Calcium hypophosphite and water-soluble phosphate salt for use in a method of treatment and / or prophylaxis of oral and / or dental diseases

Abstract

The present invention relates to calcium hypophosphite combined with at least one water-soluble phosphate salt for use in a method of treatment and / or prophylaxis of oral and / or dental diseases, to a composition comprising calcium hypophosphite and at least one water-soluble phosphate salt, to an oral care product comprising the composition, to an oral care product comprising a composition that comprises calcium hypophosphite and a composition that comprises at least one phosphate salt, and to uses of the composition and / or of the oral care products.

Description

[0001] Calcium hypophosphite and water-soluble phosphate salt for use in a method for treating and / or preventing diseases of the mouth and / or teeth

[0002] The present invention relates to calcium hypophosphite in combination with at least one water-soluble phosphate salt for use in a method for treating and / or preventing diseases in the oral cavity and / or teeth, a composition comprising calcium hypophosphite and at least one water-soluble phosphate salt, an oral care product comprising the composition, an oral care product comprising a composition comprising calcium hypophosphite and a composition comprising at least one water-soluble phosphate salt, and uses of the composition and / or oral care products.

[0003] Dental care is becoming increasingly important, simply because of the increasing carbohydrate content of diets worldwide. In addition to aesthetic aspects, greater emphasis is being placed on preventative care, with the primary focus being on reducing or even preventing plaque, caries, and / or halitosis (bad breath), as well as healthy gums. There is a high demand for tooth-regenerating dental care products, particularly due to the high prevalence of caries and the widespread occurrence of dental defects such as molar-incisor hypomineralization (MIH), but also due to modern dietary habits (i.e., erosion damage caused by acidic drinks and foods) and the natural wear of tooth enamel with increasing age.

[0004] Healthy gums are characterized, among other things, by their cervical surroundings. The gums surround the neck of the tooth, sealing the point where the tooth enters the jawbone of the oral cavity. The gums thus serve, among other things, to protect and support the tooth.

[0005] The different parts of a natural tooth are the crown, neck, and root, each of which is made up of several layers. Of these layers, only the outer enamel is visible in a healthy tooth, which encloses the dentin and other layers. In order to be able to bite or grind food, for example, without damaging the teeth, the enamel is very hard. It consists of approximately 97% by weight of hydroxyapatite (HAP), which has the molecular formula Cas(PO4)3(OH). Dentin is also considered the hard substance of the tooth and is also made up of about two-thirds hydroxyapatite. In addition to hydroxyapatite, dentin also contains proteins (e.g. collagen) and water and is therefore softer than enamel.

[0006] It is documented that saliva, due to its supersaturation of Ca 2+- and pores in a bioavailable form has a remineralizing effect. However, the remineralizing effect induced by saliva is not only slow but also apparently insufficient to protect individuals from caries and / or remineralize existing dental lesions without the addition of mineralization-enhancing additives.

[0007] Dental diseases such as caries can be caused by the formation of bacterial microfilms and / or bacterial inflammation. Although often preventable through preventive care, caries remains one of the most common chronic diseases in children and adults worldwide, and there is a great global need for products to prevent and treat caries-affected teeth.

[0008] Caries is considered a multifactorial disease, particularly affecting tooth enamel and dentin, involving microorganisms. In the initial stage, a precipitate, also called a pellicle, can form on the tooth surface. It consists of saliva protein, among other substances. The rougher the tooth surface, the easier it is for this precipitate to form and adhere to it. Over time, this pellicle then forms a film a few micrometers thick covering the tooth surface. Bacteria can then multiply and spread on this film. This film can be considered a biofilm.

[0009] The bacteria can produce organic acids, such as gluconic and lactic acid, from low-molecular-weight carbohydrates commonly found in today's diet. Both these organic acids produced by bacteria and acids ingested through food, such as fruit acids, can cause erosion of tooth structure.

[0010] This process dissolves, among other things, calcium phosphates from the tooth enamel. If this process is not stopped, or preferably even reversed, demineralization of the tooth enamel and possibly also of the dentin can occur over time. A defect in the tooth structure caused in this way is referred to as a carious lesion. Carious lesions in the dentin layer, for example, can be recognized by a yellow to brown discoloration of the affected area of ​​the tooth. While carious lesions in the enamel alone can often be reduced or eliminated by re-mineralization of the enamel, in the case of carious lesions that affect other layers in addition to the enamel, the damaged part of the tooth is usually removed and the resulting hole (caries lesion) is closed with a filling material.

[0011] In summary, caries formation can be promoted by the interaction of the following factors:

[0012] - special bacteria that adhere to the pellicle

[0013] - poor tooth quality or mineral quality of the tooth

[0014] - Plaque

[0015] - food containing low molecular weight carbohydrates

[0016] - Time.

[0017] One possible approach to caries prevention could therefore be the administration of calcium phosphate compounds, particularly hydroxyapatite, to improve tooth quality. Furthermore, there are various approaches, all aimed at preventing caries in order to avoid the aforementioned treatments. Caries prevention with fluoride-containing dental care products can be considered the current standard. J.M. ten Cate: "Contemporary perspective on the use of fluoride products in caries prevention", British Dental Journal, February 23, 2013, vol. 214, no. 4, pp. 161-167, describes in a review the use and effectiveness of fluoride-containing dental care products such as toothpaste and mouthwash.

[0018] It is particularly noted that the reduction of caries is achieved through regular use of such fluoride-containing dental care products. The model assumes that fluoride accelerates natural remineralization from saliva.

[0019] Various fluoride compounds, such as sodium fluoride, stannous fluoride, amine fluorides, and sodium monofluorophosphate, are suitable as fluoride sources in the aforementioned dental care products. J.M. ten Cate: “The Need for Antibacterial Approaches to Improve Caries Control," Adv Dent Res 21:8-12, August 2009, pp. 8-12, describes that fluoride provision alone may not be sufficient to achieve adequate caries prevention, since, as mentioned above, bacteria also play a crucial role in caries formation. For this reason, caries prophylactic compositions are being considered that contain one or more antimicrobial substances in addition to fluoride. One example is chlorhexidine (CHX), whose antimicrobial effect in the oral cavity has been investigated in many studies.

[0020] The use of fluorides in dental care products is controversial, however, due to concerns about negative side effects. One example is dental fluorosis, which occurs due to excessive fluoride intake during tooth formation. Acute toxic effects include nausea, vomiting, and diarrhea. Other examples are bone fluorosis, which is characterized by thickening of the outer bone layer and the associated loss of elasticity and resilience, and enamel fluorosis, which is recognizable by the appearance of whitish enamel spots on the tooth surface. Furthermore, it has been reported that swallowing high-dose dental care products, especially in children, can trigger acute fluoride poisoning, which can occasionally even be fatal. In a recent evaluation of in vivo human studies by the National Toxicology Program of the USDepartments of Health and Human Services have clearly established that the higher the mother's fluoride exposure during pregnancy, the lower the IQ score of her children.

[0021] Furthermore, the WHO is not yet able to establish a value for daily fluoride requirements, as fluoride is not an essential trace element. Therefore, there are no diagnostic parameters and no corresponding evidence for the existence of clinical symptoms of "fluoride deficiency."

[0022] The use of an antimicrobial substance such as chlorhexidine in dental care, especially for caries prevention, is also controversial. It has been reported that a relevant effect for caries prevention is not always reproducible and only occurs in a portion of the studied cases. Furthermore, the antimicrobial effect of chlorhexidine is not limited to the bacteria in the mouth that contribute to caries formation, but also includes beneficial bacteria. Furthermore, long-term treatment with products containing chlorhexidine leads to undesirable side effects, such as tooth discoloration and impaired taste.

[0023] Biomimetic tooth and mouthwashes with artificial enamel, which may contain the active ingredient hydroxyapatite, are also known. Hydroxyapatite-based products can reduce initial bacterial colonization on the enamel surface without possessing antimicrobial properties that can disrupt the oral cavity's ecological balance. Furthermore, these products are said to remineralize and repair microscopic defects in the enamel, as well as form a protective layer.

[0024] Biomimetic dental care products based on the use of hydroxyapatite are also known. For example, WO 2018 / 024649 A1, DE 10 2017 009 626 A1, and DE 10 2018 102 365 describe oral care compositions containing synthetic hydroxyapatite. Hydroxyapatite, as indicated above, is a bioactive and biocompatible material with a similar chemical composition to the hydroxyapatite of human tooth enamel.

[0025] However, due to the above-mentioned limitations of both the homeostatic mechanism of the body's own saliva and the fluoride-based approaches to caries prevention and remineralization, there is a need for alternative active ingredients or combinations of active ingredients, compositions and / or oral care products that are at least equivalent to the efficiency of fluoride supplementation in mineralization, but without the corresponding undesirable side effects.

[0026] Furthermore, there continues to be a need for active ingredients or combinations of active ingredients, compositions and / or oral care products for the treatment or prevention of various diseases affecting the teeth.

