EP1660028A1

EP1660028A1 - Oral and dental hygiene product

Info

Publication number: EP1660028A1
Application number: EP04764416A
Authority: EP
Inventors: Adolf-Peter Barth; Christian Kropf; Tilo Poth
Original assignee: Henkel AG and Co KGaA; Sustech GmbH and Co KG
Current assignee: Henkel AG and Co KGaA; Sustech GmbH and Co KG
Priority date: 2003-09-01
Filing date: 2004-08-24
Publication date: 2006-05-31
Also published as: CN1845719A; JP2007504186A; CA2534963A1; WO2005027863A1; DE10340542A1; US20060222602A1; BRPI0414018A

Abstract

The invention relates to oral and dental hygiene products comprising a) a composite material containing poorly water-soluble calcium salts in the form of nanoparticulate primary particles which are between 5 and 150 nm long and have a cross-section of between 2 and 50 nm, and protein constituents selected from proteins, protein hydrolysates and protein hydrolysate derivatives, and b) between 0.1 and 9 wt. % of a cleaning agent, in relation to the total weight of the product. The inventive oral and dental hygiene product ensures an effective and long-lasting remineralisation of the surface of the tooth, and a protective cleaning action of the cleaning or polishing agent.

Description

"Oral and dental care products"

The invention relates to oral and dental care products containing special composite materials and cleaning agents which ensure gentle cleaning with simultaneous remineralization of the tooth surface.

Mouth and tooth cleaning agents are already known which contain a composite material made from poorly soluble, nanoparticulate calcium salts and protein components in combination with cleaning and polishing agents. For example, a toothpaste based on 10% by weight of abrasive silicas and 5% by weight of a composite material has been proposed in WO 01/01930 A1. The effect of the composite material is based on the biomineralization of bone and tooth material by sealing dental lesions on the tooth surface. Abrasive substances, on the other hand, are essential components of every toothpaste formulation and are responsible for cleaning the teeth and removing tooth contamination and deposits from abrasion.

From the disclosure of EP 786 245 A1, numerous oral and dental care formulations are known which relate to the combination of a nanoparticulate hydroxylapatite and a cleaning agent. Hydroxyapatite is responsible for the remineralization of lesions on the tooth surface and for the prevention of caries. Aluminum hydroxides and calcium phosphates are used as cleaning agents, which are used in high concentrations.

In practice, the use of toothpaste formulations according to WO 01/01930 A1 and EP 786 245 A1 has proven to be problematic because the effects of the abrasive and the remineralizing component run counter to one another. It was observed that the depot effect of the remineralizing component was limited by the cleaning and polishing action of the abrasive, particularly when a toothpaste had a short exposure time of around two to three minutes. Apparently the deposited Neralizing component largely removed by the abrasives during the cleaning process.

It is therefore important that the remineralizing component has very good remineralizing properties so that the remineralizing effect during the cleaning process is satisfactory. The comparison of different remineralizing components such as conventional hydroxyapatite, nanoscale hydroxyapatite or the composite material according to the invention in FIG. 1 shows clear differences with regard to their remineralizing properties.

Figure 1 shows the time course of the pH value, measured in a 0.1% dispersion of the respective material in artificial saliva at 37 ° C. For the present study, artificial saliva was used, which consists of an aqueous solution of 14mM Na ⁺ , 4.7mM P0 ₄ , 21mM K ⁺ , 30mM Cl ^" , 1.8mM Ca ²⁺ and is therefore supersaturated with calcium phosphate. The pH value was monitored using a pH electrode (Inlab 410, Mettler Toledo; measuring instrument: Consort, Multi Parameter Analyzer C833).

The change in pH over time results from the formation of hydroxyapatite from saliva (i.e. the remineralization effect), which satisfies the following equation:

10 CaCI ₂ + 6 Na ₂ HPO ₄ + 2 H ₂ 0 ► Caι ₀ (OH) ₂ (PO ₄ ) ₆ + 12 NaCI + 8 HCl

This reaction releases acid, the pH value drops, and the stronger the remineralizing effect of the tested material, the stronger.

The significantly steeper decrease in pH in the case of the composite material compared to conventional hydroxyl papatite or nanoscale hydroxylapatite shows the superior remineralizing properties of the composite material. It is therefore ideally suited as a remineralizing component in a toothpaste formulation in which the depot effect of the remineralizing component always stands in the way of the cleaning and polishing effect of an abrasive. In addition to remineralization, the mouth and tooth cleaning agents according to the invention should also ensure gentle cleaning.

However, both the amount and the type and composition of the cleaning agent have an influence on the remineralization, which is why the object of the present invention was to produce a mouth and tooth cleaning agent that allows gentle treatment of the teeth, so that a good depot effect of the remineralizing component satisfactory cleaning performance is achieved at the same time.

Surprisingly, by combining the composite material with a low content of cleaning agent mixture, an oral and dental care agent was produced which, with the depot effect of the composite material remaining constant, has a constant cleaning effect (in comparison to the examples of WO 01/01930). This ensures a particularly gentle but satisfactory cleaning of the tooth surface with simultaneous remineralization.

In addition, the compositions according to the invention are notable for a repair effect. Unevenness and damage to the tooth enamel, for example scratches on the tooth enamel due to mechanical action, are smoothed out by being “filled in” by hydroxyapatite. In addition to repairing damaged tooth enamel surfaces, this leads to an aesthetically pleasing surface. In addition, pain-sensitive teeth are prevented, so that the teeth according to the invention Compositions enable sensitive cleaning.

