic polymers [including polyacrylates and copolymers of maleic anhydride or methyl vinyl ether (e.g. GANTREZ®), as described, for example, in Pat. US No. 4,627,977 to Gaffar et al; as well as, for example, polyamino-propanesulfonic acid (AMPS)], zinc citrate trihydrate, diphosphonates (eg, EHDP, AHP), polypeptides (such as polyaspartic and polyglutamic acids) and mixtures thereof.
    [0041] An abrasive or particulate polishing material can also be included in toothpaste compositions. The abrasive polishing material contemplated for use in the compositions of the present invention can be any material that does not excessively abrasion the dentin. Typical abrasive polishing materials include silicas including gels, precipitates and hydrated silica; aluminum; Aluminum oxide; iron oxide; perlite; plastic particles, for example, polyethylene; phosphates including orthophosphates, polymetaphosphates and pyrophosphates. Specific examples include sodium bicarbonate, dicalcium orthophosphate dihydrate, calcium pyrophosphate, tricalcium phosphate, calcium polymetaphosphate, insoluble sodium polymetaphosphate, hydrated alumina, beta calcium pyrophosphate, calcium carbonate, calcium phosphate (for example, dicalcium dihydrate) and resinous abrasive materials such as condensation products on urea and formaldehyde particles, and others such as disclosed in U.S. Pat. No. 3,070,510. Combinations of two or more abrasives can be used.
    [0042] Silica dental abrasives of various types are suitable due to their unique benefits of exceptional cleaning and polishing performance without unduly damaging tooth enamel or dentin. The silica abrasive polishing materials of the present invention, as well as other abrasives, generally have an average particle size ranging between 0.1 to 30 microns and preferably between 5 and 15 microns. The abrasive can be precipitated silica or silica gels such as the silica xerogels described in U.S. Pat. US No. 3,538.23 and Pat. US No. 3,862,307. Examples are silica xerogels marketed under the trade name "SYLOID®" by W. R. Grace & Company, Davison Chemical Division. Precipitated silica materials such as those marketed by J. M. Huber Corporation under the trade name "ZEODENT®" are also preferred, particularly silica bearing the designation "Zeodent 119". The types of silica dental abrasives useful in the toothpastes of the present invention are described in more detail in U.S. Pat. No. 4,340,583. Silica abrasives are also described in Rice, Pat. US Nos. 5,589,160; 5,603,920; 5,651,958; 5,658,553; and 5,716,601. The abrasive in the toothpaste compositions described herein is generally present at a level of 6% to 70%, or 15% to 70% by weight of the composition. Typically, toothpastes contain 10% to 50% abrasive, by weight of the toothpaste composition.
    [0043] The present invention can include a bleaching agent, for example, a group selected from the group consisting of peroxides, metal chlorites, perborates, percarbonates, peroxyacids, hypochlorites and combinations thereof. In one embodiment, the bleaching agent is a source of peroxide. The peroxide source is selected from the group consisting of hydrogen peroxide, calcium peroxide, urea peroxide and mixtures of these. The preferred source of peroxide is calcium peroxide. The following amounts represent the amount of peroxide raw material, although the peroxide source may contain ingredients other than the peroxide raw material. The present composition may contain from 0.01% to 10%, preferably from 0.1% to 5%, more preferably from 0.2% to 3% and more preferably from 0.3% to 0.8% of a peroxide source, by weight of toothpaste composition.
    [0044] The compositions may contain anionic, cationic, non-ionic and / or zwitterionic surfactants, for example: i. Water-soluble salts of higher fatty acid monoglyceride monosulfates, such as the sodium salt of the monoglyceride monoglyceride of hydrogenated coconut oil fatty acids such as sodium N-methyl-N-cocoyl-taurate, sodium cocomonoglyceride sulphate, ii. Higher alkyl sulfates, such as sodium lauryl sulfate, iii. Higher alkyl ether sulfates, for example, of the formula CH3 (CH2) mCH2 (OCH2CH2) nOSO3X, where m is 6-16, for example, 10, n is 1-6, for example, 2, 3 or 4 and X is Na or K, for example sodium laureth-2 sulfate iv. Higher alkylaryl sulfonates such as sodium dodecylbenzenesulfonate (sodium laurylbenzenesulfonate) v. Higher alkyl sulfoacetates, such as sodium lauryl sulfoacetate (sodium dodecyl sulfoacetate), 1,2-dihydroxypropane sulfonate higher fatty acid esters, sulfocolaurate (sulfoacetamide N-2-ethyl laurate) and sulfoacetamide lauryl sulfate sodium.