[0027] Furthermore, the use of the provided active ingredients or combinations of active ingredients, compositions and / or oral care products should not significantly disturb the ecological balance in the oral area and / or risk tooth discoloration or taste disturbance.

[0028] The object of the invention is therefore to provide a novel active ingredient or a novel combination of active ingredients for use in a method for effective in situ tooth regeneration and for caries prevention, which avoids the above-described disadvantages of the prior art. In particular, neomineralization, i.e., calcium phosphate formation on the teeth, is to be achieved. Furthermore, novel compositions and / or an oral care product, in particular a toothpaste or mouthwash, are to be provided that fulfill the above-mentioned objects.

[0029] In particular, the aim is to provide a combination of active ingredients, a composition, or an oral care product, preferably a toothpaste or mouthwash, whose use leads to effective remineralization of the teeth. Furthermore, existing, minor caries lesions are to be mineralized and / or microscopic defects in the tooth enamel are to be repaired (repair effect) and filled (filling effect). Furthermore, a protective layer is to be applied to the tooth and / or open dentin tubules are to be closed. To this end, the aforementioned effects are to be achieved while avoiding the disadvantages that can accompany the use of fluoride. Furthermore, the adhesion of bacteria to the tooth enamel is to be advantageously reduced without significantly disturbing the ecological balance in the oral cavity and / or risking tooth discoloration or taste disturbance.The composition, the oral care product and the combination of active ingredients should also not have any irritating effect on the mucous membranes when used.

[0030] These objects are achieved according to the invention by calcium hypophosphite in combination with at least one water-soluble phosphate salt for use in a method for the treatment and / or prevention of diseases in the oral cavity and / or the teeth and / or for the care of the oral cavity and throat, in particular the teeth. These objects are further achieved by the composition according to the invention and oral care products according to the invention comprising calcium hypophosphite and at least one water-soluble phosphate salt. In addition, at least one compound selected from the group comprising antibacterial substances, moisturizing or caring substances, desensitizing substances, surfactants, and abrasive agents can be contained in the composition according to the invention and / or in an oral care product according to the invention.

[0031] A first aspect of the invention therefore relates to calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use in a method for the treatment and / or prevention of diseases in the oral cavity and / or the teeth and / or for the care of the oral cavity and throat, in particular the teeth, wherein the water-soluble phosphate salt has a solubility between > 10 g / L and < 2000 g / L in water at 20 °C. The diseases to be treated and / or prevented are preferably selected from reduced salivation, for example in xerostomia, chalky teeth and / or fluorosis, caries, sensitive teeth, teeth damaged by erosion, in particular by acids, and / or demineralized teeth, ie the treatment has a remineralizing effect.

[0032] Phosphinic acid, also known as hypophosphorous acid, is one of the phosphorus acids and has the molecular formula H3PO2. Its salts are called phosphinates or hypophosphites. In scientific literature, the term calcium hypophosphite is also used as a synonym. Calcium hypophosphite has the molecular formula Ca(H2PO2)2.

[0033] According to the invention, calcium hypophosphite (A) is used in combination with at least one water-soluble phosphate salt (B) in a method for treating and / or preventing diseases of the oral cavity and / or teeth and / or for caring for the oral and pharyngeal cavity, especially the teeth. Hydrogen phosphates and dihydrogen phosphates are included. Sodium phosphates or potassium phosphates are preferred.

[0034] Preferred are water-soluble phosphate salts selected from the group consisting of sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium phosphate, or any mixtures thereof, including the corresponding hydrates. Disodium hydrogen phosphate and / or dipotassium hydrogen phosphate are particularly preferred.

[0035] Other water-soluble phosphate salts that can be used are, for example, ammonium phosphate, iron(III) phosphate, zinc phosphate, aluminum phosphate, sodium hexametaphosphate, tetrasodium pyrophosphate, magnesium dihydrogen phosphate, magnesium hydrogen phosphate, magnesium glycerophosphate or magnesium phosphate, in particular also in combination with the above-mentioned particularly preferred water-soluble phosphate salts.

[0036] According to the invention, one or more water-soluble phosphate salt(s) (B) with a solubility between > 10 g / L and < 2000 g / L at 20 °C in water are preferred. Phosphate salts with a solubility between > 20 g / L and < 1500 g / L at 20 °C in water are preferred. Phosphate salts with a solubility between > 50 g / L and < 650 g / L at 20 °C in water are particularly preferred.

[0037] According to the invention, it is preferred that calcium hypophosphite (A) and the at least one water-soluble phosphate salt (B) react with each other in the oral region, thereby preferably forming calcium phosphates, particularly preferably hydroxyapatite. These calcium phosphates formed in situ can contribute to the remineralization of the teeth.

[0038] It is therefore preferred according to the invention that (A) and (B) are present at least partially dissolved, preferably predominantly dissolved, particularly preferably completely dissolved in at least one composition before use.

[0039] In order to enable the reaction in the oral region, it is preferred according to the invention that (A) and (B) are in a state before use in which they do not or predominantly do not react with each other to form calcium phosphates. It is further preferred that a reaction of (A) with (B), preferably to form calcium phosphates, particularly preferably to form hydroxyapatite, is enabled immediately before or during use in the oral region. According to the invention, this can preferably be achieved by activating a composition comprising (A) and (B), or by contact of (A) with (B), wherein (A) and (B) are previously spatially separated in different compositions.

[0040] Surprisingly, it was experimentally demonstrated within the scope of the invention (see Example 3) that upon contact of a composition containing (A) calcium hypophosphite with a composition containing (B) a water-soluble phosphate salt, in this case disodium hydrogen phosphate, at a pH value of >5.5, hydroxyapatite is formed.

[0041] In a preferred embodiment of the invention, (A) and (B) are present together in a composition. It is further preferred that the composition has an initial pH of 3.5 to 5.5. The acidic pH at least partially prevents the precipitation of calcium phosphates. The composition is preferably in the form of an oral care product.

[0042] Preferably, (A) and (B) react after activation by increasing the pH of the composition in the oral region to >5.5, preferably 5.5-9.5, more preferably 6-8.5, particularly preferably 6.5-7.5, and in the process preferably form calcium phosphates, in particular hydroxyapatite. The pH is preferably increased by contact of the composition according to the invention with saliva in the oral cavity, e.g., during tooth brushing or mouth rinsing. Alternatively, the pH can be increased by adding one or more pH-changing formulations or compositions to the composition. Preferably, the pH-changing formulation(s) are added immediately before use, or contact of the composition according to the invention with the pH-changing composition only occurs in the oral region.Preferred pH-changing formulations for this purpose are mouthwashes, toothpastes and oral gels containing sodium hydroxide, potassium hydroxide, calcium carbonate, sodium carbonate or any mixtures thereof.

[0043] A further aspect of the invention relates to a composition for topical application comprising

[0044] (A) 0.0001 to 20 wt.% calcium hypophosphite, and

[0045] (B) at least one phosphate salt with a solubility between > 10 g / L and < 2000 g / L in water at 20 °C.

[0046] The composition according to the invention preferably has a pH in the range of 3.5 to 5.5. It is further preferred that the composition be activatable by increasing the pH to >5.5, preferably 5.5-9.5, more preferably 6-8.5, particularly preferably 6.5-7.5. "Activatable" here means that, as described above, a reaction of (A) with (B) is promoted, preferably to form calcium phosphates, particularly preferably to form hydroxylapatite.

[0047] The composition according to the invention is intended for topical application, particularly in the oral cavity. The composition according to the invention is particularly preferably designed for use in dental and oral care. The composition according to the invention is particularly preferably in the form of an oral care product.

[0048] A further aspect of the invention relates to an oral care product comprising the composition according to the invention, wherein the oral care product is preferably a toothpaste, a mouthwash, an oral gel, a chewing gum, a tooth varnish, or a polishing paste. According to the invention, it is preferred that in all embodiments of the invention in which (A) and (B) are present together in a composition, the molar ratio of calcium in calcium hypophosphite to phosphorus in the water-soluble phosphate salt in the composition is between 3:2 and 1:2 (calcium:phosphorus), preferably 3:2, 1:1, or 1:2, and particularly preferably 1:1.

[0049] In a preferred embodiment, the calcium hypophosphite and the water-soluble phosphate salt are present in the same formulation as described above (single-phase product). However, the calcium hypophosphite and the water-soluble phosphate salt can also be spatially separated from each other.

[0050] In an alternative preferred embodiment, the invention therefore relates to calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use in a method for the treatment and / or prevention of diseases in the oral cavity and / or the teeth and / or for the care of the oral cavity and throat, in particular the teeth, wherein the water-soluble phosphate salt has a solubility between > 10 g / L and < 2000 g / L in water at 20 °C, and wherein (A) and (B) are spatially separated in two different compositions which are applied simultaneously or sequentially in the oral region.