The invention therefore relates to an oral and dental care product based on a) a composite material comprising - calcium salts which are sparingly soluble in water in the form of nanoparticulate primary particles with a length of 5 to 150 nm and a cross section of 2 to 50 nm and - protein components from proteins, protein hydrolyzates and protein hydrolyzate derivatives, and b) 0.1 to 9% by weight of a cleaning agent, based on the total weight of the agent. Composite materials include composites which comprise the components mentioned under a) and which represent microscopically heterogeneous, macroscopically but homogeneous aggregates and in which the primary particles of the calcium salts are associated with the structure of the protein component. The proportion of the protein component (s) in the composite materials is between 0.1 and 60% by weight, but preferably between 5 and 50% by weight, in particular between 20 and 50% by weight, based on the total weight of the composite materials.

The crystallites, i.e. understood the individual crystallites of the calcium salts mentioned. Here the pond diameter is to be understood as the diameter of the division in the direction of its greatest length extension. The mean particle diameter is to be understood as a value averaged over the total amount of the composite. The determination of the particle diameter can be determined by methods familiar to the person skilled in the art, for example by means of Scherrer analysis from X-ray diffractometric examinations.

The average particle diameter of the nanoparticulate primary particles is preferably in the range from 5 to 150 nm, and particularly preferably they are in the form of rod-shaped particles with a thickness in the range from 2 to 50 nm, in particular between 3 to 8 nm, and a length in the range from 5 to 150 nm, in particular 10 to 40 nm. Thickness here means the smallest diameter of the rods, length the largest diameter.

According to a preferred embodiment of the invention, the nanoparticulate rod-shaped crystals have an average length-to-width ratio of 3 to <, in particular approximately 4. According to the invention, the mean length-to-width ratio is to be understood to mean that the majority of the crystals have a length-to-width ratio in the range specified. The length-to-width ratio is also determined using the X-ray diffraction method. The spatial structure of the composite materials according to the invention consisting of a protein component and the sparingly soluble nanoparticulate calcium salts is clear using the example of the TEM image of a composite material made of hydroxyapatite and gelatin type A shown in FIG. 1 (200,000 times magnification; 1 cm in the figure corresponds to 40 nm). The high molecular weight protein component, which has a three-dimensional structure essentially determined by its amino acid sequence, is supported by the rod-shaped nanoparticles made of hydroxyapatite, so the nanoparticles to a certain extent depict the spatial structure of the protein component. This is clearly shown in Figure 2, which shows a TEM image of the gelatin type A - framework of the same composite material after the hydroxylapatite has been extracted with a solution of ethylenediaminetetraacetate (56,000 × magnification; 1.1 cm in the figure corresponds to 200 nm). The manner in which the inorganic particles attach to the basic structure of the protein component is determined by the primary structure (amino acid sequence) and, depending on the nature of the protein component, by its secondary, tertiary and quaternary structure. It has surprisingly been found that the spatial distribution and the quantitative extent of the attachment of the inorganic nanoparticles to the protein component can be influenced by the type and amount of the amino acids present in the protein component and thus by the selection of the protein components. For example, by selecting protein components that are rich in amino acids, aspartic acid, glutamic acid or cysteine, a particularly high loading with the poorly soluble calcium salt can be achieved. Depending on the spatial distribution of these amino acids in the protein structure, a spatially structured loading of the protein component with the sparingly soluble calcium salt can also be achieved.

The composite materials according to the invention are thus structured composite materials in contrast to that in RZ Wang et al. Composite of hydroxyapatite and collagen described, in which evenly distributed hydroxyapatite nanoparticles are present. Another significant difference between the subject matter of the present invention and the prior art is the size and morphology of the inorganic component. The in the RZ Wang et al. Hydroxyapatite particles described have a size of 2-10 nm. Hydroxyapatite particles in this size range belong to the range of amorphous or partially X-ray amorphous substances.

Surprisingly, the present invention succeeded in producing composite materials with crystalline inorganic nanoparticles in which the nanoparticles have a crystalline morphology which is clearly visible under the microscope. Figure 1 shows the rod-shaped structure of the inorganic nanoparticles. It has also been found that the structured composite materials according to the invention, in contrast to the prior art, lead to a particularly effective biomineralization process. This is believed to be related to the microstructure of the composite material and in particular the size and morphology of the calcium salt crystals. It is assumed that the longitudinal axis of the calcium salt nanoparticles is a preferred direction for the further crystal growth during the biomineralization.

Salts which are sparingly soluble in water are understood to be those which are less than 1 g / l soluble at 20 ° C. Preferred suitable calcium salts are calcium hydroxyphosphate (Ca ₅ [OH (P0 ₄ ) 3]) or hydroxylapatite, calcium fluorophosphate (Ca ₅ [F (P0 ₄ ) ₃ ]) or fluoroapatite, fluorine-doped hydroxyapatite of the general composition Ca. ₅ (P0) (OH, F) and calcium fluoride (Ca F ₂ ) or fluorite (fluorspar); Hydroxyapatite and / or fluoroapatite are particularly preferred.

One or more salts in the mixture selected from the group of phosphates, fluorides and fluorophosphates, which can optionally additionally contain hydroxyl and / or carbonate groups, can be present in the mixture as the calcium salt in the composite materials according to the invention.

In the context of the present invention, proteins are basically all proteins regardless of their origin or their production. Examples of proteins of animal origin are keratin, elastin, collagen, fibroin, albumin, casein, whey protein, placental protein. According to the invention preferably from these are collagen, keratin, casein, whey protein, proteins of plant origin such as, for example, wheat and wheat germ protein, rice protein, soy protein, oat protein, pea protein, potato protein, almond protein and yeast protein can also be preferred according to the invention.