    [0045] By "upper alkyl" is meant, for example, C6-30 alkyl. In particular embodiments, the anionic surfactant is selected from sodium lauryl sulfate and sodium lauryl sulfate ether. The anionic surfactant can be present in an amount that is effective, for example,> 0.01% by weight of the formulation, but not at a concentration that is irritating to oral tissue, for example, <10%, and the optimal concentrations depend on the particular formulation and the particular surfactant. For example, the concentrations used or a mouthwash are typically in the order of a tenth that you used for toothpaste. In one embodiment, the anionic surfactant is present in a toothpaste at 0.3% to 4.5% by weight, for example, 1.5%. The compositions may optionally contain mixtures of surfactants, for example, comprising anionic surfactants and other surfactants which may be anionic, cationic, zwitterionic or non-ionic. Generally, surfactants are those that are reasonably stable over a wide pH range. Surfactants are described more fully, for example, in U.S. Pat. US No. 3,959,458; Pat. US No. 3,937,807; and Pat. US No. 4,051,234. In certain embodiments, the anionic surfactants useful herein include the water-soluble salts of alkyl sulfates having 10 to 18 carbon atoms in the alkyl radical and the water-soluble salts of sulfonated monoglycerides of fatty acids having 10 to 18 carbon atoms. Sodium lauryl sulfate, sodium lauroyl sarcosinate and sodium coconut monoglyceride sulfonates are examples of anionic surfactants of this type. In a particular embodiment, the composition comprises sodium lauryl sulfate.
    [0046] The surfactant or mixtures of compatible surfactants may be present in the composition in 0.1% to 5%, in another modality 0.3% to 3% and in another modality 0.5% to 2% by weight of the total composition .
    [0047] Titanium dioxide can also be added to the present composition. Titanium dioxide is a white powder that adds opacity to compositions. Titanium dioxide generally comprises from 0.25% to 5%, by weight of the composition.
    [0048] The compositions can also contain an agent that interferes with or prevents bacterial binding, for example, solbrol or chitosan.
    [0049] The compositions may further comprise a source of calcium and phosphate selected from (i) calcium-glass complexes, for example, calcium and sodium phosphosilicates, and (ii) calcium-protein complexes, for example, casein phosphate amorphous calcium phosphate.
    [0050] The compositions may further comprise a soluble calcium salt, for example, selected from calcium sulfate, calcium chloride, calcium nitrate, calcium acetate, calcium lactate and combinations thereof.
    [0051] Coloring agents can also be added to the present composition. The coloring agent can be in the form of an aqueous solution, preferably 1% coloring agent in a water solution. The color solutions generally comprise from 0.01% to 5%, by weight of the composition.
    [0052] A flavor system can also be added to the compositions. Suitable flavoring components include sesame oil, peppermint oil, peppermint oil, clove bud oil, menthol, anethole, methyl salicylate, eucalyptol, cassia, 1-menthyl acetate, sage, eugenol, oil parsley, oxanone, alpha-irisone, marjoram, lemon, orange, propenyl guaetol, cinnamon, vanillin, ethyl vanillin, heliotropin, 4-cis-heptenal, diacetyl, methyl-to-tert-butylphenyl acetate and mixtures thereof. Soft drinks can also be part of the flavor system. The preferred cooling agents in the present compositions are the paramentan carboxamide agents such as N-ethyl-p-menthane-3-carboxamide (known commercially as "WS-3") and mixtures thereof. A flavor system is generally used in compositions at levels of 0.001% to 5%, by weight of the composition.
