? calcium carbonate reacted on the surface, and, oral care composition?

专利摘要:
CALCIUM CARBONATE REACTIONED ON THE SURFACE, AND, ORAL CARE COMPOSITION The present invention relates to surface-reacted calcium carbonate, where surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with dioxide carbon and at least one acid. Said calcium carbonate and oral compositions containing it can be used in remineralization and / or teeth whitening.
公开号:BR112016022460B1
申请号:R112016022460-4
申请日:2015-03-05
公开日:2021-02-09
发明作者:Tanja Budde；Daniel E. Gerard；Patrick A. C. Gane
申请人:Omya International Ag；
IPC主号:

专利说明:

[001] The present invention relates to new agents for the remineralization and whitening of teeth and oral care compositions including such agents and their use.
[002] Dental enamel is the hardest substance in the human body and contains about 96% of minerals, in which the remainder is composed of water and organic material. The primary mineral in enamel is hydroxyapatite, which is a crystalline calcium phosphate. The enamel is formed on the tooth while the tooth is developing inside the gum, before it leaves the mouth.
[003] Its high mineral content forms enamel, however, very vulnerable to a demineralization process, which is especially triggered by the consumption of acidic and sweet drinks. Remineralization of teeth can repair the damage to the tooth to a certain degree, but if damaged beyond what cannot be repaired by the body and lately the process of continuous demineralization results in erosion of the tooth and tooth decay. The maintenance and repair of human dental enamel is, therefore, one of the primary concerns of the dentist.
[004] A remineralization study using a toothpaste containing hydroxyapatite and sodium monofluorophosphate is published in Hornby et al., International Dental Journal 2009, 59, 325-331. US 2007/0183984 A1 is directed to an oral composition comprising a calcium phosphate salt and a combination of acids having different solubilities in the oral cavity, for mineralization or remineralization of the tooth.
[005] The typical color of the enamel varies from light yellow to gray or bluish white. Since the enamel is semi-translucent, the color of the dentin and any material underneath the enamel strongly affects the appearance of a tooth. The enamel on primary teeth has an opaque crystalline shape and thus appears whiter than on permanent teeth.
[006] On radiographs, differences in the mineralization of different portions of the teeth and that surrounds the periodontium can be observed; enamel appears lighter than dentin and pulp as it is denser than both and more radiopaque (cf. “Tooth enamel”, Wikipedia, The Free Encyclopedia, 6 March 2014).
[007] When a person ages the adult's teeth often become darker due to changes in the mineral structure of the tooth. In addition, teeth can become stained by bacterial pigments, food substances and vegetables rich in carotenoids or xanthonoids. Certain antibacterial drugs such as tetracycline can cause stains on the teeth or a reduction in enamel shine and ingestion of colored liquids such as coffee, tea, red wine or smoke can discolor the teeth (“Tooth bleaching”, Wikipedia, The Free Encyclopedia, February 5 2014).
[008] Methods for whitening teeth often involve a bleaching process using aggressive oxidizing agents such as peroxides and may require the total solid composition to remain in contact with the teeth for an extended period of time. As an alternative, toothpaste compositions provide both remineralization and whitening of teeth using calcium salts have been suggested.
[009] WO 2012/143220 A1 describes a composition that is suitable for remineralization and teeth whitening, which comprises a source of calcium and calcium salt from the regeneration source. A toothpaste composition that comprises a source of calcium insoluble in water and / or slightly soluble in water and an organic acid or its pharmaceutically acceptable salt, is described in WO 2013/034421 A2. WO 2012/031786 A2 refers to oral care compositions with composite particle assets having a core and a coating, so the coating interacts with phosphate ions to produce calcium and phosphate reaction products that are suitable for adhere to the enamel and / or dentin of the tooth to improve the characteristics of the teeth.
[0010] In view of the foregoing, there is an ongoing need for agents that are useful in remineralizing teeth and / or whitening teeth.
[0011] Consequently, it is an object of the present invention to provide an agent that is suitable for remineralizing and whitening teeth and is compatible with conventional oral care compositions. It should also be desirable to provide a remineralizing and / or bleaching agent, which is smooth to use and easy to apply. It should also be desirable to provide a remineralizing and / or bleaching agent, which does not necessarily require treatments in the office, but can be used at home, for example, on a daily basis.
[0012] It is also an objective of the present invention to provide a remineralizing and / or bleaching agent that is more resistant to the acid challenge. It should also be desirable to provide a remineralizing and / or bleaching agent that does not necessarily need to have a particle size in the nano size range. It should also be desirable to provide a remineralizing and / or bleaching agent that provides the added benefit of being a carrier material for active agents.
[0013] The precedent and other objectives are resolved by the matter as defined here in the independent claims.
[0014] In accordance with an aspect of the present invention, a surface-reacted calcium carbonate for use in mineralization and / or teeth whitening is provided, wherein the surface-reacted calcium carbonate is a reaction product of calcium carbonate natural or synthetic with carbon dioxide and at least one acid.
[0015] In accordance with another aspect of the present invention, an oral care composition for use in mineralizing and / or whitening teeth is provided, comprising a surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid.
[0016] Still in accordance with another aspect of the present invention, a surface-reacted calcium carbonate for use in tooth mineralization is provided, where the surface-reacted calcium carbonate is a reaction product of natural calcium carbonate or synthetic with carbon dioxide and at least one acid.
[0017] Still according to another aspect of the present invention, a surface-reacted calcium carbonate for use in teeth whitening is provided, wherein the surface-reacted calcium carbonate is a reaction product of natural calcium carbonate or synthetic with carbon dioxide and at least one acid.
[0018] The advantageous embodiments of the present invention are defined in the corresponding subclaims.
[0019] According to one embodiment, at least one acid is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, citric acid, oxalic acid, acetic acid, formic acid and mixtures thereof, preferably the at least one acid is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid and mixtures thereof and more preferably the at least one acid is phosphoric acid.
[0020] According to one embodiment, the calcium carbonate reacted on the surface is in the form of particles having an average grain diameter in volume (d50) equal to or less than 15 μm, preferably from 1 to 10 μm, more preferably from 2 to 8 μm and more preferably 3 to 7 μm and / or a cut-off top particle size determined in volume (d98) equal to or less than 25 μm, preferably from 7 to 22 μm, more preferably from 10 to 20 and more preferably 15 to 18 μm. According to another embodiment, the surface-reacted calcium carbonate is in the form of particles having a specific surface area of 5 m2 / g to 200 m2 / g, more preferably 20 m2 / g to 80 m2 / g and even more preferably 30 m2 / g to 60 m2 / g, measured using nitrogen and the BET method according to ISO 9277.
[0021] According to one embodiment, the surface-reacted calcium carbonate is used in combination with a fluoride compound, preferably selected from the group consisting of sodium fluoride, stannous fluoride, sodium monofluorophosphate, potassium fluoride, stannous potassium, sodium fluorostannate, stannous chlorofluoride, amine fluoride and mixtures thereof and more preferably the fluoride compound is sodium monofluorophosphate and / or sodium fluoride. According to another embodiment, at least one active agent is associated with the surface-reacted calcium carbonate, preferably the active agent is at least one additional desensitizing agent and more preferably the at least one additional desensitizing agent is selected from the group that consists of potassium nitrate, gluteraldehyde, silver nitrate, zinc chloride, strontium chloride hexahydrate, sodium fluoride, stannous fluoride, strontium chloride, strontium acetate, arginine, hydroxyapatite, sodium calcium phosphosilicate, potassium oxalate , calcium phosphate, calcium carbonate, bioactive glasses and mixtures thereof.
[0022] According to one embodiment, the calcium carbonate reacted on the surface is obtained by a process that comprises the steps of: (a) providing a suspension of natural or synthetic calcium carbonate, (b) adding at least one acid having a pKa value of 0 or less at 20 ° C or having a pKa value of 0 to 2.5 to 20 ° C at the suspension of step a) and (c) treating the suspension of step (a) with carbon dioxide before, during or after step (b). According to another embodiment, the calcium carbonate reacted on the surface is obtained by a process comprising the steps of: (A) providing a natural or synthetic calcium carbonate, (B) providing at least one water-soluble acid, (C) supplying gaseous CO2, (D) contacting said natural or synthetic calcium carbonate from step (A) with at least one acid from step (B) and with the CO2 from step (C), characterized in that: ( i) the at least one acid from step B) has a pKa greater than 2.5 and less than or equal to 7 to 20 ° C, associated with the ionization of its first available hydrogen and a corresponding anion is formed in the loss of its first available hydrogen capable of forming a water-soluble calcium salt and (ii) it follows the contact of at least one acid with natural or synthetic calcium carbonate, at least one water-soluble salt, which in the case of a salt containing hydrogen has a pKa greater than 7 at 20 ° C, associated with the ionization of the first available hydrogen and uranium n of salt that is capable of forming water-insoluble calcium salts is additionally provided.
[0023] According to one embodiment, the oral care composition comprises from 1 to 40% by weight, preferably from 1.5 to 35% by weight, more preferably from 2 to 30% by weight of the surface-reacted calcium carbonate , based on the total weight of the composition. According to another embodiment, the oral care composition is a toothpaste, a dental powder or a mouthwash and in which the surface-reacted calcium carbonate is preferably a reaction product of natural or synthetic calcium carbonate with dioxide carbon and phosphoric acid.
[0024] According to one embodiment, the oral composition further comprises a fluoride compound, preferably the fluoride compound is selected from the group consisting of sodium fluoride, stannous fluoride, sodium monofluorophosphate, potassium fluoride, stannous potassium fluoride , sodium fluorostannate, stannous chlorofluoride, amine fluoride and mixtures thereof and more preferably the fluoride compound is sodium monofluorophosphate and / or sodium fluoride. According to a further embodiment, the oral care composition further comprises an additional remineralizing and / or bleaching agent, preferably selected from the group consisting of hydroxyapatite, for example, nanohydroxyapatite, calcium carbonate, for example, carbonate of amorphous calcium and combinations of these with casein phospholipids, hydrogen peroxide, carbamide peroxide, fluoride compounds and mixtures thereof. According to yet another embodiment, the oral care composition has a pH between 7.5 and 10, preferably between 8 and 9.
[0025] It should be understood that for the purpose of the present invention, the following terms have the following meaning.
[0026] For the purpose of the present invention, an "acid" is defined as Br0nsted-Lowry acid, that is, it is a supplier of H3O + ion. An "acid salt" is defined as an H3O + ion supplier, for example, a hydrogen-containing salt, which is partially neutralized by an electropositive element. A "salt" is defined as an electrically neutral ionic compound formed from anions and cations. A "partially crystalline salt" is defined as a salt that, in XRD analysis, presents an essentially different diffraction pattern.
[0027] According to the present invention, pKa, is the symbol that represents the acid dissociation constant associated with a given ionizable hydrogen in a given acid and is indicative of the natural degree of dissociation of this hydrogen from this acid in equilibrium in water at a given temperature. Such pKa values can be observed in reference textbooks, such as Harris, D.C. “Quantitative Chemical Analysis: 3rd Edition”, 1991, W.H. Freeman & Co. (USA), ISBN 0-7167-21708.
[0028] "Soil calcium carbonate" (GCC) in the meaning of the present invention is a calcium carbonate obtained from natural sources, such as limestone, marble, dolomite or chalk and processed through a wet and / or dry treatment, such as such as crushing, evaluation and / or fractionation, for example, by a cyclone or classification.