In the context of the present invention, protein hydrolyzates are to be understood as degradation products of proteins such as collagen, elastin, casein, keratin, almond, potato, wheat, rice and soy protein, which are produced by acid, alkaline and / or enzymatic hydrolysis of the proteins themselves or their degradation products such as gelatin can be obtained. All hydrolytically acting enzymes are suitable for the enzymatic degradation, such as, for. B. alkaline proteases. Further suitable enzymes and enzymatic hydrolysis processes are described, for example, in K. Drauz and H. Waldmann, Enzyme Catalysis in Organic Synthesis, VCH-Verlag, Weinheim 1975. During the breakdown, the proteins are split into smaller subunits, the breakdown being carried out via the stages of the polypeptides can go through the oligopeptides down to the individual amino acids. The less degraded protein hydrolyzates include, for example, the gelatin preferred in the context of the present invention, which can have molar masses in the range from 15,000 to 250,000 D. Gelatin is a polypeptide that is primarily obtained by hydrolysis of collagen under acidic (gelatin type A) or alkaline (gelatin type B) conditions. The gel strength of the gelatin is proportional to its molecular weight, i.e. that is, a more hydrolyzed gelatin gives a lower viscous solution. The gel strength of the gelatin is given in Bloom numbers. When the gelatin is cleaved enzymatically, the polymer size is greatly reduced, which leads to very low Bloom numbers.

Furthermore, in the context of the present invention, the protein hydrolysates which are customary in cosmetics and have an average molecular weight in the range from 600 to 4000, particularly preferably from 2000 to 3500, are preferred as protein hydrolysates Domsch in Soap Oils Fette Waxes 108, (1982) 177 and Cosm.Toil. 99, (1984) 63, by HW Steisslinger in Parf.Kosm. 72, (1991) 556 and F. Aurich et al. in Tens.Surf.Det. 29, (1992) 389. Protein hydrolyzates from collagen, keratin, casein and vegetable proteins are preferably used according to the invention, for example those based on wheat gluten or rice protein, the production of which is described in the two German patents DE 19502167 C1 and DE 19502168 C1 (Henkel).

In the context of the present invention, protein hydrolyzate derivatives are to be understood as meaning chemically and / or chemoenzymatically modified protein hydrolyzates, such as, for example, those under the INCI names Sodium Cocoyl Hydrolyzed Wheat Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein, Potassium Cocoyl Hydrolyzed Collagen, Potassium Undecylenoyl Hydrolyzed Collagen and Laurdimone Hydroxypropyl hydrolyzed collagen known compounds. According to the invention, derivatives of protein hydrolyzates of collagen, keratin and caseins and vegetable protein hydrolyzates are preferably used, such as. B. Sodium Cocoyl Hydrolyzed Wheat Protein or Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein.

Further examples of protein hydrolyzates and protein hydrolyzate derivatives that fall within the scope of the present invention are described in CTFA 1997 International Buyers' Guide, John A. Wenninger et al. (Ed.), The Cosmetic, Toiletetry, and Fragrance Association, Washington DC 1997, 686-688.

The protein component can be formed in each of the composite materials according to the invention by one or more substances selected from the group of proteins, protein hydrolyzates and protein hydrolyzate derivatives.

Preferred protein components are all structure-forming proteins, protein hydrolyzates and protein hydrolyzate derivatives, which are to be understood as meaning those protein components which, due to their chemical constitution, form certain three-dimensional spatial structures which are familiar to the person skilled in the art from protein chemistry under the terms secondary, tertiary or also quaternary structure are. For the production of the composite material, reference is expressly made to the disclosure of WO 01/01930 A1. The content of the composite material in the oral and dental care products according to the invention is 0.01 to 10% by weight, preferably 0.01 to 2% by weight, based on the total weight of the composition.

The oral and dental care products according to the invention further contain 0.1 to 9% by weight, in particular 2 to 8% by weight, of at least one cleaning agent.

Cleaning agents are an essential part of a toothpaste and, depending on their intended function, are available alone or in combination with other cleaning agents or polishing agents. They serve to mechanically remove the unscaled dental plaque and should ideally lead to a glossy finish on the tooth surface (polishing effect) with at the same time minimal abrasive effect (abrasion effect) and damage to the tooth enamel and dentin. The abrasion behavior of the polishing agents and cleaning bodies is essentially determined by their hardness, particle size distribution and surface structure. When selecting suitable cleaning bodies, those which have a minimal abrasion effect with high cleaning performance are therefore particularly preferred.

Nowadays, mainly cleaning materials are used which have small grain sizes, are largely free of sharp corners and edges and whose hardness and mechanical properties do not stress the tooth or tooth substance too much.

Water-insoluble inorganic substances are usually used as cleaning bodies or polishing agents. The use of very finely divided polishing agents with an average grain size of 1 - 200 μm, preferably 1 - 50 μm and in particular 1 - 10 μm is particularly advantageous.

In principle, the polishing agents according to the invention can be selected from silicas, aluminum hydroxide, aluminum oxide, silicates, organic polymers or mixtures thereof. Furthermore, so-called metaphosphates, Alkaline earth metal carbonates or hydrogen carbonates and calcium-containing polishing components can be contained in the agents according to the invention.

It can be preferred according to the invention to use silicas as polishing agents in toothpastes or liquid tooth cleaning agents. A distinction is basically made between silica polishing agents between gel silicas, hydrogel silicas and precipitated silicas. Precipitated and gel silicic acids are particularly preferred according to the invention because they can be varied widely in their production and are particularly well tolerated with fluoride active ingredients. They are also particularly well suited for the production of gel or liquid toothpastes.