    [0053] Sweetening agents can be added to the compositions. These include saccharin, dextrose, sucrose, lactose, xylitol, maltose, levulose, aspartame, sodium cyclamate, D-tryptophan, dihydrocalcones, acesulfame and mixtures thereof. Various coloring agents can also be incorporated into the present invention. Sweetening agents and coloring agents are generally used in toothpastes at levels of 0.005% to 5%, by weight of the composition.
    [0054] Arginine, when present, can be present at levels of, for example, 0.1% to 20% (expressed by weight of free base), for example, 1% to 10% by weight.
    The present invention can also include other agents, such as antimicrobial agents. Included among these agents are water-insoluble non-cationic antimicrobial agents such as halogenated diphenyl ethers, phenolic compounds including phenol and their homologs, mono and polyalkyl and aromatic halophenols, resorcinol and its derivatives, bisphenolic compounds and halogenated salicylanilides, benzoic esters and Carbanylides halogenated, polyphenols and herbs. Water-soluble antimicrobials include quaternary ammonium salts and bis-bikinianide salts, among others. Triclosan monophosphate is an additional preferred water-soluble antimicrobial agent. Quaternary ammonium agents include those in which one or two of the substituents on the quaternary nitrogen have a carbon chain length (typically alkyl group) of 8 to 20, typically 10 to 18 carbon atoms, while the remaining substitutes (typically group alkyl or benzyl) have a lower number of carbon atoms, such as 1 to 7 carbon atoms, typically methyl or ethyl groups. Dodecyltrimethylammonium bromide, tetradecylpyridinium chloride, domifene bromide, N-tetradecyl-4-ethylpyridinium chloride, dodecyl dimethyl (2-phenoxyethyl) ammonium, benzyl dimethylstearylammonium chloride, 5-ammonium chloride, cetyl chloride -hexyl) -5-methyl-hexahydropyrimidine, benzalkonium chloride, benzethonium chloride and methyl benzethonium chloride are examples of typical quaternary ammonium antibacterial agents. Other compounds are bis [4-R-amino) -1-pyridinium] alkanes as disclosed in U.S. Pat. US No. 4,206,215, issued June 3, 1980, to Bailey.
    [0056] Other antimicrobials such as copper bisglycinate, copper glycinate, zinc citrate and zinc lactate may also be included. Enzymes, including endoglycosidase, papain, dextranase, mutanase and mixtures thereof, are also useful. These agents are disclosed in Pat. US No. 2,946,725, of July 26, 1960, to Norris et al. and in Pat. US No. 4,051,234, of September 27, 1977, to Gieske et al. Specific antimicrobial agents include chlorhexidine, triclosan, triclosan monophosphate and flavoring oils such as thymol. Triclosan is a preferred antimicrobial agent for inclusion in the present compositions. Triclosan and other agents of this type are disclosed in Parran, Jr. et al., Pat. No. 5,015,466, issued May 14, 1991, and U.S. Pat. US No. 4,894,220, of January 16, 1990, to Nabi et al. Water-insoluble antimicrobial agents, water-soluble agents and enzymes can be present in both the first and second dentifrice compositions. Quaternary ammonium agents, stannous salts and substituted guanidines are preferably present in the second toothpaste composition. These agents can be present at levels between 0.01% and 1.5%, by weight of the toothpaste composition.
    [0057] An herbal agent, including, but not limited to golden thread extract, honeysuckle extract and mixtures thereof, may also be present in the compositions contained here at levels of 0.01% to 0.05%. Such herbal agents are believed to provide anti-bacterial efficacy. Polyphenols can also be included at levels between 0.01% and 2%. A preferred polyphenol is tea polyphenol.
    [0058] An effective amount of a desensitizing agent can also be incorporated into the present compositions. Desensitizing agents include those selected from alkali metal salts with a chloride, nitrate sulfate or group II metal acetate or polymerizable monomer or aluminum to occlude the tubules, alkali metal or ammonium nitrate, ammonium oxylate, citric acid and sodium citrate. Preferred salts are potassium nitrate, potassium citrate, potassium chloride and mixtures thereof. Such desensitizing agents are disclosed, for example, in U.S. Pat. No. 5,718,885.