[0029] "Precipitated calcium carbonate" (PCC) in the meaning of the present invention is a synthesized material, obtained by precipitation following the reaction of carbon dioxide and lime in an aqueous, semi-dry or humid environment or by precipitation from a source of calcium ion and carbonate in water. PCC can be in crystalline vateritic, calcitic or aragonitic form.
[0030] For the purpose of the present invention, a "surface-reacted calcium carbonate" is a material comprising calcium carbonate and a non-insoluble, at least partially crystalline calcium salt, preferably extending from the surface of at least part of the calcium carbonate. The calcium ions that form at least partially crystalline non-carbonate calcium salt that originate largely from the starting calcium carbonate material which also serves to form the reacted calcium carbonate in the surface core. Such salts can include anions of OH- and / or crystalline water.
[0031] In the meaning of the present invention, "water insoluble" materials are defined as materials that, when mixed with deionized water and filtered through a filter having a pore size of 0.2 μm at 20 ° C to recover the filtrate liquid, provides less than or equal to 0.1 g of recovered solid material following the evaporation of 95 to 100 ° C of 100 g of said liquid filtrate. "Water-soluble" materials are defined as materials that lead to recovery greater than 0.1 g of recovered solid material following the evaporation of 95 to 100 ° C of 100 g of liquid filtrate.
[0032] Throughout this document, the "particle size" of a calcium carbonate and other materials is described by its particle size distribution. The dx value represents the relative diameter at which x% by weight of the particles having diameters smaller than dx. This means that the d20 value is the particle size where 20% by weight of all particles are smaller and the d75 value is the particle size where 75% by weight of all particles are smaller. The d50 value is, in this way, the median particle size by weight, that is, 50% by weight of all grains are larger or smaller than this particle size. For the purpose of the present invention, the particle size is specified as the median particle size by weight d50 unless otherwise indicated. To determine the d50 value of the median particle size by weight, a Sedigraph can be used. For the purpose of the present invention, the "particle size" of surface reacted calcium is described as the particle size distributions determined by volume. To determine the particle size distribution determined by volume, for example, the average grain diameter in volume (d50) or the top cut particle size determined in volume (d98) of surface reacted calcium carbonate, a Malvern Mastersizer 2000 can be used. The particle size distribution determined by weight can correspond to the particle size determined by volume if the density of all particles is equal.
[0033] A "specific surface area (SSA)" of a calcium carbonate in the meaning of the present invention is defined as the surface area of the calcium carbonate divided by its mass. As used here, the specific surface area is measured by adsorption of nitrogen gas using the BET isotherm (ISO 9277: 2010) and is specified in m2 / g.
[0034] An "oral care composition" in the meaning of the present invention refers to a composition suitable for use in the mouth and for veterinary and / or human applications, but especially for use in applications for the human mouth.
[0035] For the purpose of the present invention, the term "viscosity" or "Brookfield viscosity" refers to Brookfield viscosity. The Brookfield viscosity is for this purpose measured by a Brookfield viscometer (Type RVT) at 20 ° C ± 2 ° C at 100 rpm using an appropriate bar and is specified in mPa ^ s.
[0036] A "suspension" or "paste" in the meaning of the present invention comprises insoluble solids and water and, optionally, other additives and usually contains large amounts of solids and, in this way, is more viscous and can be of high density than the liquid that is formed.
[0037] When the term "which comprises" is used in the present description and claims, other elements are not excluded. For the purposes of the present invention, the term "consisting of" is considered to be a preferred embodiment of the term "comprising of". If, afterwards, a group is defined to comprise at least a certain number of modalities, then it must also be understood to publicize a group, which preferably consists only of these modalities.
[0038] When an indefinite or defined article is used when referring to a singular name, for example, "one", "one" or "o", this includes a plural of that name unless, to some extent, it is still specifically established.
[0039] Similar terms “obtainable” or “definable” and “obtained” or “defined” are used interchangeably. This, for example, means that, unless the context clearly dictates otherwise, the term "obtained" does not mean that, for example, a modality must be obtained, for example, by the sequence of steps that follow the term “Obtained” even though such a limiting understanding is always included by the terms “obtained” or “defined” as a preferred modality.
[0040] In accordance with the present invention, a calcium carbonate reacted on the surface is used for remineralization and / or teeth whitening. Surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid.
[0041] Below, the details and preferred modalities of the calcium carbonate reacted on the inventive surface will be presented in more detail. It should be understood that these details and technical modalities also apply to the inventive method for producing surface-reacted calcium carbonate as well as the inventive compositions comprising surface-reacted calcium carbonate. Calcium carbonate reacted on the surface
[0042] According to the present invention, the surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid.
[0043] Natural (or soil) calcium carbonate (GCC) is understood to be a naturally occurring form of calcium carbonate, mined from sedimentary rocks, such as limestone or chalk, or from metamorphic marble rocks. Calcium carbonate is known to exist mainly as three types of crystalline polymorphs: calcite, aragonite and vaterite. Calcite, the most common crystalline polymorph, is considered to be the most stable crystalline form of calcium carbonate. The least common is aragonite, which has an orthorhombic polymorphic crystalline structure with a distinct or grouped needle. Vaterita is the rarest polymorph of calcium carbonate and is generally unstable. Calcium carbonate is almost exclusively from the calcitic polymorph, which is said to be trigonal-rhombohedral and represents the most stable of the calcium carbonate polymorphs. The term "source" of calcium carbonate in the meaning of the present invention refers to the naturally occurring mineral material from which calcium carbonate is obtained. The source of calcium carbonate may comprise other naturally occurring components such as magnesium carbonate, aluminum silicate, etc.
[0044] According to one embodiment of the present invention, natural calcium carbonate is selected from the group consisting of marble, chalk, dolomite, limestone and mixtures thereof.
[0045] According to an embodiment of the present invention, GCC is obtained by dry grinding. According to another embodiment of the present invention, GCC is obtained by wet grinding and, optionally, subsequent drying.
[0046] In general, the grinding step can be carried out with any conventional grinding device, for example, under conditions such that the grinding results predominantly from impacts with secondary bodies, that is, in one or more of: a ball mill , a cane mill, a vibrating mill, a roller crusher, a centrifugal impact mill, a vertical pearl mill, a friction mill, a pin mill, a hammer mill, a sprayer, a shredder, a shredder , a knife cutter or other such equipment known to the skilled man. In the case, the calcium carbonate containing mineral material comprises a wet grinding calcium carbonate containing mineral material, the grinding step can be carried out under conditions, such that autogenous grinding occurs and / or by grinding with horizontal and / or other spheres such processes known to the qualified person. The wet processed crushed calcium carbonate containing mineral material thus obtained can be washed and dehydrated by well-known processes, for example, by flocculation, filtration or forced evaporation before drying. The subsequent drying step can be carried out in a simple step, such as spray drying or in at least two steps. It is also known that such a mineral material undergoes a beneficiation step (such as a float, cripple or magnetic separation step) to remove impurities.
[0047] "Precipitated calcium carbonate" (PCC) in the meaning of the present invention is a synthesized material, generally obtained by precipitation following the reaction of carbon dioxide and lime in an aqueous environment or by precipitation from a source of calcium ion and of carbonate in water or by precipitation of calcium and carbonate ions, for example, CaCl2 and Na2CO3, out of solution. Other possible ways of producing PCC are the lime process or the Solvay process in which PCC is a by-product of ammonia production. Precipitated calcium carbonate exists in three primary crystalline forms: calcite, aragonite and vaterite and there are many different polymorphs (crystalline forms) for each of these crystalline forms. Calcite has a trigonal structure with typical crystalline forms, such as scalenehedral (S-PCC), rhombohedral (R-PCC), hexagonal, pinacoidal, colloidal (C-PCC), cubic and prismatic (P-PCC) ). Aragonite is an orthorhombic structure with crystalline shapes typical of united hexagonal prismatic crystals, as well as a diverse grouping of thin elongated prismatic crystals, curved blade, abrupt pyramidal, chisel-shaped crystals, branching tree and coral or worm-like shape . Vaterita belongs to the hexagonal crystal system. The obtained PCC paste can be mechanically dehydrated and dried.
[0048] In accordance with an embodiment of the present invention, synthetic calcium carbonate is precipitated calcium carbonate, preferably comprising aragonitic, vateritic or calcitic crystalline mineral forms or mixtures thereof.
[0049] According to an embodiment of the present invention, natural or synthetic calcium carbonate is ground before treatment with carbon dioxide and at least one acid. The grinding step can be carried out with any conventional grinding device, such as a grinding mill known to the skilled person.
[0050] According to an embodiment of the present invention, natural or synthetic calcium carbonate is in the form of particles having a median particle size in weight d50 equal to or less than 15 μm, preferably from 1 to 10 μm, more preferably from 2 to 8 μm and more preferably from 3 to 7 μm. According to a further embodiment of the present invention, natural or synthetic calcium carbonate is in the form of particles having a d98 top-cut particle size equal to or less than 25 μm, preferably from 7 to 22 μm, more preferably from 10 to 20 μm and more preferably from 15 to 18 μm.
[0051] Preferably, the surface-reacted calcium carbonate to be used in the present invention is prepared as an aqueous suspension having a pH, measured at 20 ° C, greater than 6.0, preferably greater than 6.5, more preferably greater than 7.0, even more preferably greater than 7.5.
[0052] In a preferred process for preparing the aqueous suspension of surface-reacted calcium carbonate, the finely divided natural or synthetic calcium carbonate, such as by grinding or not, is suspended in water. Preferably, the paste has a natural or synthetic calcium carbonate content within the range of 1% by weight to 90% by weight, more preferably 3% by weight to 60% by weight and even more preferably 5% by weight to 40% by weight, based on the weight of the paste.
[0053] In a next step, at least one acid is added to the aqueous suspension containing natural or synthetic calcium carbonate. The at least one acid can be any strong acid, medium-strong acid or weak acid or mixtures thereof, generating H3O + ions under the conditions of preparation. According to the present invention, the at least one acid can also be an acid salt, which generates H3O + ions under the conditions of preparation.
[0054] According to one embodiment, the at least one acid is a strong acid having a pKa of 0 or less at 20 ° C. According to another embodiment, the at least one acid is a medium-strong acid having a pKa value of 0 to 2.5 at 20 ° C. If the pKa at 20 ° C is 0 or less, the acid is preferably selected from sulfuric acid, hydrochloric acid or mixtures thereof. If the pKa at 20 ° C is 0 to 2.5, the acid is preferably selected from H2SO3, H3PO4, oxalic acid or mixtures thereof. The at least one acid can also be an acidic salt, for example, HSO4- or H2PO4-, being at least partially neutralized by a corresponding cation such as Li +, Na + or K + or HPO42-, being at least partially neutralized by a corresponding cation , such as Li +, Na +, K +, Mg2 + or Ca2 +. The at least one acid can also be a mixture of one or more acids and one or more acid salts.
[0055] Still according to another embodiment, the at least one acid is a weak acid having a pKa value greater than 2.5 and less than or equal to 7, when measured at 20 ° C, associated with the ionization of the first available hydrogen and having a corresponding anion formed in the loss of its first available hydrogen, which is capable of forming water-soluble calcium salts. According to the preferred embodiment, the weak acid has a pKa value of 2.6 from 5 to 20 ° C and more preferably the weak acid is selected from the group consisting of acetic acid, formic acid, propanoic acid and mixtures thereof. .