Gel silicic acids are generated by the reaction of sodium silicate solutions with strong, aqueous mineral acids with the formation of a hydrosol, aging to the hydrogel, washing and subsequent drying. If drying takes place under gentle conditions to water contents of 15 to 35% by weight, so-called hydrogel silicas are obtained, as are also described, for example, in US Pat. No. 4,153,680. By drying these hydrogel silicas to water contents below 15% by weight there is an irreversible shrinkage of the previously loose structure to the dense structure of the so-called xerogel. Such xerogel silicas are known, for example, from US Pat. No. 3,538,230.

A second, preferably suitable group of silicic acid polishing agents are the precipitated silicas. These are obtained by precipitating silica from dilute alkali silicate solutions by adding strong acids under conditions in which aggregation to the sol and gel cannot occur. Suitable processes for the preparation of precipitated silicas are described, for example, in DE-OS 2522 586 and in DE-OS 31 14493. A precipitated silica prepared according to DE-OS 31 14 493 with a BET surface area of 15-110 m ² / g and a particle size of 0.5 to 20 μm is particularly suitable according to the invention, with at least 80% by weight of the primary particles below 5 µm should be, and a viscosity in 30% glycerol water (1: 1) dispersion 30 - 60 Pa s (20 ° C) in an amount of 10 - 20 wt .-% of the toothpaste. Precipitated silicas of this type which are preferably suitable also have rounded corners and edges and are available, for example, under the trade name Sident ^® Ϊ2 DS from Degussa.

Other precipitated silicas of this type are Sident ^® 8 from Degussa and Sorbosil ^® AC 39 from Crosfield Chemicals. These silicas are characterized by a lower thickening effect and a somewhat higher average particle size of 8 - 14 μm with a specific surface area of 40 - 75 m ² / g (according to BET) and are particularly suitable for liquid toothpastes. These should have a viscosity (25 ° C, shear rate D = 10 s ^"1 ) of 10 - 100 Pa s.

Furthermore, the silicas of the type Zeodent ^® Huber-Corp., Tixosil® Rhodia and other Sorbosil® types can be used in the agents. Zeodent ^® 113, Tixosil ^® 123 and Sorbosil ^® AC39 are particularly preferred.

Toothpastes that have a significantly higher viscosity of more than 100 Pa s (25 ° C, D = 10 s ^"1 ), on the other hand, require a sufficiently high proportion of silicas with a particle size of less than 5 μm, preferably at least 3% by weight. % of a silica with a particle size of 1 to 3 μm. Toothpastes are therefore preferably added in addition to the precipitated silicas mentioned, more finely divided, so-called thickening silicas with a BET surface area of 150-250 m ² / g. As examples of commercial products that Sipernat ^® 22 LS or Sipemat ^® 320 DS from Degussa should be mentioned in particular.

A weakly calcined alumina with a content of α- and γ-aluminum oxide in an amount of approximately 0.01 to 5% by weight, preferably 0.1 to 2% by weight, based on the aluminum oxide polishing agent, is preferred Total weight of the product. Suitable weakly calcined clays are produced by calcination from aluminum hydroxide. Aluminum hydroxide passes through calcination into the α-Al ₂ 0 _{3 which is} thermodynamically stable at temperatures above 1200 ° C. The thermodynamically unstable AI ₂ θ ₃ modifications occurring at temperatures between 400 and 1000 ° C are called gamma forms (cf. Ullmann, Encyclopedia of Technical Chemistry, 4th edition (1974), volume 7, page 298) , By selecting the temperature and the duration of the calcination, the degree of calcination, ie the conversion into the thermodynamically stable α-Al ₂ 0 ₃ , can be set to any desired level. Weak calcination gives an alumina with a γ-Al ₂ O ₃ content which is lower, the higher the calcination temperature and the longer the calcination time. Weakly calcined clays differ from pure CC-AI2O _{3 in} that the agglomerates have a lower hardness, a larger specific surface area and larger pore volumes.

The dentin abrasion (RDA) of the weakly calcined clays to be used according to the invention with a proportion of 10-50% by weight γ-AI ₂ 0 ₃ is only 30-60% of the dentin abrasion of a strongly calcined, pure -AI ₂ 0 ₃ ( measured in a standard toothpaste with 20 wt .-% alumina as the only polishing agent).

In contrast to α-AI ₂ 0 ₃ , the γ-AI ₂ 03 can be colored red with an aqueous ammoniacal solution of Alizarin S (1, 2-dihydroxy-9,10-anthraquinone-4-sulfonic acid). You can choose the degree of dyeability as a measure of the degree of calcination or the proportion of δ-Al ₂ 0 ₃ in a calcined clay: approx. 1 g of Al ₂ O ₃ , 10 ml of a solution of 2 g / l Alzarin S in water and 3 drops of an aqueous, 10% by weight solution of NH3 are placed in a test tube and boiled briefly. The AI ₂ O ₃ is then filtered off, washed, dried and assessed under a microscope or evaluated colorimetrically.

Suitable, weakly calcined clays with a content of 10-50% by weight of γ-Al ₂ O ₃ can be colored slightly to deep pink using this process. Aluminum oxide polishing agents of various degrees of calcination, fineness and bulk density are commercially available, for example the "polishing clay" from Giulini-Chemie or ALCOA.

A preferred suitable quality “polishing clay P10 finest” has an agglomerate size of less than 20 μm, an average primary crystal size of 0.5-1.5 μm and a bulk density of 500-600 g / l.