[0051] According to the invention, it is preferred that contact between (A) and (B) is established in the oral region and / or immediately prior to application in the oral region. It is further preferred that (A) and (B) react with each other upon contact in the oral region, thereby preferably forming calcium phosphates, particularly preferably hydroxyapatite.

[0052] In a preferred embodiment, the spatially separated compositions containing (A) and (B) are applied simultaneously in the oral region, with contact of (A) with (B) occurring immediately before or during application in the oral region. Accordingly, a reaction of the calcium hypophosphite with the water-soluble phosphate salt occurs during or immediately after application.

[0053] In this case, the following packaging and formulation techniques are preferred: Dual-chamber tubes: These tubes have two separate chambers containing different ingredients. When the tube is squeezed, the ingredients are brought together and mixed.

[0054] Microcapsules: Ingredients can be enclosed in microcapsules that only break open and release the ingredients when you brush your teeth.

[0055] Layering: Layering ingredients in the tube allows them to remain separate until they are squeezed out of the tube, where they then mix.

[0056] Gel formulations: Some ingredients can be suspended in a gel that maintains their stability until use.

[0057] Compartmentalized packaging: In addition to dual compartments, more complex packaging with multiple compartments can also be used to separate a variety of ingredients.

[0058] Sealed strips: Strips that are sealed and mix with the base paste when squeezed out.

[0059] Pump dispensers: Instead of tubes, pump dispensers can be used, allowing for more precise dosing and separation of ingredients.

[0060] Dry toothpastes: Toothpastes in powder or tablet form that are only activated upon contact with water.

[0061] Foam: A two-chamber system can be used with a foam, whereby the two reactive substances are stored in separate chambers and are only mixed and activated when the foam dispenser is triggered.

[0062] Spray: For a spray, the reagents can be stored in a dual-spray bottle, which releases the two reactive substances from separate nozzles when sprayed, combining them in the spray mist. In a chewing gum, the reactive substances could be encapsulated in microcapsules that are only mechanically broken open by chewing, thus triggering the reaction.

[0063] When using a two-chamber system, the calcium hypophosphite and the water-soluble phosphate salt are mixed immediately before the formulation is applied to the teeth.

[0064] Polylactide-co-glycolide, polyethylene glycol, chitosan, polyvinyl alcohol, polylactic acid, polyglycolic acid, polycaprolactone, polyacrylates, celluloses or any mixtures thereof are preferably used for encapsulation.

[0065] The stabilization of the calcium hypophosphite or the water-soluble phosphate salt in the composition can be achieved by chelating agents, polymers and / or surfactants.

[0066] Preferred chelating agents for stabilization are citric acid, sodium citrate, tartaric acid, phosphoric acid or any mixtures thereof.

[0067] Preferred polymers for stabilization are celluloses, polyethylene glycol, polyvinyl alcohol, polylactide-co-glycolide, chitosan, alginates, hyaluronic acid, polyacrylates, or any mixtures thereof. Preferred surfactants for stabilization are anionic or cationic surfactants.

[0068] In a further preferred embodiment, the spatially separated compositions containing (A) and (B) are applied sequentially in the oral region at intervals of 1 second to 30 minutes, either first applying the composition containing (A) and then applying the composition containing (B), or first applying the composition containing (B) and then applying the composition containing (A). The interval between the sequential applications is preferably 1 second to 10 minutes, particularly preferably 30 seconds to 5 minutes.

[0069] The composition containing (A) and the composition containing (B) can preferably be present independently of one another in the form of an oral care product, preferably selected from a capsule, mouthwash, a gel, or a toothpaste. In particular, it is preferred to use a toothpaste first and then a mouthwash or a gel. Furthermore, it is preferred that component (A) or (B) of the first-applied composition remains at least partially in the mouth area until the second composition is applied, and that contact occurs between (A) and (B) in the mouth area upon application of the second composition, which contains the respective other component (B) or (A).

[0070] Another aspect of the invention relates to an oral care product for topical application comprising

[0071] (a) a composition comprising calcium hypophosphite, and

[0072] (b) a composition comprising at least one water-soluble phosphate salt having a solubility between > 10 g / L and < 2000 g / L in water at 20 °C, wherein the compositions (a) and (b) are spatially separated in the oral care product and are designed for simultaneous or sequential application.

[0073] In a preferred embodiment of this oral care product according to the invention, compositions (a) and (b) are layered, encapsulated, spatially separated in a carrier matrix and / or in different chambers of a package. It is also possible for only one of the compositions to be encapsulated, e.g., in microcapsules, and the other composition to be contained in the carrier matrix. The preferred packaging and formulation techniques correspond to those described above for the simultaneous application of (A) and (B). It is therefore preferred for compositions (a) and (b) to be spatially separated in an oral care product in the form of a toothpaste, a gel, a foam, a spray, or chewing gum.

[0074] In another preferred embodiment of the oral care product according to the invention, composition (a) and composition (b) are each present independently of one another in the form of an oral care product selected from a capsule, mouthwash, gel, or toothpaste. For example, the oral care product may comprise a combination of toothpaste and gel or toothpaste and mouthwash. Sequential application of compositions (a) containing (A) and composition (b) containing (B), as described above for the sequential application of (A) and (B), is preferred. The compositions according to the invention are described in more detail below.Unless further restricted, the following features apply both to compositions described in connection with the first aspect of the invention - relating to calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use in a method for the treatment and / or prevention of diseases in the oral cavity and / or teeth and / or for the care of the oral cavity and throat, in particular the teeth - and for all preferred embodiments of this aspect of the invention, as well as to all compositions according to the invention and compositions in oral care products according to the invention.

[0075] Insofar as a composition according to the invention is intended for use in the oral or mouth area, the terms “composition according to the invention” and “oral care product” can be used interchangeably herein.

[0076] "Free" in the context of the present invention means that the composition according to the invention may contain unavoidable impurities of the substance designated "free from." "Substantially free" in the context of the present application means "< (less than) 10 ppm."

[0077] A calcium hypophosphite-containing composition according to the invention preferably contains calcium hypophosphite in an amount of 0.0001 to 20.0 weight percent (wt%), preferably 0.001 to 15 wt%, more preferably 0.01 to 15 wt%, particularly preferably 0.1 to 8 wt%, and especially 2.5 wt%, in each case based on the total weight of the composition. A preferred toothpaste or mouthwash formulation contains 1.0-5.0 wt% calcium hypophosphite based on the total weight of the composition.

[0078] In a composition according to the invention, calcium hypophosphite is preferably at least partially dissolved, more preferably predominantly dissolved, and most preferably completely dissolved. It is known that the solubility of calcium hypophosphite in water is approximately 154 g / l (Robertson, DS Magnesium or calcium hypophosphite could be a treatment for obesity in humans. Med. Hypotheses 2006, 66, 439-440). It is therefore preferred that all calcium hypophosphite in the composition according to the invention be dissolved up to a concentration of approximately 154 g / l. A composition according to the invention which contains at least one water-soluble phosphate salt contains water-soluble phosphate salt preferably in an amount of 0.0001 to 40.0 percent by weight (wt%), preferably from 0.001 to 20.0 wt%, more preferably 0.01 to 10 wt%, particularly preferably 0.1 to 8 wt% and in particular 2.5 wt%, in each case based on the total weight of the composition.

[0079] A composition according to the invention preferably comprises a carrier system. The carrier system preferably contains at least one substance selected from remineralizing substances, antibacterial substances, moisturizing or conditioning substances, desensitizing substances, and abrasive agents. Furthermore, any mixtures of these substances can be included in the carrier system according to the invention.

[0080] The carrier system particularly preferably comprises at least one additional calcium phosphate. Generally, calcium phosphate, also known as tricalcium orthophosphate or tricalcium phosphate (Ca3(PO4)2), refers to a calcium salt of orthophosphoric acid and belongs to the phosphates. The term tricalcium phosphate is occasionally used for the very similar compound pentacalcium hydroxytriphosphate (CasPO^sOH) (=hydroxyapatite).

[0081] According to the invention, in addition to calcium hypophosphite and the water-soluble phosphate salt, at least one calcium phosphate compound can be included in a composition according to the invention, which is preferably in particulate form and is selected from the group consisting of monocalcium phosphate monohydrate (MCPM), monocalcium phosphate anhydrate (MCPA), dicalcium phosphate dihydrate (DCPD, brushite), dicalcium phosphate anhydrate (DCPA, monetite), octacalcium phosphate (OCP), α-tricalcium phosphate (α-TCP), β-tricalcium phosphate (β-TCP), amorphous calcium phosphate (ACP;also as CPP-ACP complex = casein phosphopeptide - amorphous calcium phosphate), amorphous calcium phosphate (ACP), calcium-deficient hydroxyapatite (CDHA), hydroxyapatite (HA or HAP), tetracalcium phosphate (TTCP) and calcium pyrophosphate, preferably from the group consisting of monocalcium phosphate monohydrate (MCPM), monocalcium phosphate anhydrate (MCPA), dicalcium phosphate dihydrate (DCPD, brushite), dicalcium phosphate anhydrate (DCPA, monetite), octacalcium phosphate (OCP), amorphous calcium phosphate (ACP;Also known as CPP-ACP complex (casein phosphopeptide - amorphous calcium phosphate), amorphous calcium phosphate (ACP), calcium-deficient hydroxyapatite (CDHA), hydroxyapatite (HA or HAP), and tetracalcium phosphate (TTCP), and any mixtures of these compounds. Hydroxyapatite is particularly preferred. The at least one calcium phosphate compound can be present in different crystal forms, including mixtures of these crystal forms, with rounder crystal forms being preferred over more pointed crystal forms (e.g., needle-shaped crystals). Likewise, they can have different crystal and aggregate sizes, including mixed forms, and different crystallinities, also mixed forms.