[0056] In this case, a weak acid is used, after adding said acid to the aqueous suspension containing the natural or synthetic calcium carbonate, at least one water-soluble salt, which in the case of a hydrogen-containing salt has a higher pKa than 7, when measured at 20 ° C, associated with the ionization of the first available hydrogen and the salt anion that is capable of forming water-insoluble calcium salts, is additionally added. The cation of said water-soluble salt is preferably selected from the group consisting of potassium, sodium, lithium and mixtures thereof. In a more preferred embodiment, said cation is sodium. It is noteworthy that depending on the anion charge, more than one of said cations may be present to provide an electrically neutral ionic compound. The anion of said water-soluble salt is preferably selected from the group consisting of phosphate, dihydrogen phosphate, monohydrogen phosphate, oxalate, silicate, mixtures thereof and hydrates thereof. In a more preferred embodiment, said anion is selected from the group consisting of phosphate, dihydrogen phosphate, monohydrogen phosphate, mixtures thereof and hydrates thereof. In a more preferred embodiment, said anion is selected from the group consisting of dihydrogen phosphate, monohydrogen phosphate, mixtures thereof and hydrates thereof. The addition of water-soluble salt can be carried out in drops or in one step. In the case of the addition to the drops, this addition preferably takes place within a period of 10 minutes. It is more preferred to add said salt in one step.
[0057] According to an embodiment of the present invention, the at least one acid is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, citric acid, oxalic acid, acetic acid, formic acid and mixtures of themselves. Preferably the at least one acid is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfuric acid, phosphoric acid, oxalic acid, H2PO4-, being at least partially neutralized by a corresponding cation such as Li +, Na + or K +, HPO42- , being at least partially neutralized by a corresponding cation such as Li +, Na +, K +, Mg2 + or Ca2 + and mixtures thereof, more preferably the at least one acid is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfuric acid, acid phosphoric, oxalic acid, or mixtures thereof, and more preferably, the at least one acid is phosphoric acid. Without being bound by any theory, the inventors believe that the use of phosphoric acid can be beneficial in remineralizing and / or whitening teeth.
[0058] The at least one acid can be added to the suspension as a concentrated solution or a more diluted solution. Preferably, the molar ratio of at least one acid to natural or synthetic calcium carbonate is 0.05 to 4, more preferably 0.1 to 2.
[0059] As an alternative, it is also possible to add at least one acid to the water before the natural or synthetic calcium carbonate is suspended.
[0060] In accordance with the present invention, surface-reacted calcium carbonate is obtained by treating natural or synthetic calcium carbonate with carbon dioxide. Carbon dioxide can be formed in situ by acid treatment and / or can be supplied from an external source. If a strong acid such as sulfuric acid or hydrochloric acid or medium to strong acid such as phosphoric acid is used for the treatment of natural or synthetic calcium carbonate acid, carbon dioxide is automatically formed. Alternatively or additionally, carbon dioxide can be supplied from an external source.
[0061] According to one embodiment, the calcium carbonate reacted on the surface is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid, in which carbon dioxide is formed in situ as a result of contacting at least one acid with natural or synthetic calcium carbonate and / or is supplied from an external source.
[0062] The treatment of the acid and treatment with carbon dioxide can be carried out simultaneously which is the case when a strong or medium to strong acid is used. It is also possible to carry out the treatment of the acid first, for example with a medium to strong acid having a pKa in the range of 0 to 2.5 to 20 ° C, in which carbon dioxide is formed in situ, and thus the treatment with carbon dioxide it will automatically be carried out simultaneously with the treatment of the acid, followed by the additional treatment with carbon dioxide supplied from an external source.
[0063] Preferably, the concentration of carbon dioxide gas in the suspension is, in terms of volume, such that the ratio (volume of the suspension) :( volume of CO2 gas) is from 1: 0.05 to 1:20, still more preferably from 1: 0.05 to 1: 5.
[0064] In a preferred embodiment, the acid treatment step and / or the carbon dioxide treatment step are repeated at least once, more preferably several times. According to one embodiment, the at least one acid is added over a period of time of at least 30 min, preferably at least 45 min and more preferably at least 1 h.
[0065] Subsequent to the acid treatment and carbon dioxide treatment, the pH of the aqueous suspension, measured at 20 ° C, naturally reaches a value greater than 6.0, preferably greater than 6.5, more preferably greater than than 7.0, even more preferably greater than 7.5, therefore preparing the surface-reacted calcium carbonate as an aqueous suspension having a pH greater than 6.0, preferably greater than 6.5, more preferably greater than than 7.0, even more preferably greater than 7.5. If the aqueous suspension is allowed to reach equilibrium, the pH is greater than 7. A pH greater than 6.0 can be adjusted without the addition of a base when stirring the aqueous suspension is continued for a sufficient period of time, preferably 1 hour to 10 hours, more preferably 1 to 5 hours.
[0066] Alternatively, before reaching equilibrium, which occurs at a pH greater than 7, the pH of the aqueous suspension can be increased to a value greater than 6 by the addition of a subsequent base by treatment with carbon dioxide. Any conventional base such as sodium hydroxide or potassium hydroxide can be used.
[0067] Additional details surrounding the preparation of surface-reacted natural calcium carbonate are disclosed in WO 00/39222 A1 and US 2004/0020410 A1, where surface-reacted natural calcium carbonate is described as a filler for manufacturing of the paper. The preparation of surface-reacted calcium carbonate with weak acids is disclosed in EP 2 264 108 A1. The preparation of surface-reacted calcium carbonate and its use in the purification processes is disclosed in EP 1 974 806 A1, EP 1 982 759 A1 and EP 1 974 807 A1. The use of surface-reacted calcium carbonate as a carrier for controlled release of active agents is described in WO 2010/037753 A1.
[0068] Similarly, precipitated calcium carbonate reacted on the surface is obtained. As it can be used in detail in EP 2 070 991 A1, the precipitated calcium carbonate reacted on the surface is obtained to contact the calcium carbonate precipitated with H3O + ions and with anions being solubilized in an aqueous medium and being able to form calcium salts insoluble in water, in an aqueous medium to form a paste of precipitated calcium carbonate reacted on the surface, wherein said precipitated calcium carbonate reacted on the surface comprises an insoluble calcium salt, at least partially crystalline from said anion formed on the surface of at least part of the precipitated calcium carbonate.
[0069] Said solubilized calcium ions correspond to an excess of solubilized calcium ions relative to solubilized calcium ions naturally generated in the dissolution of calcium carbonate precipitated by H3O + ions, where said H3O + ions are supplied only in the form of a counter -ion to the anion, that is, through the addition of anion in the form of an acid or salt of acid other than calcium and in the absence of any calcium ion or source of calcium ion generation.
[0070] Said excess solubilized calcium ions are preferably supplied by the addition of a soluble acid or neutral calcium salt, or by the addition of an acid or salt other than acid or neutral calcium which generates a soluble acid or neutral calcium salt in situ.
[0071] Said H3O + ions may be supplied by the addition of an acid or an acid salt of said anion, or by the addition of an acid or an acid salt which simultaneously serves to supply all or part of said excess of solubilized calcium ions .
[0072] In accordance with an embodiment of the present invention, surface-reacted calcium carbonate is obtained by a process comprising the steps of: a) providing a suspension of natural or synthetic calcium carbonate, b) adding at least one acid having a pKa value of 0 or less at 20 ° C or having a pKa value of 0 to 2.5 to 20 ° C at the suspension of step a) and c) treating the suspension of step a) with carbon dioxide before, during or after step b).
[0073] According to one embodiment, at least one acid having a pKa value of 0 or less at 20 ° C is added in step b) to the suspension in step a). According to another embodiment, at least one acid having a pKa value of 0 to 2.5 at 20 ° C is added in step b) to the suspension in step a).
[0074] The carbon dioxide used in step c) can be formed in situ by treating the acid in step b) and / or can be supplied from an external source.
[0075] In accordance with an embodiment of the present invention, calcium carbonate reacted on the surface is obtained by a process comprising the steps of: A) providing a natural or synthetic calcium carbonate, B) providing at least one acid soluble in water, C) supplying gaseous CO2, D) contacting said natural or synthetic calcium carbonate from step A) with at least one acid from step B) and with CO2 from step C), characterized in that: i) the hair minus one acid from step B) has a pKa greater than 2.5 and less than or equal to 7 to 20 ° C, associated with the ionization of this first available hydrogen and a corresponding anion is formed in the loss of this first available hydrogen capable to form a water-soluble calcium salt and ii) it follows the contact of at least one acid with natural or synthetic calcium carbonate, at least one water-soluble salt, which in the case of a hydrogen-containing salt has a pKa greater than 7 to 20 ° C, associated with the ionization of the first available hydrogen and the salt anion which is capable of forming the water-insoluble calcium salts, is additionally provided.
[0076] The calcium carbonate reacted on the surface can be kept in the suspension, optionally still stabilized by a dispersant. Conventional dispersants known to that skilled person can be used. A preferred dispersant is polyacrylic acid and / or carboxymethylcellulose.
[0077] Alternatively, the aqueous suspension described above can be dried, therefore obtaining the natural or synthetic calcium carbonate reacted on the solid surface (ie dry or containing the minimum of water that is not in a fluid form) in the form of granules or a powder.
[0078] According to an embodiment of the present invention, the surface-reacted calcium carbonate has a specific surface area of 5 m2 / g to 200 m2 / g, more preferably 20 m2 / g to 80 m2 / g and even more preferably 30 m2 / g 60 m2 / g, measured using nitrogen and the BET method according to ISO 9277.
[0079] According to an embodiment of the present invention, the surface-reacted calcium carbonate is in the form of particles having an average grain diameter in volume (d50) equal to or less than 15 μm, preferably from 1 to 10 μm , more preferably from 2 to 8 μm and more preferably from 3 to 7 μm. According to another embodiment of the present invention, the surface-reacted calcium carbonate is in the form of particles having a top cut particle size determined in volume (d98) equal to or less than 25 μm, preferably from 7 to 22 µm. μm, more preferably from 10 to 20 μm and more preferably from 15 to 18 μm. According to a preferred embodiment of the present invention, the surface-reacted calcium carbonate is in the form of particles having an average grain diameter in volume (d50) equal to or less than 15 μm, preferably from 1 to 10 μm, more preferably from 2 to 8 μm and more preferably from 3 to 7 μm and having a top cut particle size determined in volume (d98) equal to or less than 25 μm, preferably from 7 to 22 μm, more preferably from 10 to 20 μm and more preferably from 15 to 18 μm. The average grain diameter in the volume (d50) and top cut particle size determined in the volume (d98) can be determined by laser diffraction measurements, for example, using a Malvern Mastersizer 2000.
[0080] According to an embodiment of the present invention, the surface-reacted calcium carbonate comprises an insoluble calcium salt, at least partially crystalline from an anion of at least one acid, which is formed on the surface of natural calcium carbonate or synthetic. According to one embodiment, the insoluble, at least partially crystalline salt of an anion of at least one acid coats the surface of natural or synthetic calcium carbonate at least partially, preferably completely. Depending on the use of at least one acid, the anion can be sulfate, sulfite, phosphate, citrate, oxalate, acetate, formate and / or chloride.
[0081] According to a preferred embodiment, the surface-reacted calcium carbonate is a reaction product of natural calcium carbonate and at least one acid, preferably phosphoric acid.
[0082] Calcium carbonate reacted on the surface has a good loading capacity and can be used as a carrier in oral hygiene. For example, calcium carbonate reacted on the surface is capable of associating and transporting an active agent. The association is preferably an adsorption on the surface of the calcium carbonate reacted on the surface particles, either on the internal or external surface of the particles or an absorption on the particles, which is possible due to its porosity.