The use of silicates as polishing agent components can also be preferred according to the invention. They are used as cleaning bodies, particularly in modern practice. Examples of silicates which can be used according to the invention are aluminum silicates and zirconium silicates. In particular, the sodium aluminum silicate of the empirical formula Naι (Al02) i2 (Si0 ₂ ) i2 x 7H ₂ 0 can be suitable as a polishing agent, such as the synthetic zeolite A.

Examples of water-insoluble metaphosphates according to the invention are, in particular, sodium metaphosphate, calcium phosphate such as, for example, tricalcium phosphate, calcium hydrogen phosphate, calcium hydrogen phosphate dihydrate and calcium pyrophosphate.

In addition, according to the invention, magnesium carbonate, magnesium hydrogen phosphate, trimagnesium phosphate or sodium hydrogen carbonate can be used as the polishing agent, in particular as a mixture with other polishing agents.

Another polishing agent that is suitable for use in the oral and dental care products according to the invention is calcium phosphate dihydrate (CaHP0 ₄ x 2H ₂ O). Calcium phosphate dihydrate occurs naturally as brushite and is commercially available as a polishing agent in suitable grain sizes from 1 to 50 μm.

Oral and dental care products are preferred according to the invention which additionally support 0.1 to 10% by weight, preferably 0.1 to 5% by weight and in particular 0.1 to 3% by weight to support the remineralization process through the composite material. % of a remineralization promotion component, each based on the total weight of the composition.

The remineralization promoting component promotes the remineralization of the tooth enamel and the sealing of dental lesions in the agents according to the invention and is selected from fluorides, microparticulate phosphate salts of calcium such as. B. calcium glycerol phosphate, calcium hydrogen phosphate, hydroxyapatite, fluorapatite, F-doped hydroxyapatite, dicalcium phosphate dihydrate and calcium fluoride. But also magnesium salts such as. B. magnesium sulfate, magnesium fluoride or magnesium monofluorophosphate have a remineralizing effect.

Remineralization promoting components preferred according to the invention are magnesium salts.

Suitable embodiments of the oral and dental care agent according to the invention are solid, liquid or semi-liquid toothpastes and tooth gels.

According to a further preferred embodiment, the oral and dental care compositions according to the invention contain additional toothpaste ingredients such as surfactants, humectants, binders, flavorings and active ingredients against tooth and gum diseases.

Surface-active surfactants or surfactant mixtures are usually used to improve the cleaning effect and the foaming of the oral and dental care products according to the invention. They promote the rapid and complete dissolution and distribution of toothpastes in the oral cavity and at the same time support the mechanical removal of dental plaque, especially in areas that are difficult to access with a toothbrush. In addition, they promote the incorporation of water-insoluble substances, such as aromatic oils, stabilize the polishing agent dispersion and support the anti-caries effect of fluorides. In principle, anionic surfactants, zwitterionic and ampholytic surfactants, nonionic surfactants, cationic surfactants or mixtures of these compounds can be used as surfactants in toothpaste formulations. According to the invention, toothpastes preferably contain at least one surfactant from the group of anionic surfactants.

In the compositions according to the invention, the surfactant or the surfactant mixture is usually present in an amount of 0.1-10% by weight, preferably 0.3-7% by weight and in particular 1-5% by weight, based on the total weight of the Composition used.

Anionic surfactants

Suitable surfactants with good foaming action are anionic surfactants, which also have a certain enzyme-inhibiting effect on the bacterial metabolism of the plaque.

These include, for example, alkali or ammonium salts, in particular sodium salts, of C ₈ -C ₈ -alkanecarboxylic acids, of alkyl polyglycol ether sulfates with 12-16 C atoms in the linear alkyl group and 2-6 glycol ether groups in the molecule, of linear alkane (Ci ₂ -Cι ₈ ) -sulfonates, sulfosuccinic acid monoalkyl (Ci2- Cι ₈ ) esters, sulfated fatty acid monoglycerides, sulfated fatty acid alkanolamides, sulfoacetic acid alkyl (C ₂ -Ci ₆ ) esters, acyl sarcosines, acyl taurides and acyl isethionates, each with 8-18 C atoms the acyl group.

It is preferred to use at least one anionic surfactant, in particular a sodium lauryl alkyl sulfate with 12-18 C atoms in the alkyl group. Such a surfactant is sodium lauryl sulfate which is commercially available for example under the name Texapon.RTM ^® K12 G commercially. Zwitterionic and ampholytic surfactants

It can be preferred according to the invention to use zwitterionic and / or ampholytic surfactants, preferably in combination with anionic surfactants. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the, N-alkyl-N, N-dimethylammonium glycinate, for example f rimethylammonium glycinate, cocoalkyldimethylammonium glycinate, N-acylamino-propyl-N, N-dimethyl-ammonium glycinate, for example cocoacylaminopropyldimethylammonium, ammonium and 2-alkyl-3-carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and also the cocoacylaminoethylethylethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred. Such products are commercially available, for example, under the names Tego-Betain ^® BL 215 and ZF 50 and Genagen ^® CAB.

Ampholytic surfactants are surface-active compounds which, in addition to a Cβ-Ciβ-alkyl or acyl group, contain at least one free amino group and at least one -COOH or -S0 ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylisarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and Ci ₂ -Ci ₈ acyl sarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred. Nonionic surfactants

Non-ionic surfactants are particularly suitable according to the invention for supporting the cleaning action. Those nonionic surfactants which are selected from at least one of the following groups are particularly preferred:

- Adducts of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group;

- C12-C18 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;

- Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids with 6 to 22 carbon atoms and their ethylene oxide addition products;

- Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogues;

- Adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

- polyol and especially polyglycerol esters, e.g. Polyglycerol polyricin oleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate.