    [0059] The dentifrice compositions can be a paste, gel, or any configuration or combination thereof. The compositions of the invention can be a single phase. Another embodiment of the present invention includes double-phase or multi-phase compositions comprising the present low-water compositions as a phase and at least one separate phase comprising additional toothpaste components to further improve stability, performance and / or the aesthetics of the toothpaste product. For example, a double-phase composition can comprise a first phase comprising the present low water polyphosphate composition and a separate second phase comprising additional active agents such as a source of stannous ion, bleaching agents, preferably a source of peroxide, or a tooth surface conditioning agent to provide improved cleaning, whitening, anti-staining and mouth feel benefits.
    [0060] Examples of tooth conditioning agents are polysiloxanes and modified polysiloxanes, including diorganopolysiloxanes such as polydimethylsiloxane (PDMS); Alkyl- and alkoxy-dimethicone copolyols such as C12 to C20 alkyl dimethicone copolyols; and aminoalkylsilicones. These siloxane polymers are described, for example, in U.S. Pat. U.S. Nos. 5,759,523; 6,024,891; 6,123,950; 6,019,962; 6,139,823 all attributed to The Procter & Gamble Company.
    [0061] The dispenser for toothpaste compositions can be a tube, pump or any other suitable container for dispensing toothpaste. In a double-phase oral composition, each oral composition will be contained in a compartment physically separated from a dispenser and dispensed side by side.
    [0062] In the practice of the modalities, the user only has to apply the toothpaste composition here, to the surfaces of the teeth of a human or animal, in the desired areas, in order to obtain a desired effect, for example, whitening, refreshing the breathing, caries prevention, 0 pain relief, gum health, tartar control, erosion control, etc. The use of toothpastes to control erosion of the tooth surface, or to prevent demineralization, is known and described, for example, in U.S. Pat. US No. 6,685,920, the description of which is incorporated herein by reference in its entirety. The compositions can also be applied to other surfaces of the oral cavity, such as the gingival or mucous tissues, although the benefits are believed to be best achieved when the toothpaste compositions are applied to the teeth. The toothpaste composition can contact the surface of the tooth and / or the oral cavity directly or indirectly, however, it is preferable that the toothpaste composition is applied directly. The toothpaste composition can be applied by any means, but is preferably applied with a brush or by rinsing with a toothpaste paste.
    [0063] The manufacture of the oral composition of the present invention can be carried out by any of several standard techniques for producing such compositions. To prepare a dentifrice, a vehicle containing a humectant, for example, one or more of glycerin, glycerol, sorbitol and propylene glycol, thickening agents and antibacterial agent such as triclosan, can be prepared, and the vehicle and a mixture of anionic and amphoteric surfactants are added, followed by mixing a polishing agent, as well as fluorine salts, with the premix. Finally, the flavoring agent is added and the pH is adjusted between 6.8 and 7.0.
    [0064] The present invention provides, in a first embodiment, a composition for oral care (Composition 1) comprising: (a) a source of stannous ion; (b) a source of zinc ion; (c) polyphosphate; and (d) a thickening agent comprising: (i) 1 to 3.5% by weight of polyvinylpyrrolidone, (ii) 0.2 to 0.45% by weight of a polysaccharide gum, and (iii) 0.05 0.3% by weight of carboxymethylcellulose; for example: 1.1. Composition 1 in which the amount of stannous ions source, by weight of the composition, is 0.01% to 10%, for example 0.1% to 3%, 0.3% to 0.7%, from 0.4% to 0.6%; 1.2. Any of the preceding compositions in which the amount of the zinc ion source, by weight of the composition, is 0.5% to 5%, or 1% to 4%; 1.3. Any of the preceding compositions in which the amount of polyphosphate, by weight of the composition, is 0.1% to 30%, or 2% to 20%, or 1% to 10%, or 3% to 7% ; 1.4. Any of the preceding compositions in which the source of stannous ions is stannous fluoride, other stannous halides such as stannous chloride dihydrate, stannous pyrophosphate, stannous carboxylate