[0083] In this respect, it is believed that because of the intra and interpose structure of the calcium carbonate reacted on the surface, this material is a superior agent to previously release the ad / absorbed materials in the period of time relative to the common materials having surface areas similar specifics.
[0084] Calcium carbonate reacted on the surface can have an intra-particle porosity within the range of 5% by volume to 50% by volume, preferably from 20% by volume to 50% by volume and more preferably from 30% by volume to 50% by volume, calculated from the measurement of mercury porosimetry. From the bimodal derived pore size distribution curve, the lowest point between the peaks indicates the diameter where the intra and interparticle pore volumes can be separated. The pore volume in diameters greater than this diameter is the pore volume associated with the interparticle pores. The total pore volume minus this interparticle pore volume gives the intra-particle pore volume at which the intra-particle porosity can be calculated, preferably as a fraction of the volume of solid material, as described in Transport in Porous Media (2006) 63: 239-259.
[0085] The details added regarding the porosity of the calcium carbonate reacted on the surface and its use as an agent for material release can be seen in WO 2010/037753 A1.
In this way, generally, any agent that adapts to the intra- and / or interparticle pores of the surface-reacted calcium carbonate is suitable to be transported by the surface-reacted calcium carbonate according to the invention. For example, active agents such as those selected from the group comprising pharmaceutically active agents, biologically active agents, disinfecting agents, preservatives such as triclosan, flavoring agents, surfactants similar to surfactants, or additional desensitizing agents can be used. According to one embodiment, at least one active agent is associated with the surface-reacted calcium carbonate. According to a preferred embodiment, the active agent is at least one additional desensitizing agent, preferably selected from the group consisting of potassium nitrate, gluteraldehyde, silver nitrate, zinc chloride, strontium chloride hexahydrate, sodium fluoride, fluoride stannous, strontium chloride, strontium acetate, arginine, hydroxyapatite, sodium calcium phosphosilicate, potassium oxalate, calcium phosphate, calcium carbonate, bioactive glasses and mixtures thereof. Hydroxyapatite, also called hydroxyapatite, is a naturally occurring mineral form of calcium apatite with the formula Ca5 (PO4) 3 (OH). According to an exemplary embodiment, hydroxyapatite is a nano-sized hydroxyapatite, also called nano-hydroxyapatite. Oral care composition
The oral hygiene composition for use according to the present invention comprises a surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid.
[0088] According to an embodiment of the present invention, the composition comprises from 1 to 40% by weight, preferably from 1.5 to 35% by weight, more preferably from 2 to 30% by weight of the surface-reacted calcium carbonate , based on the total weight of the composition.
[0089] The surface-reacted calcium carbonate may consist of only one type of surface-reacted calcium carbonate or it may be a mixture of two or more types of surface-reacted calcium carbonate. The oral hygiene composition of the present invention may contain surface-reacted calcium carbonate only as a remineralizing and / or bleaching agent. Alternatively, the oral hygiene composition of the present invention may contain the surface-reacted calcium carbonate in combination with at least one additional remineralizing and / or bleaching agent.
[0090] According to one embodiment, the oral hygiene composition comprises at least one additional remineralizing agent. Preferably, the additional remineralizing agent selected from the group consisting of hydroxyapatite, for example nanohydroxyapatite, calcium carbonate, for example amorphous calcium carbonate and combinations thereof with casein phospholipids and mixtures thereof. Amorphous calcium carbonate is an amorphous and at least stable polymorph of calcium carbonate and in addition to several specialized organisms are not naturally observed.
[0091] According to another embodiment, the oral hygiene composition comprises at least one additional bleaching agent. The additional bleaching agent can be a bleaching agent, an abrasive, or a remineralizing agent and is preferably selected from the group consisting of hydrogen peroxide, carbamide peroxide, hydroxyapatite, calcium carbonate, fluoride compounds and mixtures thereof. .
[0092] In accordance with an embodiment of the present invention, the at least one additional remineralizing and / or bleaching agent is selected from the group consisting of hydroxyapatite, for example nanohydroxyapatite, calcium carbonate, for example amorphous calcium carbonate and combinations of these with casein phospholipids, hydrogen peroxide, carbamide peroxide, fluoride compounds and mixtures thereof.
[0093] According to one embodiment, the additional remineralizing and / or bleaching agent has an average particle size d50 from 10 nm to 100 μm, preferably from 0.1 to 50 μm, more preferably from 1 to 20 μm and more preferably from 2 to 10 μm.
[0094] The at least one additional remineralizing and / or bleaching agent may be present in an oral hygiene composition in an amount of 1 to 20% by weight, preferably 1.5 to 15% by weight, more preferably 2 to 10% by weight, based on the total weight of the composition.
[0095] According to one embodiment, the oral hygiene composition of the present invention comprises from 1 to 40% by weight of the surface-reacted calcium carbonate and from 1 to 20% by weight of an additional remineralizing and / or bleaching agent , based on the total weight of the composition.
[0096] The oral hygiene composition of the present invention can be, for example, a toothpaste, a dental powder, a varnish, an adhesive gel, a cement, a resin, a spray, a foam, a balm, a composition made in an adhesive mouthwash composition or mouthwash, a chewable tablet, a chewable tablet, a chewable gum, a rhombus, a drink, or a mouthwash. According to an embodiment of the present invention, the oral hygiene composition is a toothpaste, a dental powder, or a mouthwash and preferably a toothpaste.
[0097] According to a preferred embodiment, the oral hygiene composition is a toothpaste, a dental powder, or a mouth wash and the calcium carbonate reacted on the surface is a reaction product of natural or synthetic calcium carbonate with dioxide carbon and phosphoric acid. According to another preferred embodiment, the oral hygiene composition is a toothpaste, a dental powder, or a mouthwash and the surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and phosphoric acid, where the calcium carbonate reacted on the surface is in the form of particles having an average grain diameter in volume (d50) equal to or less than 15 μm, preferably from 1 to 10 μm, more preferably from 2 to 8 μm and more preferably 3 to 7 μm and / or a cut-off top particle size determined in volume (d98) equal to or less than 25 μm, preferably 7 to 22 μm, more preferably 10 to 20 and more preferably from 15 to 18 μm.
[0098] According to an embodiment of the present invention, the oral hygiene composition has a pH between 7.5 and 10, preferably between 8 and 9.
[0099] The surface-reacted calcium carbonate can be used in combination with a fluoride compound. The inventors surprisingly observed that a combination of surface-reacted calcium carbonate and a fluoride compound leads to improved remineralization and / or teeth whitening.
[00100] According to a preferred embodiment, the oral composition further comprises a fluoride compound. The fluoride compound can be selected from the group consisting of sodium fluoride, stannous fluoride, sodium monofluorophosphate, potassium fluoride, stannous potassium fluoride, sodium fluorostannate, stannous chlorofluoride, amine fluoride and mixtures thereof. Preferably, the fluoride compound is sodium monofluorophosphate and / or sodium fluoride. Good results can be achieved by using an amount of fluoride compound to provide available fluoride ion in the range of 300 to 2,000 ppm in an oral care composition, preferably around 1,450 ppm.
[00101] According to one embodiment, an oral hygiene composition, preferably toothpaste, a dental powder, or a mouthwash, for use in mineralizing and / or whitening teeth is provided, comprising a calcium carbonate reacted on the surface , where the surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid, preferably phosphoric acid and where the oral composition still comprises a fluoride compound, preferably selected from the group consisting of sodium fluoride, stannous fluoride, sodium monofluorophosphate, potassium fluoride, stannous potassium fluoride, sodium fluorostanate, stannous chlorofluoride, amine fluoride and mixtures thereof and most preferably selected from sodium monofluorophosphate and / or sodium fluoride.
[00102] In addition to the calcium carbonate reacted on the surface, the optional additional remineralization and / or bleaching agent and the optional fluoride compound, the oral hygiene composition can still comprise bioadhesive polymers, surfactants, binders, humectants, desensitizing agents, flavoring agents, sweetening agents and / or water.
[00103] In accordance with an embodiment of the present invention, the oral hygiene composition comprises a bioadhesive polymer. The bioadhesive polymer can include any polymer that promotes the adhesion of the calcium carbonate reacted on the surface to the surface of the teeth or tooth and remains on the surface of the teeth or tooth for an extended period of time, for example, 1 hour, 3 hours, 5 hours , 10 hours, 24 hours. In certain embodiments, the bioadhesive polymer can become more adhesive when the oral hygiene composition is moistened with, for example, water or saliva. In other embodiments, the bioadhesive polymer is a material or combination of materials that enhances the retention of the active ingredient on the surface of the teeth or tooth in which a composition is provided. Such bioadhesive polymers include, for example, hydrophilic organic polymers, hydrophobic organic polymers, silicone gums, silicas and combinations thereof. According to one embodiment, the bioadhesive polymer is selected from the group consisting of hydroxyethyl methacrylate, PEG / PPG copolymers, polyvinylmethylether / maleic anhydride copolymers, polyvinylpyrrolidone (PVP), crosslinked PVP, shellac, polyethylene oxide, methacrylate, methacrylate oxide, methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, methacrylate. acrylate copolymers, methacrylic copolymers, vinylpyrrolidone / vinyl acetate copolymers, polyvinyl caprolactam, polylactides, silicone resins, silicone adhesives, chitosan, milk proteins (casein), amelogenin, ester gum and combinations thereof.
[00104] Suitable surfactants are generally synthetic anionic organic surfactants over a wide pH range. Representatives of such surfactants used in the range of about 0.5 to 5% by weight, based on the total weight of the oral hygiene composition, are water-soluble salts of C10-C18 alkyl sulfates, such as sodium lauryl sulfate, of sulfonated fatty acid monoglycerides, such as sodium monoglyceride sulphonates, of taurine fatty acid amides, such as sodium N-methyl-N-palmitoyltauride and of isethionic acid fatty esters and aliphatic acylamides, such as sarcosinate of sodium N-lauroila. However, surfactants obtained from natural sources such as cocamidopropyl betaine can also be used.
[00105] Suitable binders or thickening agents to provide the desired consistency are, for example, hydroxyethylcellulose, sodium carboxymethylcellulose, natural gums, such as gum caraia, gum arabic, gum tragacanth, xanthan gum or cellulose gum, colloidal silicates, or finely divided silica. Generally, 0.5 to 5% by weight, based on the total weight of the oral care composition, can be used.
[00106] Desensitizing agents can be selected from the group consisting of potassium nitrate, gluteraldehyde, silver nitrate, zinc chloride, strontium chloride hexahydrate, sodium fluoride, stannous fluoride, strontium chloride, strontium acetate, arginine, hydroxyapatite, sodium calcium phosphosilicate, potassium oxalate, calcium phosphate, calcium carbonate, bioactive glasses and mixtures thereof.
[00107] Various humectants known to that qualified person can be used, such as glycerin, sorbitol and other polyhydric alcohols, for example, in an amount of 20 to 40% by weight, based on the total weight of the oral hygiene composition. Examples of suitable flavoring agents include oil of wintergreen, peppermint oil, peppermint oil, clove oil, sassafras oil and the like. Saccharin, aspartame, dextrose, or levulose can be used as sweetening agents, for example, in an amount of 0.01 to 1% by weight, based on the total weight of the oral hygiene composition. Preservatives such as sodium benzoate can be present in an amount of 0.01 to 1% by weight, based on the total weight of the oral hygiene composition. Dyes such as titanium dioxide can also be added to an oral care composition, for example, in an amount of 0.01 to 1.5% by weight, based on the total weight of the oral care composition.