Mixtures of compounds from several of these classes of substances are also suitable;

- Adducts of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

- Partial esters based on linear, branched, unsaturated or saturated C ₆ - C ₂₂ fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerin, polyglycerin, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), sucrose, alkyl glucosides ( eg methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (eg cellulose); - Mono-, di- and trialkyl phosphates as well as mono-, di- and / or tri-PEG-alkyl phosphates and their salts; - wool wax alcohols; - Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives; - Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol and

- polyalkylene glycols.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters with fatty acids or with castor oil are known, commercially available products and are preferred according to the invention. These are homolog mixtures whose average degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. Ci ₂ -Ci ₈ fatty acid mono- and diesters of adducts of ethylene oxide with glycerol are known from DE-PS 2024051 as refatting agents for cosmetic preparations. Cs-Cis-alkyl mono- and oligoglycosides, their preparation and their use are from the prior art, for example from US-A-3,839,318, DE-A-20 36 472, EP-A-77 167 or WO-A-93 / 10132 known. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. With regard to the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to preferably about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products. A suitable alkyl (oligo) glycoside is preferably an alkyl (oligo) glycoside of the formula RO (C ₆ HιoO) _x -H, in which R represents an alkyl group having 12 to 14 C atoms and x is an average value of 1 to 4.

A particularly preferred example of an inventively employable, nichtio- nogenen surfactant may be mentioned, for example, PEG-glyceryl stearate, sold under the name Tagat ^® S commercially. Humectants are usually used in dental cosmetics to protect them from drying out and to regulate the consistency and low-temperature stability of the products. However, they can also be used to impart suspensions and to influence taste or gloss.

Toxicologically harmless polyols, such as, for example, sorbitol, xylitol, glycerol, mannitol, 1, 2-propylene glycol or mixtures thereof, are usually used as humectants, but polyethylene glycols with molecular weights of 400-2000 can also serve as humectant components in toothpastes.

The combination of several humectant components is preferred, the combination of glycerol and sorbitol containing 1,2-propylene glycol or polyethylene glycol being regarded as particularly preferred.

Depending on the product type, the humectant or the mixture of humectants is contained in the total composition in an amount of 10-85% by weight, preferably 15-70% by weight and in particular 25-50% by weight.

In a preferred embodiment, the agents according to the invention additionally contain at least one binding or thickening agent. These have a consistency-regulating effect and furthermore prevent the separation of the liquid and solid components.

The amounts used in the compositions according to the invention are 0.1-5% by weight, preferably 0.1-3% by weight and in particular 0.5-2% by weight.

For example, natural and / or synthetic water-soluble polymers such as alginates, carrageenans, agar-agar, guar gum, gum arabic, succinoglycan gum, guar flour, locust bean gum, tragacanth, karaya gum, xanthan, pectins, cellulose and their ionogenic and Non-ionogenic derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose or methyl hydroxypropyl cellulose, hydrophobically modified celluloses, starch and starch ethers. Water-soluble carboxyvinyl polymers (eg Carbopol ^® types), polyvinyl alcohol, polyvinylpyrrolidone and higher molecular weight polyethylene glycols (in particular those with molecular weights of 10 ² - 10 ⁶ D) are also suitable as binders or thickeners. Layered silicates and finely divided silicas (aerosilica and pyrogenic silicas) can also fulfill this function.

In a further preferred embodiment, the mouth and tooth cleaning agent according to the invention contains additional active substances against tooth and gum diseases. According to the invention, such active substances are to be understood as anti-caries substances, antimicrobial substances, tartar inhibitors, flavorings or “any combination of these substances”.

Anti-caries agents

To combat and prevent caries, fluorine compounds are particularly suitable, preferably from the group of fluorides or monofluorophosphates in an amount of 0.1-0.5% by weight of fluorine. Suitable fluorine compounds are e.g. As sodium fluoride, potassium fluoride, tin fluoride, disodium monofluorophosphate (Na ₂ Pθ ₃ F), dipotassium monofluorophosphate or the fluoride of an organic amino compound.

Antimicrobial agents

As an antimicrobial component such. B. phenols, resorcinols, bisphenol oils, salicylanilides and amides and their halogenated derivatives, halogenated carbanilides and p-hydroxybenzoic acid esters.

Among the antimicrobial components, those which inhibit the growth of PIaque bacteria are particularly suitable. For example, halogenated diphenyl ethers such as 2,4-dichloro-2'-hydroxydiphenyl ether, 4,4'-dichloro-2'-hydroxydiphenyl ether, 2,4,4'-tribromo-2'-hydroxydiphenyl ether, 2,4,4'- Trichlor-2'-hydroxydiphenyl ether (triclosan) suitable as antimicrobial agents. In addition to bromochlorophene, bisbiguanides such as chlorhexidine and alexidine, phenylsalicylic acid esters and 5-amino-1, 3-bis (2-ethylhexyl) hexahydro-5-methylpyrimidine (hexitidine), zinc and copper ions also have an antimicrobial effect, with synergistic effects in particular occur in combination with hexetidine and triclosan. Quaternary ammonium compounds, such as. B. cetylpyridinium chloride, benzalkonium chloride, domiphen bromide and dequalinium chloride can be used. Octapinol, octenidines and sanguinarine have also proven to be antimicrobial.