[0082] Hydroxyapatite is particularly preferred according to the invention. However, depending on the use of the compositions described herein, embodiments may also be preferred according to the invention that contain no other calcium phosphate compound besides calcium hypophosphite, and in particular no hydroxyapatite.

[0083] Hydroxyapatite is also known as hydroxyapatite. Accordingly, the terms are used interchangeably herein. It is a mineral from the phosphate mineral class that crystallizes in a hexagonal crystal system. Hydroxyapatite is also a member of the apatite group and forms a continuous mixed series with chloroapatite and fluorapatite.

[0084] A Cas(PO4)3(OH) suitable for the invention is described, for example, in DE 102016 114 189.5. The Cas(PO4)3(OH) used according to the invention is preferably produced synthetically. This means that the Cas(PO4)3(OH) used according to the invention is preferably not obtained by burning out the organic components from animal material, such as bone.

[0085] According to the invention, in the case of a single-phase product, a composition or an oral care product comprising calcium hypophosphite, a water-soluble phosphate salt and hydroxyapatite is particularly preferred.

[0086] The calcium phosphate compounds used according to the invention can be present in pure form as well as in the form of substituted compounds and as mixtures thereof. A pure form is present according to the invention when the ions contained in the respective calcium phosphate compound are each substituted by one or more other ions to less than 1%, preferably less than 0.5%, even more preferably less than 0.1%. For example, in pure hydroxyapatite, the Ca 2+ -ions by, for example, Mg 2+ or Zn 2+ substituted to less than 1%, preferably less than 0.5%, even more preferably less than 0.1%.

[0087] Furthermore, the calcium phosphate compounds preferably do not contain any doping agents, such as zinc carbonate doping. However, doped calcium phosphate compounds can also be used.

[0088] The X50 value of the volume-based particle size distribution of the calcium phosphate compounds is 1.0 nm to 100.0 pm, preferably 10 nm to 10.0 pm, more preferably 50 nm to 1 pm, particularly preferably 100 nm to 500 nm, wherein the X50 value of the volume-based particle size distribution is measured by laser diffraction. The maximum aspect ratio of the particles of the calcium phosphate compounds, determined by transmission electron microscopy (TEM) images, is preferably in the range 1-20, more preferably 2-15, and even more preferably 4-10.

[0089] For this purpose, a sample of calcium phosphate compounds is first subjected to ultrasonic irradiation in an ultrasonic homogenizer with an energy output of 96 W for 9 minutes, followed by a further 3 minutes in a sample preparation device. The subsequent particle size distribution measurement (laser diffraction) is performed in a particle size determination instrument at a temperature of 25 °C ± 0.3 °C, and the corresponding values ​​are calculated according to Mie theory. All measuring instruments used are commercially available.

[0090] In a preferred embodiment of the invention, the calcium phosphate compound is Cas(PO4)3(OH) and has a hexagonal crystal lattice in which the length of the a-axis is 0.930 to 0.950 nm, preferably 0.933 to 0.948 nm, particularly preferably 0.936 to 0.945 nm, and the length of the c-axis is 0.680 to 0.700 nm, preferably 0.682 to 0.696 nm, particularly preferably 0.685 to 0.692 nm. The lengths of the a-axis and the c-axis are determined by a Rietveld analysis of the corresponding X-ray powder diffractograms.

[0091] X-ray powder diffractograms themselves are obtained by measuring with a conventional powder diffractometer at routine settings.

[0092] In a preferred embodiment of the invention, the at least one calcium phosphate compound is present in aggregated form. Aggregation in this case refers to the aggregation of molecules or particles into a larger structure, the aggregate. This aggregation or aggregate is caused and held together by various forces and / or bonding types, such as ionic bonding, van der Waals forces, intermolecular forces, or other chemical bonding types. The degree of aggregation and the size of the aggregate can be determined using scanning electron microscopy.

[0093] A composition according to the invention comprises calcium phosphate compounds in an amount of 0.01 to 80 wt.%, preferably 0.1 to 20 wt.%, particularly preferably 1 to 10 wt.%, and especially 1 to 5 wt.%, based on the total weight of the oral care product. For mouthwashes, the preferred amount of calcium phosphate compounds is 1 to 5 wt.%, and for toothpastes, 10 to 20 wt.%, each based on the total weight.

[0094] A composition according to the invention or an oral care product according to the invention can contain, in addition to calcium hypophosphite and / or at least one water-soluble phosphate salt and preferably additionally hydroxyapatite, at least one further calcium compound which is preferably selected from the group consisting of calcium carbonate, calcium chloride, calcium bromide, calcium nitrate, calcium acetate, calcium gluconate, calcium lactate, calcium tartrate and their hydrates and mixtures thereof, preferably calcium carbonate.

[0095] The carrier system according to the invention preferably has a viscosity between 0 and 150,000 mP sec (mPas).

[0096] In embodiments of the invention relating to pastes and in particular toothpastes, the viscosity is preferably in the range 0 - 150,000 mPas, more preferably between 5,000 - 120,000 mPas and particularly preferably in the range 10,000 - 90,000 mPas (in each case determined 0-4 days after production).

[0097] In embodiments of the invention relating to solutions and in particular mouthwashes, the viscosity is preferably in the range 0-1,000 mPas, more preferably between 0-500 mPas, and particularly preferably in the range 10-150 mPas (determined 0-4 days after production). All viscosity data are based on measurements according to DIN 53019-1:2008-09 using a Haake RheoStressl rheometer (ThermoFisher Scientific) at 20 °C and a shear rate of 10 / s (toothpaste) and 50 / s (mouthwash) in plate-on-plate geometry.

[0098] The carrier system according to the invention has a pH between 3.0 and 9.0. The pH is preferably in the range of 4.0 to 8.0, in particular between 5.0 and 7.0. If calcium hypophosphite (A) and at least one water-soluble phosphate salt (B) are present together in a composition, the pH of the composition, and preferably of a carrier system in the composition, is preferably in a range of 3.5 to 5.5, as described above.

[0099] The pH value can be adjusted using pH regulators. pH regulators are substances that can adjust a specific pH range, preferably a range from 3.5 to 8.0.

[0100] Examples of pH regulators include acetic acid, acetates, lactic acid, lactates, malic acid, malates, fumaric acid, citric acid, citrates, tartaric acid, tartrates, orthophosphates, di-, tri-, and polyphosphates, hydrochloric acid, chlorides, sulfuric acid, sulfates, hydroxides, oxides, adipic acid, adipates, gluconic acid, gluconates, phosphoric acid, calcium carbonate, or a hydrate thereof. A preferred example of a pH regulator that can be added when a lower pH is desired is phosphoric acid (H3PO4).

[0101] Within the scope of the invention, it has surprisingly been shown that calcium hypophosphite and the at least one water-soluble phosphate salt act synergistically and effectively remineralize tooth enamel and dentin and protect against caries. In particular, neomineralization of the teeth occurs, i.e., calcium phosphate formation on the teeth. In this way, age-related tooth enamel wear, erosion damage, or other tooth defects are effectively regenerated. Dentin tubules are also effectively sealed, and sensitive teeth are effectively prevented. Furthermore, chalky teeth or teeth affected by fluorosis are also effectively remineralized. The combination of calcium hypophosphite and a water-soluble phosphate salt surprisingly shows a significantly higher remineralizing effect compared to other water-soluble calcium compounds in combination with the same phosphate salts.Furthermore, it was surprisingly found that the composition according to the invention already achieves its full effect during brushing the teeth (2-3 minutes) or rinsing the mouth (30-60 seconds), so that there is no need to wait until the full effect occurs.

[0102] In combination with hydroxyapatite, a surprising synergistic effect was observed. The addition of calcium hypophosphite and at least one water-soluble phosphate salt unexpectedly significantly increases the remineralization performance of the active ingredient hydroxyapatite.

[0103] A composition comprising calcium hypophosphite, at least one water-soluble phosphate salt and hydroxyapatite is particularly preferred.

[0104] A composition comprising calcium hypophosphite, at least one water-soluble phosphate salt, hydroxyapatite and moisturizing or caring substances as described herein represents a preferred embodiment of the invention.