salts such as tin format, acetate, gluconate, lactate, tartrate, oxalate , malonate and citrate, ethylene stannous cloxide, or a mixture thereof; 1.5. Any of the preceding compositions in which the source of zinc ion is zinc fluoride, zinc chloride, zinc chlorofluoride, zinc acetate, zinc hexafluorozirconate, zinc sulfate, zinc tartrate, zinc gluconate, zinc citrate, lactate zinc, zinc malate, zinc glycinate, zinc pyrophosphate, zinc metaphosphate, zinc oxalate, zinc phosphate, zinc carbonate, zinc oxide, zinc or a mixture thereof; 1.6. Any of the preceding compositions in which the polyphosphate is tetrasodium pyrophosphate (TSPP), sodium tripolyphosphate (STPP), sodium acid pyrophosphate (SAPP), or a mixture thereof; 1.7. Any of the preceding compositions in which the total amount of thickening agent is 1% to 5% by weight of the composition; 1.8. Any of the foregoing compositions in which the polysaccharide gum is xanthan gum, arabic gum, guar gum, locust bean gum, tragacanth gum, gellan gum, tare gum or a mixture thereof; 1.9. Any of the preceding compositions in which the amount of polyvinylpyrrolidone by weight of the composition is from 1% to 3.5%, or from 2.75% to 3.25%, or from 1% to 1.5%, the amount of polysaccharide gum by weight of the composition is 0.2% to 0.45%, or 0.35% to 0.45%, or 0.2% to 0.3% and the amount of carboxymethylcellulose by weight of the composition is 0.05% to 0.3%, or 0.05% to 0.15%, or 0.2% to 0.3%; 1.10. Any of the preceding compositions having an elastic limit of 15 Pa to 70 Pa or 20 Pa to 50 Pa and a viscosity of 150,000 cP (150,000 mPa.s) to 1,000,000 cP (1,000,000 mPa.s) or 200,000 cP ( 200,000 mPa.s) at 700,000 cP (700,000 mPa.s), measured by a Brookfield viscometer at 25 ° C; 1.11. Any of the preceding compositions in which the oral hygiene composition exhibits an increase in viscosity of less than 70% over the initial viscosity at a temperature of 25 ° C seven days after preparation of the composition; Or it exhibits a viscosity increase of less than 60% over the initial viscosity at a temperature of 25 ° C seven days after preparation of the composition; Or it exhibits a viscosity increase of 40% - 60% over the initial viscosity at a temperature of 25 ° C seven days after preparation of the composition. 1.12. Any of the foregoing compositions further comprising an effective amount of fluoride, for example, wherein fluoride is a salt selected from stannous fluoride, sodium fluoride, potassium fluoride, indium fluoride, zinc fluoride, sodium monofluorophosphate, sodium fluorosilicate sodium, ammonium fluorosilicate, amine fluoride For example, N'- octadecyltrimethylenediamine-N, N, N-tris (2-ethanol) - dihydrofluoride), ammonium fluoride, titanium fluoride, hexafluorosulfate and combinations thereof; 1.13. Any of the preceding compositions comprising L-arginine in the form of a free or orally acceptable salt; 1.14. Any of the preceding compositions comprising buffering agents, for example, citric acid buffer or sodium phosphate buffer (for example, monobasic sodium phosphate and disodium phosphate); 1.15. Any of the preceding compositions comprising a humectant, for example, selected from glycerin, sorbitol, propylene glycol, polyethylene glycol, xylitol and mixtures thereof; 1.16. Any of the preceding compositions further comprising an abrasive or particulate; 1.17. The immediately preceding composition in which the abrasive or particles is selected from sodium bicarbonate, calcium phosphate (eg, dicalcium phosphate dihydrate), calcium sulphate, precipitated calcium carbonate, calcium pyrophosphate, silica (for example, silica hydrated), iron oxide, plastic particles, for example, polyethylene, and combinations thereof; 1.18. Any of the preceding compositions comprising an abrasive in an amount of 6 to 70%, or 15% to 70%, or 10% to 50%, of the total weight of the composition; 1.19. Any of the preceding compositions comprising one or more surfactants, for example, selected from anionic, cationic, zwitterionic and non-ionic surfactants, and mixtures thereof, for example, comprising an anionic surfactant, for example, a surfactant selected from sodium lauryl sulfate, sodium lauryl sulfate ether, and mixtures thereof, for example, in an amount of 0.3% to 4.5% by weight; 1.20. Any of the preceding compositions in the form of a toothpaste or tooth gel; 1.21. Any of the preceding compositions further comprising flavorings, fragrances and / or colors; 