The oral hygiene composition of the present invention may also contain a material selected from the group consisting of silica, precipitated silica, alumina, aluminum silicate, metaphosphate, calcium triphosphate, calcium pyrophosphate, crushed calcium carbonate, precipitated calcium carbonate , sodium bicarbonate, bentonite, kaolin, aluminum hydroxide, calcium hydrogen phosphate, hydroxyapatite and mixtures thereof. Said material can be present in an amount of 1 to 40% by weight, based on the total weight of the oral hygiene composition. According to one embodiment, the oral hygiene composition contains a material being selected from crushed calcium carbonate and / or precipitated silica. According to another embodiment, the oral hygiene composition contains a material being selected from the group consisting of crushed calcium carbonate, precipitated calcium carbonate, aluminum hydroxide, calcium hydrogen phosphate, silica, hydroxyapatite and mixtures thereof. According to a preferred embodiment of the present invention, the oral hygiene composition comprises surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid and calcium carbonate, preferably crushed calcium carbonate and / or precipitated calcium carbonate.
[00109] According to an embodiment of the present invention, the oral hygiene composition is a toothpaste. The toothpaste can be produced by a method that comprises the following steps: I) supply the mixture of water and humectants and optionally at least one of a thickener, a preservative, a fluoride and a sweetener, II) add a reacted calcium carbonate on the surface and optionally a dye, to the mixture of step I), in which the calcium carbonate reacted on the surface is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid, III) add a surfactant to the mixture from step II) and IV) optionally, add a flavoring agent to the mixture from step III).
[00110] However, the toothpaste of the present invention can also be produced by any other method known to that skilled person. Cosmetic and therapeutic use
[00111] It has been observed that calcium carbonate reacted on the surface can be used for remineralization and / or whitening of teeth. According to an embodiment of the present invention, a surface-reacted calcium carbonate for use in tooth mineralization is provided, where the surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid. According to another embodiment of the present invention, a surface-reacted calcium carbonate for use in whitening tooth enamel is provided, wherein the surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid. In accordance with yet another embodiment of the present invention, a surface-reacted calcium carbonate for use in mineralizing and whitening teeth is provided, wherein the surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid.
[00112] In accordance with an additional aspect of the present invention, an oral hygiene composition for use in mineralizing and / or whitening teeth is provided, comprising a surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid. According to one embodiment, an oral hygiene composition for use in the mineralization of teeth is provided, comprising a surface-reacted calcium carbonate, in which the surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid. According to another embodiment, an oral hygiene composition for use in whitening tooth enamel is provided, comprising a surface-reacted calcium carbonate, in which the surface-reacted calcium carbonate is a reaction product of calcium carbonate natural or synthetic with carbon dioxide and at least one acid. Still according to another modality, an oral hygiene composition for use in the mineralization and whitening of teeth is provided, comprising a surface-reacted calcium carbonate, in which the surface-reacted calcium carbonate is a reaction product of calcium carbonate natural or synthetic with carbon dioxide and at least one acid.
[00113] The inventors of the present invention surprisingly note that surface-reacted calcium carbonate is useful in remineralizing and / or whitening teeth. The surface-reacted calcium carbonate differs from conventional calcium carbonate in several aspects. For example, uneven conventional calcium carbonate, surface-reacted calcium carbonate comprises a porous lamellar or plaque structure. Without being bound by any theory, it is believed that during the application of the calcium carbonate reacted on the surface, for example, on the teeth of a patient, the calcium carbonate reacted on the surface breaks into parts, whereby the elements of the lamellar or porous plate structures are cleaved from the surface of the reacted calcium carbonate on the surface. Said structure elements of the cleaved porous lamellar surface or plaque can provide improved adherence to tooth enamel.
[00114] In addition, the surface treatment makes the calcium carbonate reacted on the surface more resistant to acids. Therefore, the calcium carbonate reacted on the surface may be more stable under acidic conditions, for example, during the consumption of acidic drinks, such as soft drinks or acidic dishes, such as salads with vinegar-based seasonings. Another advantage of calcium carbonate reacted on the surface of the present invention is that it can be used in a micrometer particle size range and in this way, the use of nano-sized particles can be avoided.
[00115] It has also been surprisingly observed by the inventors that the calcium carbonate reacted on the surface is useful to uniform the surfaces of the tooth. Without being bound by any theory, it is believed that the structure elements of the lamentable surface or cleaved porous plaque, generated by the breakdown of the reacted calcium carbonate on the surface, adhere to the enamel surface and seal the surface defects and thus make the surface of the enamel more uniform. It is still believed that the more uniform surface can prevent or reduce the adhesion of bacteria and strains, which in turn, can reduce the risk of bad breath and weakening of the tooth.
[00116] According to an additional aspect, a surface-reacted calcium carbonate for use in the uniformization of a tooth surface is provided, where the surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid. In accordance with another additional aspect, an oral hygiene composition for use in the uniformization of a tooth surface is provided, comprising a surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a carbonate reaction product. of natural or synthetic calcium with carbon dioxide and at least one acid.
[00117] The calcium carbonate reacted on the surface of the present invention and / or oral compositions comprising the same can be used in treatment in a professional office or in a home treatment.
[00118] According to one embodiment, calcium carbonate reacted on the surface for use in mineralizing and / or whitening teeth is used in a method that comprises the step of administering at least one patient's tooth in a therapeutically effective amount of calcium carbonate reacted on the surface at least once a day, preferably twice a day and more preferably three times a day. A "therapeutically effective" amount of calcium carbonate reacted on the surface is an amount that is sufficient to have the desired prophylactic or therapeutic effect on the human patient to whom the active agent is administered, without inappropriate adverse side effects (such as toxicity, irritation, or allergic response), providing a reasonable benefit / risk ratio when used in the manner of this invention. The specific effective amount will vary with such factors as the particular condition being treated, the physical condition of the individual, the nature of the concurrent therapy (if any), the specific dosage form, the oral hygiene composition used and the desired dosage regimen.
[00119] According to one embodiment, the oral composition for use in mineralizing and / or whitening teeth is used in a method that comprises the step of applying the composition to at least one patient's tooth for an effective amount of time, preferably the composition remains at least one tooth for at least 1 min, at least 15 min, at least 30 min, at least 1 hour, at least 2 hours, at least 12 hours or at least 24 hours.
[00120] Calcium carbonate reacted on the surface of the present invention or an oral composition comprising calcium carbonate reacted on the surface of the present invention can be effective for teeth whitening even in the absence of any oxidizing bleaching compound. According to a preferred embodiment of the present invention, the oral hygiene composition does not contain an oxidizing bleaching compound.
[00121] According to one embodiment, the calcium carbonate reacted on the surface of the present invention or an oral composition comprising the calcium carbonate reacted on the surface of the present invention is used in a cosmetic method for teeth whitening, which comprises the step of applying the composition to at least one tooth of an individual for an effective amount of time, preferably the composition remains on at least one tooth for at least 1 min, at least 15 min, at least 30 min, at least 1 hour, at least 2 hours, at least 12 hours or at least 24 hours.
[00122] The scope and interest of the present invention will be better understood based on the following figures and examples which are intended to illustrate certain embodiments of the present invention and are not limiting. Description of the figure:
[00123] Fig. 1 shows a plot of the results of measurements of micro surface hardness (SMH) for the toothpaste samples prepared from Example 1.
[00124] Fig. 2 shows a graph of the CIELAB L * coordinate values determined by the toothpaste samples prepared from Example 1.
[00125] Fig. 3 shows a graph of the CIELAB b * coordinate values determined for the toothpaste samples prepared from Example 1.
[00126] Fig. 4 shows a scanning electron microscope (SEM) micrograph of a sample of demineralized bovine enamel.
[00127] Fig. 5 shows a scanning electron microscope (SEM) micrograph of a sample of demineralized bovine enamel.
[00128] Fig. 6 shows a scanning electron microscope (SEM) micrograph of a sample of demineralized bovine enamel, which was treated with sample 1 of the inventive toothpaste of Example 1.
[00129] Fig. 7 shows a scanning electron microscope (SEM) micrograph of a sample of demineralized bovine enamel, which was treated with sample 1 of the inventive toothpaste of Example 1. EXAMPLES 1. Measurement methods
[00130] In the following, the measurement methods implemented in the examples are described. Particle size distribution
[00131] The size distribution of unreacted calcium carbonate particles on the surface, for example, crushed calcium carbonate, was measured using a Sedigraph 5100 from the company Micromeritics, USA. The method and instrument are known to the skilled person and are commonly used to determine the size of filler grains and pigments. The measurement was carried out in an aqueous solution comprising 0.1% by weight of Na4P2O7. The samples were dispersed using a high speed and supersonic stirrer. For the measurement of dispersed samples, no additional dispersing agent was added.
[00132] The average grain diameter in the volume (d50) of surface-reacted calcium carbonate was determined using a Malvern Mastersizer 2000 Laser Diffraction System (Malvern Instruments Plc., Great Britain). Specific surface area (SSA)
[00133] The specific surface area is measured using the BET method according to ISO 9277 using nitrogen, following the conditioning of the sample by heating at 250 ° C for a period of 30 minutes. Before such measurements, the sample is filtered into a Büchner funnel, rinsed with deionized water and dried overnight at 90 to 100 ° C in an oven. Subsequently, the dry cake is carefully crushed in a mortar and the resulting powder placed in a moisture balance at 130 ° C until a constant weight is reached. Scanning electron microscope (SEM) micrographs
[00134] The prepared bovine enamel samples were examined by a Sigma VP field emission scanning electron microscope (Carl Zeiss AG, Germany) and a secondary variable pressure electronic detector (VPSE) with a chamber pressure of about 50 Pa. 2. MCC materials: surface-reacted calcium carbonate based on crushed calcium carbonate and phosphoric acid (d50 = 6.54 μm, d98 = 16.8 μm, SSA = 25.1 m2 / g). The crushed calcium carbonate was obtained from Orgon, France, (d50 = 3 μm, d98 = 12 μm) and is commercially available from Omya AG, Switzerland. GCC: natural crushed calcium carbonate obtained from Avenza-Carrara, Italy (d50 = 5 μm, d98 = 30 μm), commercially available from Omya AG, Switzerland. 3. Examples Example 1 - Toothpaste compositions
[00135] Toothpaste samples 1 to 4 were produced according to the following procedure using the ingredients and amounts compiled in Table 1 below. Step A: Water and sorbitol were mixed in a beaker. Xanthan gum, sodium benzoate, sodium monofluorophosphate (phoskadent Na 211, BK Giulini, Germany) and sodium saccharin were mixed and the mixture obtained was added to the beaker. Step B: MCC or GCC, respectively, and titanium dioxide were moistened with water and subsequently added to the mixture in step A. The mixture was homogenized until a uniform mixture was obtained. Step C: Sorbosil TC 15 silica (PQ Corporation, USA) was added to the mixture from step B under homogenization conditions, thus, the mixture was heated strongly. The mixture was stirred until it was cooled to room temperature. Step D: the sodium lauryl sulfate surfactant was added as a 25% solution to the mixture of step C under slow stirring. Step E: 0.8% by weight (2.4 g) of mint flavor was added to the mixture from step D.