[0105] A composition comprising calcium hypophosphite, at least one water-soluble phosphate salt, hydroxyapatite and cleaning agents as described herein represents a preferred embodiment of the invention.

[0106] During the tooth cleaning process, abrasives, usually together with the toothbrush, remove plaque and harmful bacteria from the tooth surface and can provide a whitening effect. Abrasives or abrasives are contained in toothpastes in quantities of up to 15% by weight, or more, based on the total weight of the toothpaste. Examples of abrasives are whiting, marble powder, and / or silicate compounds such as silica. Polysilicic acids (hydrated silica) and calcium carbonate are the most commonly used abrasives worldwide. The disadvantage is that – with the exception of calcium phosphate compounds (e.g., hydroxyapatite) – all types of abrasives are foreign to the body and do not correspond to the natural tooth mineral (hydroxyapatite). For example, abrasives with a high relative hardness can cause irreparable damage to the tooth structure.If the abrasive body is too hard, the cleaning performance of the overall toothpaste formulation may be too low to effectively remove plaque during brushing (increased risk of caries and periodontitis).

[0107] A composition comprising calcium hypophosphite, at least one water-soluble phosphate salt and hydroxyapatite and gum care substances as described herein represents a preferred embodiment of the invention.

[0108] The aforementioned active ingredients and groups of active ingredients can be combined freely and independently of one another with calcium hypophosphite and / or at least one water-soluble phosphate salt and in particular calcium hypophosphite, at least one water-soluble phosphate salt and hydroxyapatite.

[0109] Anionic, non-ionic, cationic, and zwitterionic surfactants can be used as surfactants. Non-ionic surfactants are often avoided due to their adverse effects on the antibacterial compound. Likewise, cationic and zwitterionic surfactants are often avoided because they can stain or darken teeth. Accordingly, anionic surfactants are preferred as the cleansing component in the composition or oral care product. Sodium lauryl sulfate and other higher alkyl sulfates containing 10 to 18 carbon atoms in the alkyl group are preferred, although other known sulfated and sulfonated surfactants can also be used partially or entirely as such.

[0110] Preferably, a composition according to the invention or an oral care product according to the invention contains at least one surfactant selected from the group consisting of taurates, glycinates, sarcosinates and quaternary ammonium compounds, preferably sodium methyl cocoyl taurate, sodium cocoyl glycinate, sodium lauroyl sarcosinate, benzalkonium chloride, cetylpyridinium chloride or any mixtures thereof.

[0111] A composition according to the invention may comprise antibacterial substances, for example hydrogen peroxide. Preferably, the composition according to the invention or the oral care product contains less than 0.1% hydrogen peroxide. More preferably, the composition or oral care product is substantially free of hydrogen peroxide.

[0112] One aspect of the invention relates, as described, to an oral care agent or oral care product comprising the composition described herein. The oral care agent or product is preferably a toothpaste, an oral gel, or a mouthwash.

[0113] A toothpaste, also known as tooth cream, can be used in combination with a toothbrush for the mechanical cleaning of teeth and gums and is a soft or semi-solid composition for oral application. An oral gel is used in the same way but has a gel-like composition. A mouthwash, also known as a mouth rinse, is a liquid formulation that can be used, among other things, for the prevention of caries and other diseases in the oral cavity. A composition or oral care product according to the invention can accordingly be intended to remain on the teeth and / or for rinsing. A composition according to the invention can also be in the form of a tooth varnish or polishing paste.

[0114] However, since sodium lauryl sulfate can also be irritating to the mucous membranes at concentrations above 1.0% by weight, the oral care product according to the invention can also be free of sodium lauryl sulfate and instead be surfactant-free or contain other surfactants that are less irritating to the mucous membranes than sodium lauryl sulfate, such as taurates, preferably sodium methyl cocoyl taurate, glycinates, preferably sodium cocoyl glycinate, sarcosinates, preferably sodium lauroyl sarcosinate or quaternary ammonium compounds, preferably benzalkonium chloride or cetylpyridinium chloride. The information about the respective surfactants also includes all variants thereof (different alkyl chains, branches in the alkyl chains, counterions, etc.). Surfactants are important for a toothpaste because they help distribute the active ingredients in the oral cavity while brushing. Surfactants are also important for consumer convenience.

[0115] Furthermore, it was unexpectedly found that the inventive use of the combination of (A) and (B) and / or of oral care products according to the invention can advantageously mineralize smaller caries lesions and / or repair microfine defects in the tooth enamel, particularly in patients with dry mouth / lack of saliva, e.g., xerostomia. Furthermore, oral care products according to the invention can apply a protective layer to the tooth, and it was further found that the tooth enamel exhibits advantageous solubility and resistance to acid after application of the oral care products according to the invention. Furthermore, the present composition does not require antimicrobial substances (such as chlorhexidine) as excipients.In this way, excellent caries prophylaxis can be ensured without, for example, disturbing / destroying the bacterial balance in the oral cavity and without risking unpleasant side effects. Furthermore, it was unexpectedly found that use of the inventive combination of (A) and (B), preferably in the form of an oral care product according to the invention, prevents caries and can also remineralize lesions down to deeper layers of the tooth, particularly the enamel. Furthermore, by using oral care products according to the invention, a protective layer can be applied to the tooth and over exposed dentin, and in particular, open dentin tubules can be closed. Furthermore, it was found that the tooth enamel exhibits significantly reduced or no longer detectable structural damage after use. Furthermore, fluoride application can be completely dispensed with with the present oral care products.In this way, the above-mentioned positive aspects can be ensured without, for example, disturbing / destroying the bacterial balance in the oral cavity and without risking undesirable side effects that can occur, for example, when using fluoride-containing oral care products (see above). The subject of the present invention is an active ingredient combination and / or oral care products for the mineralization and remineralization of teeth, in particular of tooth enamel and dentin, but also of non-mineralized tooth components in the case of so-called mineralization defects. This includes, for example, "molar incisor hypomineralization" (MIH, also called "chalky teeth"). Alternatively, chalky teeth are also referred to in the professional world as "molar hypomineralization" (MH). Accordingly, the terms can be used interchangeably herein.

[0116] The oral care product according to the invention is intended for daily use with 1-4 applications per day. 2-3 applications per day are particularly preferred.

[0117] If at least one component of the oral care product is in the form of an oral gel, it does not need to be spit out, but can be absorbed over a longer period of time of more than 3 minutes, preferably between 5 minutes and 12 hours, particularly preferably between 10 minutes and 1 hour. Due to the gel-like composition, the adhesion of the calcium hypophosphite and / or water-soluble phosphate salt directly to the tooth (enamel, dentin, cementum) is supported, so that the calcium hypophosphite and / or the active ingredient combination is in direct contact therewith over a longer period of time, thereby achieving a high remineralization rate. The oral gel according to the invention is preferably used 1-3 times daily, particularly preferably once daily. Use in the evening is then again preferred. In other embodiments, application can also be made once per week.

[0118] It is also possible for compositions and / or oral care products according to the invention to be substantially free, preferably free, of fluorides and / or tin salts and / or chlorhexidine and / or triclosan. "Free" within the meaning of the present invention means that the composition according to the invention may contain unavoidable impurities of the substance designated "free from." "Substantially free" within the meaning of the present application means "< (less than) 10 ppm."

[0119] It has been found that the active ingredient combination according to the invention and / or oral care products according to the invention can be used in the treatment and / or prevention of numerous dental diseases.

[0120] In a preferred embodiment of the invention, the active ingredient combination according to the invention and / or oral care products according to the invention can be used for the treatment of (dental) diseases / conditions selected from caries, tooth erosion, tooth abrasion, attrition, bruxism, molar-incisor hypomineralization (MIH; chalky teeth), amelogenesis imperfecta, dentinogenesis imperfecta, and fluorosis. Particularly preferred is the use for the prophylaxis of caries and for the treatment of MIH-affected teeth.

[0121] The term "caries" is familiar to experts. It is generally understood as a destructive disease of the hard dental tissue, enamel, and dentin.

[0122] Tooth erosion refers to damage to the hard tooth substance caused by acids, in other words defects in the tooth enamel and / or dentin caused by dental erosion, which, if treated too late, can lead to irreversible damage.

[0123] (Tooth) abrasion refers to the loss of tooth substance due to friction. Attrition is a subtype of abrasion, namely the loss of tooth substance due to reflexive contact of the teeth.

[0124] Bruxism is the unconscious grinding or clenching of teeth, usually at night but also during the day. This can result in wear not only of the teeth but also of the periodontal ligament and masticatory muscles. Molar-incisor hypomineralization (MIH), also known as "chalky teeth," is an enamel disorder, i.e., structural damage to the tooth enamel.

[0125] Amelogenesis imperfecta is considered a genetic disorder that disrupts tooth enamel formation. As a result, teeth are at increased risk of caries and are particularly sensitive to temperature.