The antimicrobial active ingredients are preferably used in amounts of 0.01-1% by weight in the agents according to the invention. Irgacare ^® MP is particularly preferred in an amount from 0.01 to 0.3 wt .-% is used. Tartar inhibitors

Tartar is mineral deposits that are very similar to natural tooth enamel. In order to inhibit tartar formation, substances are added to the tooth cleaning agents according to the invention which specifically intervene in the crystal nucleation and prevent existing germs from continuing to grow. These are, for example, condensed phosphates, which are preferably selected from the group of tripolyphosphates, pyrophophates, trimetaphosphates or mixtures thereof. They are used in the form of their alkali or ammonium salts, preferably in the form of their sodium or potassium salts. Aqueous solutions of these phosphates typically have an alkaline reaction, so that the pH of the dentifrices according to the invention is adjusted to values of 7.5-9, if necessary by adding acid. As acids z. B. citric acid, phosphoric acid or acidic salts, e.g. B. NaH ₂ P0 ₄ can be used. The desired pH of the dentifrice can also be achieved by adding acidic salts of the condensed phosphates, e.g. B. K ₂ H ₂ P ₂ O ₇ can be set.

Mixtures of different condensed phosphates and / or hydrated salts of the condensed phosphates can also be used according to the invention. Tartar inhibitors are usually used in amounts of 0.1-5% by weight, preferably 0.1-3% by weight and in particular 0.1-2% by weight in the agents according to the invention.

Other suitable tartar inhibitors are organophosphonates such as 1-azacycloheptane-2,2-diphosphonate (Na salt), 1-hydroxyethane-1, 1-diphosphonate (Na salt) and zinc citrate. Active substances against hypersensitive teeth

The agents according to the invention preferably also contain active substances against hypersensitive teeth, they are selected from potassium and strontium salts such as potassium chloride, potassium sulfate, potassium bicarbonate, potassium citrate, potassium acetate, potassium nitrate, strontium chloride, strontium nitrate, strontium citrate, strontium acetate and strontium lactate and eugenol lactate.

The eugenol can be mixed with aromatic oils in the oral and dental care products. It is preferably contained in the compositions in the form of clove bud oil.

The oral and dental care products according to the invention preferably contain at least 0.5% by weight of potassium or strontium ions in the form of a dissolved salt and at least 0.01% by weight of eugenol in pure form or in the form of clove bud oil.

Flavorings The agents according to the invention preferably contain flavorings, to which e.g. B. sweeteners and / or aromatic oils.

Suitable sweeteners are, for example, saccharinates (in particular sodium saccharinate), cyclamates (in particular sodium cyclamate) and sucrose, lactose, maltose or fructose.

Aromatic oils that can be used are all natural and synthetic aromas that are common for oral and dental care products. Natural flavors can be used both in the form of the essential oils (mixture) isolated from the drugs and in the form of the individual components isolated from them. At least one aromatic oil from the group of peppermint oil, spearmint oil, anise oil, stemanis oil, caraway oil, eucalyptus oil, fennel oil, cinnamon oil, clove oil, geranium oil, sage oil, allspice oil, thyme oil, marjoram oil, basil oil, citrus oil, Gaultheria oil or one or more synthetically isolated or should be preferred produced components of these oils be included. The most important components of the oils mentioned are e.g. B. menthol, carvone, anethole, cineol, eugenol, cinnamaldehyde, caryophyllene, geraniol, citronellol, linalool, salvos, thymol, terpinene, terpinol, methylchavicol and methyl salicylate. Other suitable flavors are e.g. B. menthyl acetate, vanillin, jonone, linalyl acetate, rhodinol and piperiton.

Finally, other conventional aids to improve the stability and the sensory properties of the oral and dental care products can be included. Examples of such aids are:

Vitamins, e.g. B. retinol, biotin, tocopherol, ascorbic acid and their deri. , vate, (e.g. esters, salts);

• pigments, e.g. B. titanium dioxide or zinc oxide;

• Colored pigment particles, for example colored silica particles, such as those e.g. B. are commercially available under the sales name Sorbosil ^® BFG 51, BFG 52 and BFG 53 or Sorbosil ^® 2352. Mixtures of differently colored pigment particles can also be used. Such, e.g. B. strong orange, red or blue colored silica particles can be present in the agents according to the invention in amounts of 0.1-1.0% by weight; • bleaching agents such as hydrogen peroxide and hydrogen peroxide precursors; • dyes; • pH adjusting agents and buffer substances, e.g. B. sodium citrate, sodium bicarbonate or potassium and sodium phosphates, • preservatives, for example methyl, ethyl or - propyl p-hydroxybenzoate, sodium sorbate, sodium benzoate, bromochlorophene or triclosan; • wound healing and anti-inflammatory substances such. B. allantoin, urea, panthenol, azulene or chamomile extract, acetylsalicylic acid derivatives, alkali rhodanides; • Mineral salts such as zinc, magnesium and manganese salts, for example - sulfates. All of these optional toothpaste ingredients are contained in the compositions according to the invention in an amount of about 2 to 10% by weight, based on the total weight.

A second subject of the invention is the cosmetic use of the mouth and tooth cleaning agent according to the invention for the sensitive cleaning of the teeth.

Cosmetic use is understood to mean the non-therapeutic use of the mouth and tooth cleaning agent according to the invention for daily cleaning and care of the teeth and the oral cavity.

Sensitive cleaning means the gentle cleaning of the tooth surface due to the low cleaning agent content. The enamel and the dentin are not attacked by the abrasive effect of the cleaning agent being too high, and a deposit of the remineralization component is guaranteed at the same time.

A third subject of the invention is the cosmetic use of the mouth and tooth cleaning agent according to the invention for the prevention and control of hypersensitive teeth.

A fourth object of the invention is the cosmetic use of the oral and dental care agent according to the invention for whitening the teeth and for preventing discoloration and recoloring.