Table 1: Ingredients and amounts of toothpaste samples from 1 to 4. Percentages refer to percentages by weight based on the total weight of the composition. Example 2 - Remineralization study
[00136] The bovine enamel samples were prepared as follows:
[00137] The blocks of bovine enamel (4 mm x 4 mm) were cut, plane-parallel folded and polished manually. The average baseline micro surface hardness (SMH) value was determined using a MicroMet 5103 hardness testing machine with a Knoop indenter and MicroMet MHT Software (Buehler Ltd., USA) with a load of 50 g, indentation time of 10 s and 5 indentations per block.
[00138] The bovine enamel samples were demineralized for 14 days in a 1: 1 methyl cellulose / lactic acid gel system at 37 ° C and pH 4.6. After demineralization, the SMH of each sample was measured. The samples were stratified into 10-block cells, in which for each of the four toothpaste samples from Example 1 a cell was supplied. In addition, a commercially available non-fluoride silica toothpaste sample (Boots Smile non fluoride freshmint toothpaste, commercially available from Boots UK Ltd., Great Britain) was tested as sample 5 in an additional cell and three more cells were tested. used to cover friction.
[00139] The samples were subjected to a 5-minute treatment with a water paste: 3: 1 toothpaste containing 5 IU / ml phosphatase, 30 minutes with an acidic buffer (50 mM acetic acid, 1.50 mM calcium chloride dihydrate, 0.90 mM potassium dihydrogen orthophosphate, 130 mM potassium chloride, pH 5.0) and 10 minutes with a neutral buffer (20 mM HEPES, 1.50 mM chloride calcium dihydrate, 0.90 mM potassium dihydrogen orthophosphate, 130 mM potassium chloride, pH 7.0). This cycle was repeated 6 times a day for 8 days.
[00140] After the cycle was finished, the samples were left samples in the neutral buffer overnight. Efficacy was estimated by the SMH analysis of the samples, before an pH circulation. Ten readings were taken per sample and remineralization was expressed as a change in SMH. The CIELAB L * a * b * coordinates of all blocks in the SMH baseline measurement, after demineralization and after remineralization, were recorded using a CR321 Konika Minolta chromometer (Konica Minolta, Inc., Japan). In addition, the surface structure of the samples was examined by a Sigma VP field emission scanning electron microscope (Carl Zeiss AG, Germany) and a secondary variable pressure electronic detector (VPSE) with a chamber pressure of about 50 Pan.
[00141] The results of the remineralization studies are shown in Figures 1 to 7.
[00142] It can be gathered from the results of the measurements of micro surface hardness (SMH) shown in Fig. 1 that both samples of fluoridated toothpaste (samples 1 and 3) promoted remineralization to a point significantly greater than those control formulations other than fluoride.
[00143] CIELAB coordinate measurements revealed that after demineralization, the L * value of all tested samples was increased (post-demineralization: after demineralization; post-remineralization: after remineralization). This is caused by the decalcification of the enamel, in which the so-called white spot lesions are developed. With the exception of toothpaste sample 4 (GCC without fluoride), the L * value (luminance cube) of all tested samples decreased after remineralization (see Fig. 2), which is evidence for remineralization.
[00144] The measurement of the b * coordinate shown in Fig. 3, revealed that all enamel samples had a negative b * value (post-demineralization: after demineralization; post-remineralization: after remineralization). A negative b * value means that the registered figure had a blue tint, meaning that all enamel samples had a bluish white, which is usually perceived as a very bright white. The enamel sample that was remineralized with a toothpaste containing calcium carbonate reacted on the surface and without fluoride (sample 2) showed a more negative b * value and, thus, the best whitening effect.
[00145] Figs. 4 and 5 show scanning electron microscope (SEM) micrographs of an enamel sample after demineralization and Figs. 6 and 7 show SEM micrographs of the enamel samples, which were treated with toothpaste sample 1. While breaks and an unevenness of the enamel surface is clearly visible in Figs. 4 and 5, Figs. 6 and 7 show that the enamel surface appears more regular and more uniform after remineralization with the inventive toothpaste.