[0126] Dentinogenesis imperfecta is an autosomal dominant inherited maldevelopment / structural disorder of the dental dentition that occurs in approximately 1 in 8,000 people and results in severe tooth abrasion.

[0127] Dental fluorosis (also known as dental fluorosis) is a non-inflammatory disease ("speckled teeth") caused by excessive fluoride intake, particularly during the ontogenetic development of the teeth. It has been found that the use according to the invention can prevent the above-mentioned dental diseases and / or at least significantly slow their progression and / or achieve complete restoration of the tooth substance, particularly the hard tooth substance. In particular, it has been found that the use according to the invention, or after its application, significantly reduces or no longer detects structural damage to the tooth enamel.

[0128] In a preferred embodiment, the active ingredient combination according to the invention and / or the oral care products according to the invention can be used for both cosmetic and medicinal purposes. This means that it can be used, for example, not only for the treatment of the above-mentioned (dental) diseases, but also for cosmetic purposes such as improving the appearance of the teeth. Furthermore, the active ingredient combination according to the invention and / or the oral care products according to the invention can be used to care for the mouth and throat, in particular the teeth. Caring for the teeth maintains the healthy condition of the teeth and can also positively influence their appearance, e.g., by whitening them.

[0129] In a preferred embodiment, the active ingredient combination according to the invention and / or oral care products according to the invention are used in persons of all age groups, including children, in the case of children preferably in children aged 6 months to 14 years, in particular in children aged 10 months to 12 years.

[0130] In a preferred embodiment, the Cas(PO4)3(OH) contained in a composition according to the invention and / or in an oral care product according to the invention is the only apatite component of the composition or the oral care product.

[0131] In a preferred embodiment, a composition or oral care product according to the invention comprises 0.01 to 80 wt.%, preferably 0.2 to 40 wt.%, more preferably 0.5 to 30 wt.%, in particular 1.0 to 20 wt.% of calcium phosphate compounds. In a preferred embodiment of the invention, an oral care product according to the invention can comprise 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 20 wt.%, or 25 wt.% of calcium phosphate compounds.

[0132] Preferably, a composition according to the invention comprises one or more pharmaceutical or cosmetic ingredients such as xylitol, antimicrobial substances, pH regulators, abrasives, flavorings and humectants, in particular xylitol, pH regulators, abrasives and flavorings.

[0133] Xylitol can minimize the number of caries bacteria and inhibit their growth. Furthermore, xylitol can stimulate saliva flow. The increased amount of saliva results in an increased amount of phosphate. This phosphate can react with the calcium (ions) of the calcium hypophosphite-containing composition according to the invention to form hydroxyapatite. An oral care product according to the invention can contain xylitol in an amount of 0.01 to 15 wt.%, preferably 1.0 to 10.0 wt.%, in particular about 7.0 wt.%, based on the total weight of the oral care product. In addition to xylitol, the oral care product according to the invention can contain other sugar alcohols such as sorbitol.

[0134] Antimicrobial substances are substances that can kill microorganisms, such as bacteria, or significantly reduce their proliferation. In addition to antimicrobial substances with a non-specific defense against bacteria and fungi, there are also antimicrobial substances that, for example, only act against specific bacteria. The use of antimicrobial substances can also be used to combat bad breath, for example. Antimicrobial substances can preferably be contained in an oral care product according to the invention in an amount of 0.01 to 2.0 wt.%, more preferably 0.05 to 1.0 wt.%.

[0135] In a further preferred embodiment, an oral care product according to the invention contains a pH regulator in an amount of 0.05 to 3.0% by weight, more preferably 0.1 to 2.5% by weight, particularly preferably 0.2 to 1.5% by weight, in each case based on the total weight of the oral care product.

[0136] In a preferred embodiment, an oral care product according to the invention contains one or more flavoring agents that can impart the desired taste. This one or more flavoring agents can be natural, nature-identical, synthetic flavoring agents, and / or mixtures thereof.

[0137] Flavorings can be contained in an oral care product according to the invention preferably in an amount of 0 to 5% by weight, preferably 0.1 to 3% by weight, based on the total weight of the oral care product according to the invention.

[0138] Humectants are additives that prevent an oral care product according to the invention from drying out by binding water added during production (i.e., preventing evaporation) or by absorbing atmospheric moisture during storage. Examples of humectants are glycerin, propane-1,2-diol, hexane-1,2-diol, egg yolk, aloe vera gel, honey, molasses, especially glycerin and hexane-1,2-diol. Humectants can be present in the oral care product according to the invention preferably in an amount of 0 to 25 wt.%, more preferably 0.1 to 20 wt.%, based on the total weight of the oral care product according to the invention.

[0139] In a preferred embodiment, an oral care product according to the invention contains

[0140] - 0.0001 to 20.0 wt.%, preferably from 0.001 to 10.0 wt.% and particularly preferably from 0.01 to 5.0, in particular 1.0 to 2.5 wt.% calcium hypophosphite,

[0141] - 0.0001 to 40.0 wt.%, preferably 0.001 to 20 wt.%, more preferably 0.01 to 10 wt.%, even more preferably 0.1 to 8 wt.%, particularly preferably 0.8 to 2.5 wt.% water-soluble phosphate salt, in particular disodium hydrogen phosphate and / or dipotassium hydrogen phosphate, - 0.3 to 3 wt.% surfactants, preferably about 1.0 wt.% sodium cocoyl glycinate or sodium methyl cocoyl taurate,

[0142] - 0.5 to 15% by weight, preferably 1 to 10% by weight, in particular about 7.0% by weight of xylitol,

[0143] - 0 to 2.0 wt.%, preferably 0.01 to 2.0 wt.%, more preferably 0.05 to 1.0 wt.% antimicrobial substance, in particular cetylpyridinium chloride and / or zinc chloride,

[0144] - 0 to 5 wt.%, preferably 0.3 to 2.0 wt.%, pH regulator, in particular phosphoric acid,

[0145] - 0 to 5% by weight, preferably 0.1 to 3% by weight, flavoring,

[0146] - From 0 to 25% by weight, preferably 0.1 to 20% by weight, of humectant, in particular glycerin and / or hexane-1,2-diol, where the percentages in weight refer to the total weight of the oral care product. The remainder is optionally distilled water.

[0147] If an oral care product according to the invention is designed as an oral gel, it contains gel formers, wherein the gel former consists of synthetic and / or natural polymer materials.

[0148] It is advantageous that the gelling agent is selected from the group containing cellulose and cellulose derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, agarose, agar, pectins, sclerotium gum, xanthan gum, guar gum, carrageenan, alginic acid, polyvinyl alcohol, polyvinylpyrrolidone and mixtures thereof.

[0149] Such an oral gel preferably contains gelling agents in an amount of 1.0 to 4.0 percent by weight, particularly preferably 1.5 to 3.0 percent by weight, and especially about 2.0 percent by weight, based in each case on the total weight of the oral gel. Description of the figures:

[0150] FIG. 1: The laser image of a bovine incisor, acquired using a confocal laser scanning microscope, shows exposed dentin tubules. The overview image of the embedded tooth specimen (right, top) shows the position of the laser image acquisition (yellow rectangle).

[0151] FIG. 2: (la): The laser image of a bovine incisor, acquired using a confocal laser scanning microscope, shows open dentin tubules as black circles. Figure (lb) shows the corresponding color image. After sequential treatment with toothpaste formulation 1A and oral gel formulation 1A (Ha), (Hb)), significant closure of the dentin tubules is evident. The overview image of the embedded tooth specimen shows the position of the laser image (yellow rectangle).

[0152] FIG. 3: la): The image section of the laser image from Figure 2 la) shows exposed

[0153] Dentin tubules with a diameter of < 1 pm (blue arrows). Image section Ha) of the laser image from Figure 2 Ha) shows the closure of small dentin tubules (< 1 pm) after sequential treatment with toothpaste formulation 1A and oral gel formulation 1A.

[0154] FIG. 4: Example of particle analysis of an untreated

[0155] Tooth surface (left) and a treated tooth surface (right) based on Figure 2 (la) and (ha). Analysis parameters: Image type: 8-bit; Circular area: 4.0 to 25.0 pm 2 ; Circularity: 0.20 to 1.00.

[0156] FIG. 5: The laser image of a bovine incisor, recorded using a confocal laser scanning microscope, shows microfine defects on the enamel surface before brushing. After the toothbrushing simulation (Ha), the formation of a white mineral is visible in the microdefects of the enamel. The overview image of the tooth sample (laser image, top right) shows the position of the laser image (yellow rectangle). FIG. 6: I) The X-ray diffractogram of the purified solid from Example 3 shows characteristic signals of the crystal planes of hydroxyapatite with Miller indices of the planes (100), (200), (002), (300), and (004). II) The scanning electron micrograph shows crystals with a cylindrical structure characteristic of hydroxyapatite.

[0157] Examples

[0158] The invention is explained below using examples.