1.22. Any of the preceding compositions comprising still less than 15% water; 1.23. Any of the foregoing compositions comprising one or more antibacterial agents, for example, comprising an antibacterial agent selected from halogenated diphenyl ether (for example, triclosan), herbal extracts and essential oils (for example, rosemary extract, tea extract, extract magnolia, thymol, menthol, eucalyptol, geraniol, carvacrol, citral, hinokitol, catechol, methyl salicylate, epigallocatechin gaiate, epigallocatechin, gallic acid, miswak extract, sea buckthorn extract), bisguidide antiseptic, eg or octenidine), quaternary ammonium compounds (eg, cetylpyridinium benzalkonium chloride, tetradecylpyridinium chloride (TPC), N-tetradecyl-4-ethylpyridinium chloride (TDEPC)), phenolic antiseptics, hexetidine, octenidine, bloodstream iodine, delmopinol, salifluor, metal ions, (eg zinc citrate, tin salts, copper salts, iron salts), sanguine, propolis and age oxygenating agents (for example, hydrogen peroxide, sodium peroxborate buffer or peroxycarbonate), phthalic acid and its salts, monopertallic acid and its salts and esters, ascorbyl stearate, oleoyl sarcosine, alkyl sulfate, dioctyl sulfosuccinate, salicylanilide, bromicylanilide, bromicylanilide domifene, delmopinol, octapinol and other piperidine derivatives, nicine preparations, chlorite salts; and mixtures of any of the above; for example, comprising triclosan or cetylpyridinium chloride; 1.24. Any of the preceding compositions further comprising a bleaching agent, for example, a group selected from the group consisting of peroxides, metal chlorites, perborates, percarbonates, peroxyacids, hypochlorites and combinations thereof; 1.25. Any of the preceding compositions further comprising hydrogen peroxide or a source of hydrogen peroxide, for example, urea peroxide or a peroxide or complex salt (for example, such as peroxyphosphate, peroxycarbonate, perborate, peroxysilicate or persulfate salts, for example example, calcium peroxyphosphate, sodium perborate, sodium carbonate peroxide, sodium peroxyphosphate and potassium persulfate); 1.26. Any of the foregoing compositions further comprising an agent that interferes with or prevents bacterial binding, for example, solbrol or chitosan; 1.27. Any of the preceding compositions further comprising a source of calcium and phosphate selected from (i) calcium-glass complexes, for example, sodium calcium phosphates, and (ii) calcium-protein complexes, for example calcium phosphate casein phosphate phosphate; 1.28. Any of the foregoing compositions further comprising a soluble calcium salt, for example, selected from calcium sulfate, calcium chloride, calcium nitrate, calcium acetate, calcium lactate and combinations thereof; 1.29. Any of the foregoing compositions further comprising a physiologically or orally acceptable potassium salt, for example, potassium nitrate or potassium chloride, in an amount effective to reduce tooth sensitivity; 1.30. Any of the preceding compositions further comprising a breath freshener, fragrance or flavoring; 1.31. Any of the previous compositions effective after application to the oral cavity, for example, with brushing, to (i) reduce tooth hypersensitivity, (ii) reduce plaque accumulation, (iii) reduce or inhibit demineralization and promote remineralization of the teeth, (iv) inhibit the formation of microbial biofilm in the oral cavity, (v) reduce or inhibit gingivitis, (vi) promote the healing of wounds or cuts in the mouth, (vii) reduce the levels of bacteria producing acid, (viii) increase the relative levels of non-cariogenic and / or non-plaque bacteria, (ix) reduce or inhibit the formation of dental caries, (x) reduce, repair or inhibit precarious enamel lesions, (xi) treat, relieve or reduce dry mouth, (xii) clean teeth and oral cavity, (xiii) reduce erosion, (xiv) whiten teeth; and / or (xv) promoting systemic health, including cardiovascular health, for example, reducing the potential for systemic infection through oral tissues; 1.32. Composition obtained or obtainable by combining the ingredients according to any of the preceding compositions; 1.33. Any of the preceding compositions in which the composition is a toothpaste optionally further comprising one or more of one or more of water, abrasives, surfactants, foaming agents, vitamins, polymers, enzymes, humectants, thickeners, antimicrobial agents, preservatives, flavorings , dyes and / or their combinations.