权利要求:
Claims (16)
[0001]
1. Surface-reacted calcium carbonate for use in mineralization and / or teeth whitening, characterized by the fact that surface-reacted calcium carbonate is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least an acid, wherein the surface-reacted calcium carbonate is a material comprising calcium carbonate and an insoluble non-carbonate calcium salt, at least partially crystalline, extending from the surface of at least part of the calcium carbonate.
[0002]
2. Surface-reacted calcium carbonate according to claim 1 or 2, characterized in that the at least one acid is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, citric acid, acid oxalic, acetic acid, formic acid and mixtures thereof, preferably the at least one acid is selected from the group consisting of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid and mixtures thereof and more preferably at least one acid is phosphoric acid.
[0003]
3. Surface reacted calcium carbonate according to claim 1 or 2, characterized in that the surface reacted calcium carbonate is in the form of particles having an average grain diameter in volume (d50) equal to or less than than 15 μm, preferably from 1 to 10 μm, more preferably from 2 to 8 μm and more preferably from 3 to 7 μm and / or a top cut particle size determined in volume (D98) equal to or less than 25 μm , preferably from 7 to 22 μm, more preferably from 10 to 20 and more preferably from 15 to 18 μm.
[0004]
4. Surface-reacted calcium carbonate according to any of claims 1 to 3, characterized in that the surface-reacted calcium carbonate is in the form of particles having a specific surface area of 5 m2 / g to 200 m2 / g, more preferably 20 m2 / g to 80 m2 / g and even more preferably 30 m2 / g to 60 m2 / g, measured using nitrogen and the BET method according to ISO 9277.
[0005]
Surface-reacted calcium carbonate according to any one of claims 1 to 4, characterized in that the surface-reacted calcium carbonate is used in combination with a fluoride compound, preferably selected from the group consisting of fluoride of sodium, stannous fluoride, sodium monofluorophosphate, potassium fluoride, stannous potassium fluoride, sodium fluorostanate, stannous chlorofluoride, amine fluoride and mixtures thereof and more preferably the fluoride compound is sodium monofluorophosphate and / or sodium fluoride.
[0006]
6. Surface-reacted calcium carbonate according to any one of claims 1 to 5, characterized in that at least one active agent is associated with the surface-reacted calcium carbonate, preferably the active agent is at least a desensitizing agent additional and more preferably the at least one additional desensitizing agent is selected from the group consisting of potassium nitrate, gluteraldehyde, silver nitrate, zinc chloride, strontium chloride hexahydrate, sodium fluoride, stannous fluoride, strontium chloride, strontium acetate, arginine, hydroxyapatite, sodium calcium phosphosilicate, potassium oxalate, calcium phosphate, calcium carbonate, bioactive glasses and mixtures thereof.
[0007]
Surface-reacted calcium carbonate according to any one of claims 1 to 6, characterized in that the surface-reacted calcium carbonate is obtained by a process comprising the steps of: a) providing a carbonate suspension natural or synthetic calcium, b) add at least one acid having a pKa value of 0 or less at 20 ° C or having a pKa value of 0 to 2.5 to 20 ° C to the suspension from step a) and c) treat the suspension from step a) with carbon dioxide before, during or after step b).
[0008]
Surface-reacted calcium carbonate according to any one of claims 1 to 7, wherein the surface-reacted calcium carbonate is obtained by a process comprising the steps of: A) providing a natural or synthetic calcium carbonate, B) supply at least one water-soluble acid, C) supply gaseous CO2, D) contact said natural or synthetic calcium carbonate from step A) with at least one acid from step B) and with CO2 from step C) , characterized by the fact that: i) the at least one acid from step B) has a pKa greater than 2.5 and less than or equal to 7 to 20 ° C, associated with the ionization of its first available hydrogen and a corresponding anion is formed on the loss of its first available hydrogen capable of forming a water-soluble calcium salt and ii) followed by contacting at least one acid with natural or synthetic calcium carbonate, at least one water-soluble salt, which in the case of a hydrogen-containing salt it has a pKa greater than 7 to 20 ° C , associated with the ionization of the first available hydrogen and the salt anion that is capable of forming water-insoluble calcium salts, is additionally provided.
[0009]
9. Oral care composition for use in mineralization and / or teeth whitening, characterized by the fact that it comprises a surface-reacted calcium carbonate, in which the surface-reacted calcium carbonate is a reaction product of natural calcium carbonate or synthetic with carbon dioxide and at least one acid.
[0010]
10. Oral care composition according to claim 9, characterized in that the oral care composition comprises from 1 to 40% by weight, preferably from 1.5 to 35% by weight, more preferably from 2 to 30% by weight of the surface-reacted calcium carbonate, based on the total weight of the composition.
[0011]
An oral care composition according to claim 9 or 10, characterized in that the oral care composition is a toothpaste, a dental powder or a mouthwash, and in which preferably the calcium carbonate reacted on the surface is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and phosphoric acid.
[0012]
12. Oral care composition according to any of claims 9 to 11, characterized in that the oral composition still comprises a fluoride compound, preferably the fluoride compound is selected from the group consisting of sodium fluoride, fluoride stannous, sodium monofluorophosphate, potassium fluoride, stannous potassium fluoride, sodium fluorostanate, stannous chlorofluoride, amine fluoride and mixtures thereof and more preferably the fluoride compound is sodium monofluorophosphate and / or sodium fluoride.
[0013]
13. Oral care composition according to any of claims 9 to 12, characterized in that the oral care composition still comprises an additional remineralizing and / or bleaching agent, preferably selected from the group consisting of hydroxyapatite, for example. example, nanohydroxyapatite, calcium carbonate, for example, amorphous calcium carbonate and combinations of these with casein phospholipids, hydrogen peroxide, carbamide peroxide, fluoride compounds and mixtures thereof.
[0014]
14. Oral care composition according to any of claims 9 to 13, characterized in that the oral care composition has a pH between 7.5 and 10, preferably between 8 and 9.
[0015]
15. Calcium carbonate reacted on the surface for use in the mineralization of teeth, characterized by the fact that calcium carbonate reacted on the surface is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid.
[0016]
16. Calcium carbonate reacted on the surface for use in whitening tooth enamel, characterized by the fact that calcium carbonate reacted on the surface is a reaction product of natural or synthetic calcium carbonate with carbon dioxide and at least one acid .