[0159] Example 1 : Closure of dentin tubules by sequential application of calcium hypophosphite with a water-soluble phosphate salt

[0160] The following example tests the efficacy of sequential application of a toothpaste formulation containing calcium hypophosphite and an oral gel containing disodium hydrogen phosphate, followed by a smear-on application (Table 1.1). Sealing dentin tubules is an effective method for relieving tooth sensitivity.

[0161] Table 1.1: Composition of toothpaste formulation 1A and oral gel formulation 1A from Example 1 (values ​​in wt.%). For the targeted closure of exposed dentin tubules, the labial side of a bovine incisor is sectioned and embedded in epoxy resin. The tooth is ground down to the dentin in several steps (grit: 600 to 4000, 150 rpm) and polished. The embedded specimen is cleaned for 3 minutes in an ultrasonic bath (DK Sonic 3L, 40 kHz) and dried in a stream of air.

[0162] The sample is pre-characterized under a confocal laser scanning microscope (VK-X 1100, Keyence) (Fig. 1). The pre-characterization in Figure 1 shows exposed dentin tubules as black, circular elements. Some tubules exhibit a bright inner surface. These tubules are flush with the base and are therefore considered "non-exposed."

[0163] The cleaned dentin sample is brushed for 6 seconds with an electric toothbrush (Oral-B Vitality Pro, Braun) using toothpaste formulation 1A (contains calcium hypophosphite, see Table 1.1). Immediately after brushing, a drop of Oral Gel formulation 1A is applied to the tooth and massaged in with the finger for 10 seconds (contains disodium hydrogen phosphate, see Table 1.1). In a washing process, the tooth is immersed in demineralized water with stirring (20 mL, 20 seconds, 150 rpm). This application cycle is repeated five times. The tooth is air-dried and examined again using laser scanning microscopy (Fig. 2).

[0164] The sequential application shows a coverage of exposed dentin tubules after application (Fig. 2, 11a), 11b). The color images show that white mineral has deposited on the tooth surface after the sequential application (cf. Fig. 2, 11b) and 11b).

[0165] Surprisingly, even exposed dentin tubules with a diameter of less than 1.0 pm can be successfully sealed (Fig. 3, blue arrows). This offers an advantage over particulate approaches, where the intrinsic size of the particles limits the sealing of small dentin tubules.

[0166] To quantify tubule occlusion, a particle analysis is performed (Fig. 4). An evaluation of different laser images of the untreated and treated tooth surfaces using the image processing program ImageJ reveals an overall reduction in exposed dentin tubules of (84.4 ± 12.2)% after repetitive application. This example demonstrates that a significant reduction in exposed dentin tubules is possible through sequential application of the described invention, eliminating the need for predefined particles with a limiting size distribution.

[0167] Example 2: Effects on tooth surfaces with microfine defects using a combination system of calcium hypophosphite and a water-soluble phosphate salt

[0168] This example describes the effect of the described invention when applied to tooth surfaces with microdefects. A combination system of calcium hypophosphite and disodium hydrogen phosphate is used in a toothbrushing simulation.

[0169] The procedure involves brushing teeth with a special toothpaste formulation containing calcium hypophosphite and disodium hydrogen phosphate (Table 2.1 , Toothpaste Formulation A).

[0170] Table 2.1: Composition of the toothpaste formulation from Example 2 (values ​​in wt.%).

[0171] To investigate the effect of the model toothpaste on tooth surfaces with microfine defects, bovine incisors are pre-characterized using laser scanning microscopy (Fig. 5).

[0172] The pre-characterized tooth is installed in a toothbrushing simulator (ZM-3, SD Mechatronik) and rinsed with artificial saliva (10 mL, composition: see Table 2.2) and stored in it for one hour.

[0173] Table 2.2: Composition of the artificial saliva used (in % by weight).

[0174] After one hour in the artificial saliva solution, the toothpaste formulation (0.3 g) is applied to a toothbrush and the inserted tooth is brushed (6 cycles, 12 cycles, ZM-3, SD Mechatronik). The brushed tooth is rinsed with demineralized water, and the process is repeated ten times. The sample is dried and examined under a laser scanning microscope (Fig. 5).

[0175] Surprisingly, the use of the described toothpaste formulation in artificial saliva leads to mineral deposition in microfine defects of the tooth enamel.

[0176] The example shows that the use of dissolved calcium hypophosphite and disodium hydrogen phosphate in a model toothpaste can be used under artificial saliva to remineralize microfine defects on enamel surfaces.

[0177] Example 3: Production of hydroxyapatite by combining a composition comprising calcium hypophosphite with a composition comprising a water-soluble phosphate salt

[0178] The present example shows the formation of hydroxyapatite during the reaction of a calcium hypophosphite solution with a composition according to the invention comprising a water-soluble phosphate salt, more precisely disodium hydrogen phosphate (Na2HPO4).

[0179] In the in vitro experiment, a solution of calcium hypophosphite (1.0 wt%, 59.4 mM, cap = 40.0 mL, pH = 5.6) is added dropwise to a Na2HPO4 solution (59.4 mM, 1 / 4 Na2HPO4 = 100.0 mL, pH = 9.2) while stirring (400 rpm). Upon penetration of the droplets into the Na2HPO4 solution, an immediate turbidity is observed. This process is comparable to the interaction of the two dissolved components in the oral cavity, for example, during sequential application of toothpaste and mouthwash. The resulting suspension is purified by centrifugation (2500 rpm, 10 min) and threefold redispersion in water, and dried. The dried solid is examined by X-ray diffraction (PXRD) and scanning electron microscopy (SEM) (Fig. 6 I), II).

[0180] Surprisingly, PXRD of the purified solid shows characteristic signals of hydroxyapatite, for example, at 20 = 10.82 (100), 21.82 (200), 25.88 (002), 32.90 (300), and 53.15 (004), as well as characteristic cylindrical crystal structures in SEM images (Fig. 6 I), II). The SEM image confirms the formation of rod-shaped crystals, which are characteristic of hydroxyapatite. The formation of sheet-like structures, which are characteristic of CaHPLC crystals, is not observed.

[0181] This example shows that, surprisingly, hydroxyapatite is formed upon contact of calcium ions from calcium hypophosphite with phosphate ions from Na2HPO4 under the conditions of the invention. As shown in Examples 1 and 2, hydroxyapatite produced under in situ conditions can serve as a remineralization agent on tooth surfaces and seal the smallest dentin tubules.

Claims

Patent claims 1. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use in a method for the treatment and / or prevention of diseases in the oral cavity and / or teeth and / or for the care of the oral cavity and throat, in particular the teeth, wherein the water-soluble phosphate salt has a solubility between > 10 g / L and < 2000 g / L in water at 20 °C.

2. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to claim 1, wherein (A) and (B) react with each other in the oral region and thereby preferably form calcium phosphates, particularly preferably hydroxyapatite.

3. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein (A) and (B) are at least partially dissolved, preferably predominantly dissolved, particularly preferably completely dissolved in at least one composition prior to use.

4. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein (A) and (B) are present together in a composition.

5. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to claim 4, wherein the composition has an initial pH of 3.5 to 5.

5.

6. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of claims 4 to 5, wherein (A) and (B) react after increasing the pH of the composition to >5.5, preferably 5.5 - 9.5 in the oral region and thereby preferably form calcium phosphates, particularly preferably hydroxyapatite.

7. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to claim 6, wherein the pH is increased to 6 - 8.5, preferably 6.5 - 7.

5.

8. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of claims 6 to 7, wherein the increase in pH occurs by contact of the composition with saliva in the oral region.

9. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of claims 6 to 7, wherein the pH is increased by contact with another composition immediately before application or in the oral region.

10. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of claims 4 to 9, wherein the molar ratio of calcium in (A) to phosphorus (B) in the composition is between 3:2 and 1:2 (calcium:phosphorus), preferably 3:2, 1:1 or 1:2 and particularly preferably 1:

1.

11. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of claims 4 to 10, wherein the composition is in the form of an oral care product, which is preferably a toothpaste, a mouthwash, an oral gel, a chewing gum, a tooth varnish or a polishing paste.

12. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of claims 1 to 3, wherein (A) and (B) are spatially separated in two different compositions which are applied simultaneously or sequentially in the oral region.

13. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to claim 12, wherein contact of (A) with (B) is established in the oral region and / or immediately before application in the oral region.

14. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to claim 13, wherein (A) and (B) react with each other upon contact in the oral region and thereby preferably form calcium phosphates, particularly preferably hydroxyapatite.

15. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of claims 12 to 14, wherein the compositions are applied simultaneously in the oral region and contact of (A) with (B) occurs immediately before or during application in the oral region.

16. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to claim 15, wherein the compositions are layered, encapsulated and / or present in different chambers of a package prior to use.

17. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of claims 15 to 16, wherein the compositions are spatially separated in a toothpaste, a gel, a foam, a spray or in a chewing gum.

18. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of claims 12 to 14, wherein the compositions are applied sequentially at intervals of 1 second to 30 minutes in the oral region, either first applying the composition containing (A) and then applying the composition containing (B), or first applying the composition containing (B) and then applying the composition containing (A).

19. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to claim 18, wherein component (A) or (B) of the first composition applied remains at least partially in the mouth area until application of the second composition and upon application of the second composition containing the respective other component (B) or (A), contact between (A) and (B) occurs in the mouth area.

20. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of claims 18 to 19, wherein the interval between the application of the first and second composition is 1 second to 10 minutes, preferably 30 seconds to 5 minutes.

21. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of claims 18 to 20, wherein the composition containing (A) and the composition containing (B) are independently in the form of a capsule, mouthwash, gel or toothpaste.

22. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein the calcium hypophosphite-containing composition contains 0.0001 to 20 wt.%, preferably 0.001 to 20 wt.%, more preferably 0.01 to 15 wt.%, particularly preferably 0.1 to 8 wt.% calcium hypophosphite.

23. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein the composition containing at least one water-soluble phosphate salt contains 0.0001 to 40.0 wt.%, in particular 0.001 to 20 wt.%, preferably 0.01 to 10 wt.%, particularly preferably 0.1 to 8 wt.% water-soluble phosphate salt.

24. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein the water-soluble phosphate salt is selected from the group of sodium phosphates, potassium phosphates or magnesium phosphates.

25. Calcium hypophosphite (A) in combination with at least one water-soluble Phosphate salt (B) for use according to any one of the preceding claims, wherein the water-soluble phosphate salt is selected from sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, Potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium phosphate, including hydrates, or any mixtures thereof.

26. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein at least one of the compositions contains at least one calcium phosphate compound, preferably hydroxyapatite.

27. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein rinsing of the oral cavity is provided after use.

28. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein the at least one composition is intended to remain on the teeth after use.

29. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein at least one of the compositions contains a gelling agent, in particular celluloses and / or xanthans or corresponding derivatives.

30. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein at least one of the compositions contains one or more organic acids.

31. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein at least one of the compositions contains xylitol.

32. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein at least one of the compositions contains at least one surfactant selected from the group consisting of taurates, sarcosinates, glycinates and alkyl sulfates or mixtures thereof.

33. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein at least one of the compositions contains menthol and / or menthol derivatives.

34. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein at least one of the compositions contains silica abrasive particles, calcium carbonates and / or calcium phosphates.

35. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein at least one of the compositions contains antibacterial substances.

36. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein at least one of the compositions contains gingival care additives.

37. Calcium hypophosphite (A) in combination with at least one water-soluble phosphate salt (B) for use according to any one of the preceding claims, wherein at least one of the compositions is substantially free of fluorides.

38. Composition for topical application comprising (a) 0.0001 to 20 wt% calcium hypophosphite, and (b) at least one water-soluble phosphate salt with a solubility between > 10 g / L and < 2000 g / L in water at 20 °C.

39. A composition according to claim 38, which has a pH in the range of 3.5 to 5.

5.

40. Composition according to any one of claims 38 to 39, which is activatable by increasing the pH to >5.5, preferably 5.5 - 9.5, more preferably 6 - 8.5, particularly preferably 6.5 - 7.

5.

41. A composition according to any one of claims 38 to 40, wherein the molar ratio of calcium in calcium hypophosphite to phosphorus in the water-soluble phosphate salt in the composition is between 3:2 and 1:2 (calcium:phosphorus), preferably 3:2, 1:1 or 1:2 and particularly preferably 1:

1.

42. Composition according to any one of claims 38 to 41, which is designed for application in the oral cavity.

43. Composition according to any one of claims 38 to 42 for use in dental and oral care.

44. An oral care product comprising a composition according to any one of claims 38 to 43, wherein the oral care product is preferably a toothpaste, a mouthwash, an oral gel, a chewing gum, a dental varnish or a polishing paste.

45. Oral care product for topical application comprising (a) a composition comprising calcium hypophosphite, and (b) a composition comprising at least one water-soluble phosphate salt having a solubility between > 10 g / L and < 2000 g / L in water at 20 °C, wherein the compositions (a) and (b) are spatially separated in the oral care product and are designed for simultaneous or sequential application.

46. ​​An oral care product according to claim 45, wherein the compositions (a) and (b) are layered, encapsulated, spatially separated in a carrier matrix and / or in different chambers of a package.

47. An oral care product according to claim 46, wherein compositions (a) and (b) are spatially separated in a toothpaste, a gel, a foam, a spray or in a chewing gum.

48. An oral care product according to claim 45, wherein composition (a) and composition (b) are each independently in the form of a capsule, mouthwash, gel or toothpaste.

49. A composition according to any one of claims 38-43 or an oral care product according to any one of claims 44-48, wherein the calcium hypophosphite-containing composition contains 0.0001 to 20 wt%, preferably 0.001 to 20 wt%, more preferably 0.01 to 15 wt%, particularly preferably 0.1 to 8 wt% calcium hypophosphite.

50. Composition according to any one of claims 38-43 and 49 or oral care product according to any one of claims 44-49, wherein the composition containing at least one water-soluble phosphate salt, Contains 0.0001 to 40.0 wt.%, in particular 0.001 to 20 wt.%, preferably 0.01 to 10 wt.%, particularly preferably 0.1 to 8 wt.% water-soluble phosphate salt.

51. A composition according to any one of claims 38-43 and 49-50 or an oral care product according to any one of claims 44-50, wherein the water-soluble phosphate salt is selected from the group consisting of sodium phosphates, potassium phosphates or magnesium phosphates.

52. A composition according to any one of claims 38-43 and 49-51 or an oral care product according to any one of claims 44-51, wherein the water-soluble phosphate salt is selected from sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium phosphate, including hydrates, or any mixtures thereof.

53. A composition according to any one of claims 38-43 and 49-52 or an oral care product according to any one of claims 44-52, wherein the composition or at least one of the compositions in the oral care product contains at least one calcium phosphate compound, preferably hydroxyapatite.

54. A composition according to any one of claims 38-43 and 49-53 or an oral care product according to any one of claims 44-53, wherein the composition or oral care product is intended to be rinsed after use.

55. A composition according to any one of claims 38-43 and 49-53 or an oral care product according to any one of claims 44-53, wherein the composition or oral care product is intended to remain on the teeth after application.

56. Composition according to any one of claims 38-43 and 49-55 or oral care product according to any one of claims 44-55, wherein the composition or at least one of the compositions in the oral care product contains a gelling agent, in particular celluloses and / or xanthans or corresponding derivatives.

57. Composition according to any one of claims 38-43 and 49-56 or Oral care product according to any one of claims 44-56, wherein the composition or at least one of the compositions in the oral care product contains one or more organic acids.

58. A composition according to any one of claims 38-43 and 49-57 or an oral care product according to any one of claims 44-57, wherein the composition or at least one of the compositions in the oral care product contains xylitol.

59. A composition according to any one of claims 38-43 and 49-58 or an oral care product according to any one of claims 44-58, wherein the composition or at least one of the compositions in the oral care product contains at least one surfactant selected from the group consisting of taurates, sarcosinates, glycinates and alkyl sulfates or mixtures thereof.

60. A composition according to any one of claims 38-43 and 49-59 or an oral care product according to any one of claims 44-59, wherein the composition or at least one of the compositions in the oral care product contains menthol and / or menthol derivatives.

61. A composition according to any one of claims 38-43 and 49-60 or an oral care product according to any one of claims 44-60, wherein the composition or at least one of the compositions in the oral care product contains silica abrasive particles, calcium carbonates and / or calcium phosphates.

62. A composition according to any one of claims 38-43 and 49-61 or an oral care product according to any one of claims 44-61, wherein the composition or at least one of the compositions in the oral care product contains antibacterial substances.

63. A composition according to any one of claims 38-43 and 49-62 or an oral care product according to any one of claims 44-62, wherein the composition or at least one of the compositions in the oral care product contains gingival care additives.

64. A composition according to any one of claims 38-43 and 49-63 or an oral care product according to any one of claims 44-63, wherein the composition or at least one of the compositions in the oral care product is substantially free of fluorides.

65. Use of a composition according to any one of claims 38-43 and 49-64 or of an oral care product according to any one of claims 44-64 for the prevention and / or treatment of diseases in the oral cavity and / or of the teeth and / or for cosmetic purposes and / or for the care of the oral cavity and throat, preferably the teeth.

66. Use according to claim 65 for remineralizing teeth.

67. Use according to any one of claims 65-66 in persons with reduced salivation, for example in xerostomia.

68. Use according to any one of claims 65-67 for the treatment of chalky teeth and / or fluorosis.

69. Use according to any one of claims 65-68 for the prevention and / or Treatment of caries.

70. Use according to any one of claims 65-69 for the prevention and / or Treatment of sensitive teeth.

71. Use according to any one of claims 65-70 for protecting teeth from erosion, in particular due to exposure to acid(s).

72. Use according to claim 65 for whitening teeth.

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