    [0065] The following examples are still illustrative of the preferred embodiments, but it should be understood that the invention is not limited to them. EXAMPLES Example 1 Formula A

    Example 2 Viscosity and elastic limit Procedure
    [0066] Viscosity and elastic limit are measured for the composition of Formula A containing the varying amounts of CMC7 (degree of substitution of 0.7 carboxyl for monomer, sodium carboxymethylcellulose and polyanionic cellulose from Quimica Amtex, Mexico), PVP (Polyplasdone XL-10, a crosslinked homopolymer of N-vinyl-2-pyrrolidone whose average particle size is 110-140 µm and apparent density is 0.3 g / cm3) and xanthan gum indicated in the Results section. Viscosity is measured at 25 ° C using a Brookfield Model RVT viscometer, Spindle V74, at 1 RPM; viscosity is in centipoise (cP) (1 cP = 1 mPa.s). The yield strength is measured at 25 ° C using a Brookfield Model RVT viscometer, Spindle V74 (Ysup is elastic limit in Pa). Results Table 1 - Elastic limit
    Table 2 - Viscosity Formulation 1 - 0% PVP, 0.1% xanthan, 0.4% CMC
    Formulation 2 - 3% PVP, 0.1% xanthan, 0.4% CMC
    Formulation 3 - 3% PVP, 0.1% xanthan, 0.4% CMC
    Formulation 4 - 3% PVP, 0.4% xanthan, 0.1% CMC
    Formulation 5 - 1.5% PVP, 0.25% xanthan, 0.25% CMC


    [0067] As can be seen from the data in Table 1, Formulations 4 and 5 have an acceptable elastic limit and also show a much slower increase in viscosity over a seven day period compared to Comparative Formulation 1 -3.
    [0068] As those skilled in the art will appreciate, numerous changes and modifications can be made to the modalities described here without departing from the spirit of the invention. All of these variations are intended to be within the scope of the appended claims.
    权利要求:
    Claims (14)
    [0001]
    1. Composition for oral care, characterized by the fact that it comprises: (a) a source of stannous ion; (b) a source of zinc ion; (c) polyphosphate; and (d) a thickening agent comprising: (i) 1 to 3.5% by weight of polyvinylpyrrolidone, (ii) 0.2 to 0.45% by weight of a polysaccharide gum, and (iii) 0.05 to 0.3% by weight of carboxymethylcellulose, where% by weight is by weight of the composition; and wherein the oral care composition exhibits an increase in viscosity of less than 70% over the initial viscosity at a temperature of 25 ° C seven days after the composition is prepared.
    [0002]
    2. Composition according to claim 1, characterized by the fact that the amount of source of stannous ion, by weight of the composition, is from 0.01% to 10%, and is selected from stannous fluoride, other stannous halides such such as stannous chloride dihydrate, stannous pyrophosphate, organic stannous carboxylate salts such as formate, acetate, gluconate, lactate, tartrate, oxalate, malonate and citrate, stannous ethylene glyoxide, and a mixture thereof.
    [0003]
    Composition according to claim 1 or 2, characterized by the fact that the source of tin is stannous fluoride.
    [0004]
    Composition according to any one of claims 1 to 3, characterized in that the amount of source of zinc ion, by weight of the composition, is 0.5% to 5.0% and is selected from fluoride zinc, zinc chloride, zinc chlorofluoride, zinc acetate, zinc hexafluorozirconate, zinc sulfate, zinc tartrate, zinc gluconate, zinc citrate, zinc lactate, zinc malate, zinc glycinate, zinc pyrophosphate , zinc metaphosphate, zinc oxalate, zinc phosphate, zinc carbonate, zinc oxide, and a mixture thereof.