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同族专利:

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CA2941125C|2018-09-04|

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WO2015150011A1|2015-10-08|

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AU2015239968A1|2016-09-15|

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EP2926797B1|2017-09-06|

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MY176231A|2020-07-24|

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ZA201607254B|2018-05-30|

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MX2016012686A|2017-01-05|

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UY36036A|2015-10-30|

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RU2016142392A3|2018-05-07|

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IL247525D0|2016-11-30|

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JP2017515796A|2017-06-15|

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CA2941125A1|2015-10-08|

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CL2016002367A1|2017-02-17|

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MX352955B|2017-12-15|

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JP6453902B2|2019-01-16|

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AU2015239968B2|2017-05-25|

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RU2016142392A|2018-05-07|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

WO1998042297A1|1997-03-25|1998-10-01|Sunstar Kabushiki Kaisha|Method of recalcifying teeth|

---

FR2787802B1|1998-12-24|2001-02-02|Pluss Stauffer Ag|NOVEL FILLER OR PIGMENT OR MINERAL TREATED FOR PAPER, ESPECIALLY PIGMENT CONTAINING NATURAL CACO3, METHOD FOR MANUFACTURING SAME, COMPOSITIONS CONTAINING THEM, AND APPLICATIONS THEREOF|

---

US20040146466A1|1999-11-12|2004-07-29|The Procter & Gamble Company|Method of protecting teeth against erosion|

---

WO2007092763A2|2006-02-03|2007-08-16|Wm. Wrigley Jr. Company|Calcium phosphate salts in oral compositions suitable as a tooth remineralizing agent|

---

SI1974806T1|2007-03-21|2012-01-31|Omya Development Ag|Process for the purification of water|

---

PL1974807T3|2007-03-21|2010-08-31|Omya Int Ag|Process for the removal of endocrine disrupting compounds|

---

DK1982759T3|2007-03-21|2012-01-02|Omya Development Ag|Surface treated calcium carbonate and its use for wastewater treatment|

---

PT2093261E|2007-11-02|2013-11-26|Omya Int Ag|Use of a surface-reacted calcium carbonate in tissue paper, process to prepare a tissue paper product of improved softness, and resulting improved softness tissue paper products|

---

PT2070991E|2007-12-12|2010-10-25|Omya Development Ag|Process to make surface-reacted precipitated calcium carbonate|

---

EP2168572A1|2008-09-30|2010-03-31|Omya Development Ag|New controlled release active agent carrier|

---

TWI395595B|2009-04-01|2013-05-11|Colgate Palmolive Co|Oral compositions for treating tooth sensitivity and methods of use and manufacture thereof|

---

ES2384017T3|2009-06-15|2012-06-28|Omya Development Ag|Process to prepare calcium carbonate that reacts on the surface and its use|

---

PL2264108T3|2009-06-15|2012-07-31|Omya Int Ag|Process to prepare a surface-reacted calcium carbonate implementing a weak acid|

---

US20130171221A1|2010-09-10|2013-07-04|Yan Deng|Oral care compositions for benefiting teeth|

---

CN103476385B|2011-04-18|2015-12-09|荷兰联合利华有限公司|Remineralization of teeth oral care composition|

---

WO2012143220A1|2011-04-18|2012-10-26|Unilever Nv|Tooth remineralizing oral care compositions|

---

EP2753292B1|2011-09-08|2018-06-27|Unilever N.V.|Tooth remineralizing dentifrice|

---

JP2013067567A|2011-09-21|2013-04-18|Lion Corp|Dentifrice composition|

---

US9901755B2|2011-09-23|2018-02-27|Sancastle Worldwide Corporation|Composition for preventing or treating dentin-associated symptoms or diseases, and method using the same|

---

JP2013163656A|2012-02-10|2013-08-22|Gc Corp|Dentifrice|

---

EP2921173A1|2014-03-21|2015-09-23|Omya International AG|Surface-reacted calcium carbonate for desensitizing teeth|EP3176222A1|2015-12-01|2017-06-07|Omya International AG|Method for the production of granules comprising surface-reacted calcium carbonate|

---

EP3175835A1|2015-12-04|2017-06-07|Omya International AG|Oral care composition for remineralisation and whitening of teeth|

---

CN105640788B|2016-01-27|2018-04-24|杭州皎洁口腔保健用品有限公司|A kind of hydroxy agustite tooth-paste and preparation method thereof|

---

CN106074195B|2016-07-06|2019-08-23|杭州皎洁口腔保健用品有限公司|A kind of hydroxyl apatite and the toothpaste of calcium carbonate and preparation method thereof|

---

EP3509993A1|2016-09-08|2019-07-17|Schaefer Kalk GmbH & Co. KG|Composite powder containing calcium carbonate and having microstructured particles having inhibiting calcium carbonate|

---

CN108324578B|2017-01-17|2020-02-14|武汉大学|Liquid-phase mineralized precursor and method for repairing demineralized dentin|

---

CN107028799B|2017-02-21|2020-05-12|广州薇美姿实业有限公司|Anti-allergy whitening oral cavity smearing liquid|

---

EP3400810A1|2017-05-11|2018-11-14|Omya International AG|Surface-reacted calcium carbonate in food|

---

EP3668478A1|2017-08-18|2020-06-24|Unilever N.V.|Oral care composition|

---

CN109431834B|2018-12-20|2021-11-09|扬州倍加洁日化有限公司|Oral composition added with bioactive glass and strontium chloride and application thereof|

---

TW202042781A|2019-05-03|2020-12-01|瑞士商歐米亞國際公司|Surface-treated magnesium ion-containing materials as white pigments in oral care compositions|

---

EP3733786A1|2019-05-03|2020-11-04|Omya International AG|Surface-treated magnesium ion-containing materials as white pigments in oral care compositions|

---

CN110074988A|2019-06-12|2019-08-02|四川涑爽医疗用品有限公司|The composition of a kind of anti-dentine hypersensitivity and pre- anti-caries and oral care product comprising the composition|

---

BR112021024290A2|2019-06-28|2022-01-11|Procter & Gamble|Toothpaste compositions comprising tin ions|

---

EP3882315A1|2020-03-20|2021-09-22|Omya International AG|Surface-treated magnesium ion-containing materials as white pigments in oral care compositions|

---

US20210386643A1|2020-06-10|2021-12-16|Amarillo Junior College District|Effective teeth whitening composition utilizing bromelain enzymes|

---

US11135143B2|2020-06-25|2021-10-05|The Procter & Gamble Company|Oral care compositions comprising tin ions|

---

RU2750273C1|2020-09-30|2021-06-25|Федеральное государственное бюджетное образовательное учреждение высшего образования "Саратовский национальный исследовательский государственный университет имени Н.Г. Чернышевского"|Method for controlling quality of tooth enamel|

法律状态:
2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-07-28| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-01-12| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-02-09| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/03/2015, OBSERVADAS AS CONDICOES LEGAIS. |

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2021-03-30| B16C| Correction of notification of the grant [chapter 16.3 patent gazette]|Free format text: REF. RPI 2614 DE 09/02/2021 QUANTO AO TITULO. |

优先权:

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申请号 | 申请日 | 专利标题

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US201461972532P| true| 2014-03-31|2014-03-31|

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EP14162818.0A|EP2926797B1|2014-03-31|2014-03-31|Surface-reacted calcium carbonate for remineralisation and whitening of teeth|

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US61/972532|2014-03-31|

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EP14162818.0|2014-03-31|

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PCT/EP2015/054580|WO2015150011A1|2014-03-31|2015-03-05|Surface-reacted calcium carbonate for remineralisation and whitening of teeth|

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