The whitening of the teeth is determined by comparing teeth that have been treated with the tooth cleaning agent according to the invention and teeth that have been treated with a comparison formulation using a commercially available colorimeter (from Lange).

A fifth object of the invention is the cosmetic use of the oral and dental care agent according to the invention for the prevention of plaque adhesion and the associated reduction in the formation of new plaque on tooth surfaces. As a result, the adhesion of PIaque to the tooth surface promoted by imperfections can be reduced.

A sixth object of the invention is cosmetic use of the oral and dental care agent according to the invention for the remineralization of dental lesions.

The effect of the composite material can be enhanced by combining it with a suitable toothbrush. By choosing a suitable bristle and a suitable design of the brush, in particular the brush head and the cut, the cleaning performance of a composite dentifrice is possible with high landfill.

Tubes and dispensers, pumps and other packaging which facilitates dosing can be used as packaging for the dental care preparations according to the invention containing composite materials.

The following examples are intended to explain the subject matter of the invention in more detail without restricting it thereto.

Unless otherwise stated, the quantities used relate to% by weight.

Examples

1) Example of a semi-viscous toothpaste preparation

2) Example of a thin toothpaste preparation

) Example of a viscous (solid) toothpaste

It has been demonstrated in tests that the landfill effect is retained if an adequate and particularly gentle cleaning performance is maintained. These attempts were e.g. performed with dentine samples and the growth of hydroxyapatite assessed.

The following commercial products were used:

Neosorb ^®: INCI: sorbitol; about 70% in water; Manufacturer: Roquette Sipernat ^® FK 320 DS: INCI: Hydrated Silica; Manufacturer: Degussa ^® Sident 8: INCI: Hydrated Silica; Manufacturer: Degussa Nanit in glyceriseher Dispersion: composite material according to the invention as a 10% dispersion in glycerol Tego betaine ^® BL 215: INCI: Cocamidopropyl Betaine; AS: 30% Manufacturer: Goldschmidt Texapon.RTM ^® K12G: INCI: Sodium Lauryl Sulfate; AS. 95-99% Manufacturer: Cognis Polywachs ^® 1550: INCI: Poly ethylene glyeol; MG 1400-1600 Manufacturer: Sasol Keltrol ^® F: INCI: Xanthan Gum Manufacturer: CP Kelco Texapon ^® K1296: Sodium Lauryl Sulfate; AS: 90% Manufacturer: Cognis Tagat ^® S: INCI: PEG-30 Glyceryl Stearate Manufacturer: Tego Cosmetics Sident ^® 22S: INCI: Hydrated Silica; Manufacturer: Degussa Polydiol ^® 400: INCI: poly ethylene glyeol; MG 380-420 Manufacturer: Cognis Cekol ^® 2000H: INCI: Cellulose Gum Manufacturer: Noviant

Claims

claims

1. Oral and dentifrice containing a) a composite material containing - calcium salts sparingly soluble in water in the form of nanoparticulate primary particles with a length of 5 to 150 nm and a cross section of 2 to 50 nm and - protein components selected from proteins, protein hydrolyzates and Protein hydrolyzate derivatives, and b) 0.1 to 9% by weight of a cleaning agent, based on the total weight of the agent.

2. Oral and dental care product according to claim 1, characterized in that the calcium salts are selected from fluorapatite and / or hydroxylapatite.

3. Oral and dental care product according to one of claims 1 or 2, characterized in that the protein component is selected from structure-forming proteins such as collagen, gelatin, keratin, casein, wheat protein, rice protein, soy protein, almond protein and their hydrolyzates and hydrolyzate derivatives.

4. Oral and dental care agent according to one of claims 1 to 3, characterized in that the content of the composite material is 0.01 to 10 wt .-%, based on the total weight of the agent.

5. Oral and dental care product according to one of claims 1 to 4, characterized in that the nanoparticulate primary particles are rod-shaped.

6. Oral and dental care product according to one of claims 1 to 5, characterized in that the nanoparticulate primary particles form rod-shaped crystals with a length-to-width ratio of 3 to <5, in particular of about 4.

7. Oral and tooth care product according to one of claims 1 to 6, characterized in that the cleaning agent is selected from silicas, aluminum oxides, silicates, metaphosphates and alkaline earth metal carbonates or - hydrogen carbonates.

8. Oral and dental care product according to one of claims 1 to 7, characterized in that it contains at least one remineralization promoting component.

9. Oral and dental care product according to claim 8, characterized in that the remineralization promoting component is selected from magnesium salts.

10. Oral and dental care product according to one of claims 1 to 9, characterized in that it contains surfactants, humectants, binders and active substances against tooth and gum diseases as further toothpaste ingredients.

11. Oral and dental care agent according to one of claims 1 to 10, characterized in that the active ingredients are anti-caries agents, antimicrobial agents, tartar inhibitors, agents against hypersensitive teeth and / or mixtures of these substances.

12. Cosmetic use of a mouth and dentifrice according to one of claims 1 to 11 for the sensitive cleaning of the teeth.

13. Cosmetic use of a mouth and dentifrice according to one of claims 1 to 11 for the prevention and / or control of hypersensitive teeth.

14. Cosmetic use of a mouth and dentifrice according to one of claims 1 to 11 for whitening the teeth and / or for prevention and / or discoloration and recoloring.

15. Cosmetic use of a mouth and dentifrice according to one of claims 1 to 11 for the prevention of plaque adhesion.

16. Cosmetic use of a mouth and dentifrice according to one of claims 1 to 11 for the remineralization of dental lesions.