    [0005]
    Composition according to any one of claims 1 to 4, characterized by the fact that the source of zinc is zinc oxide.
    [0006]
    Composition according to any one of claims 1 to 5, characterized in that the amount of polyphosphate, by weight of the composition, is 0.1% to 30%, or 2% to 20%, or 1% to 10%, or 3% to 7%, and is selected from tetrasodium pyrophosphate, sodium tripolyphosphate, sodium acid pyrophosphate, and a mixture thereof.
    [0007]
    Composition according to any one of claims 1 to 6, characterized in that the amount of polyvinylpyrrolidone by weight of the composition is 2.75% to 3.25%, the amount of polysaccharide gum by weight of the composition is 0.35% to 0.45%, and the amount of carboxymethyl cellulose by weight of the composition is 0.05% to 0.15%.
    [0008]
    Composition according to any one of claims 1 to 7, characterized in that the amount of polyvinylpyrrolidone by weight of the composition is 1 - 1.5%, the amount of polysaccharide gum by weight of the composition , 2% to 0.3%, and the amount of carboxymethylcellulose by weight of the composition is 0.2% to 0.3%.
    [0009]
    Composition according to any one of claims 1 to 8, characterized in that the polysaccharide gum is xanthan gum, arabic gum, guar gum, locust bean gum, tragacanth, gelan gum, tara gum or a mixture thereof .
    [0010]
    Composition according to any one of claims 1 to 9, characterized in that the polysaccharide gum is xanthan gum.
    [0011]
    11. Composition according to any one of claims 1 to 10, characterized by the fact that it has a Brookfield elastic limit at 25 ° C of 15 Pa at 70 Pa, and a maximum Brookfield viscosity at 25 ° C after 7 dais from 150,000 cP (150,000 mPa.s) to 1,000,000 cP (1,000,000 mPa.s).
    [0012]
    Composition according to any one of claims 1 to 11, characterized in that it further comprises a fluoride salt selected from stannous fluoride, sodium fluoride, potassium fluoride, indium fluoride, zinc fluoride, sodium monofluorophosphate , sodium fluorosilicate, ammonium fluorosilicate, amine fluoride (e.g., N'-octadecyltrimethylenediamine- N, N, N'-tris (2-ethanol) -dihydrofluoride), ammonium fluoride, titanium fluoride, hexafluorosulfate, and combinations of the same.
    [0013]
    13. Composition according to any one of claims 1 to 12, characterized in that it further comprises an abrasive in an amount of 6 to 70%, or 15% to 70%, or 10% to 50% by weight of the total composition.
    [0014]
    Composition according to any one of claims 1 to 13, characterized in that a humectant, a bleaching agent, a bactericidal agent, a dye, any combination of two or more of
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    公开号 | 公开日
    AU2014398220A1|2016-12-22|
    CN110123669A|2019-08-16|
    AR100928A1|2016-11-09|
    US10485740B2|2019-11-26|
    PH12016502469B1|2017-04-10|
    MX2016015231A|2017-03-23|
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    CA2952916C|2021-06-22|
    KR20170021780A|2017-02-28|
    CN106413815B|2019-06-14|
    TWI674905B|2019-10-21|
    EP3157639B1|2018-12-26|
    RU2016150160A3|2018-07-27|
    WO2015195139A1|2015-12-23|
    US20190142716A1|2019-05-16|
    PH12016502469A1|2017-04-10|
    RU2016150160A|2018-07-27|
    TW201609161A|2016-03-16|
    IL249530D0|2017-02-28|
    MX358713B|2018-08-24|
    US9962322B2|2018-05-08|
    BR112016028543A2|2018-07-10|
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    CN106413815A|2017-02-15|
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    WO2021152504A1|2020-01-30|2021-08-05|3M Innovative Properties Company|Delivery system for aqueous zinc oral care compositions with fluoride|
    法律状态:
    2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-05-05| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-09-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/06/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/US2014/043420|WO2015195139A1|2014-06-20|2014-06-20|Oral compositions containing metal ions|
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