DE102006039632A1 - Composition comprising sparingly water-soluble calcium salts and / or their composite materials in an amount of 1 to 99% by weight - Google Patents

Abstract

The invention relates to a composition comprising sparingly water-soluble calcium salts and / or their composite materials in an amount of 1 to 99% by weight, based on the amount of the composition, and kits and systems containing these compositions, as well as the use and methods of use these compositions, systems and kits. The compositions according to the invention are particularly suitable for promoting the restoration of bone and tooth material, in particular enamel and dentin.

Description

The The invention relates to a composition containing sparingly water-soluble calcium salts and / or their composite materials in an amount of 1 to 99 wt .-% based on the amount of the composition, as well as kits and systems containing These compositions, as well as the use and method of Use of these compositions, systems and kits. The compositions of the invention are particularly suitable for promotion the restoration of bone and tooth material, in particular Enamel and dentin.

phosphate salts of calcium have long been considered both as abrasive components also for promotion the remineralization of the enamel the formulations of dentifrices and dentifrices. This is especially true for hydroxyapatite and fluorapatite as well as for amorphous calcium phosphates and for Brushite (dicalcium phosphate dihydrate). Also calcium fluoride is as Part of dentifrices and as a component for consolidation of tooth enamel and caries prophylaxis described several times Service.

The Availability of calcium compounds for the desired one Remineralization hangs quite decisively on the particle size of these sparingly soluble in water and in the dentifrices dispersed components. One has therefore proposed, these sparingly soluble calcium salts in the finest Use distribution.

Of the Enamel and the supporting tissue the bones are predominantly from the mineral hydroxyapatite. In the biological development process Hydroxylapatite deposits in an ordered manner to the protein matrix in the bone or tooth, which is predominantly made of collagen. The formation of hard and resilient mineral Structures are controlled by the so-called matrix proteins, which are formed by collagen other proteins, the attach themselves to the collagen and thus a structured mineralization process, which is also referred to as biomineralization effect.

bone is a combination of scleroproteins and platelet-shaped hydroxyapatite.

In the restoration of bone material, so-called bone substitutes, which promote the natural biomineralization process, play an important role. Such agents are also required for coating implants in order to achieve cohesive connections between bone and implant, with which tensile forces can also be transmitted. Of particular importance here are coatings with a high bioactivity, which lead to an effective composite osteogenesis. According to the prior art, as z. B. G. Willmann in Mat. u. Werkstofftech. 30 (1999), 317 As a rule, hydroxyapatite is applied to implants. A disadvantage of this approach, in addition to the often insufficient acceleration of the biomineralization process, the chipping of the hydroxyapatite layers and their unsatisfactory chemical stability.

For certain Applications become fluid Applicable bone replacement materials needed. Here is one special small particle size required, in the conventional Bone substitutes but not achieved in a satisfactory manner can be. about the technical disadvantages (lack of dispersibility the solid constituents), the previously available liquid applied Bone replacement materials due to the coarsely crystalline inorganic Shares as well as the lack of bioanalogous organic fractions at best a biocompatible, possibly absorbable effect. Are desired but the natural one Biomineralization and thus directly promoting bone growth, osteoinductive, osteoconductive or osteostimulating materials.

Under The bone substitutes are composites of hydroxyapatite and collagen Of particular interest, as they are the composition of the natural Imitate bone. A similar Situation prevails in the restoration of dental material: dentin consists of about 30 percent protein (essentially collagen) as well as 70 percent of mineral substances (essentially Hydroxylapatite), whereas enamel consists to about 95% of hydroxyapatite and about 5 percent from proteins.

Composite materials of the type described are accessible by synthetic routes, such as. B. from B. Flautre et al. in J. Mater. Sci .: Mater. In Medicine 7 (1996), 63 described. However, in these composites, the grain size of the calcium salts is above 1000 nm, which is too large to achieve a satisfactory biological effect as a remineralizer.

In contrast, describes RZ Wang et al., J. Mater. Sci. Lett. 14 (1995), 490 a method of manufacturing a composite of hydroxyapatite and collagen in which hydroxyapatite having a particle size in the range of 2 to 10 nm is deposited in evenly distributed form on the collagen matrix. The composite material is said to have better biological effectiveness than other hydroxyapatite-collagen composites known in the art due to the finely divided hydroxyapatite. However, as described below, RZ Wang et al. composite material described insufficient the need for composite materials which mimic the composition and the microstructure of natural bone and tooth material and are fully satisfactory for the remineralization of these natural materials.

In the EP 1 139 995 A1 It is proposed to stabilize suspensions of sparingly soluble in water calcium salts in very finely divided form during precipitation or shortly thereafter, by performing the precipitation in the presence of an agglomeration inhibitor or redispersing the dispersion in the presence of the agglomeration inhibitor, for example a Schutzkollid or surfactant.

The WO 01/01930 discloses composite materials composed of nanoparticulate sparingly soluble calcium salts and protein component which have a remineralizing effect on enamel and dentin. Gelatins of type A or B are used for this purpose.

These Composite materials can while causing a re-or neomineralization of the bone material, but the necessary exposure time is for certain applications or areas of application too large or the re-or neomineralization of the bone material takes too long.

One Another disadvantage of known from the prior art protein-containing Composite materials consists in their often expensive production. For example, in the production of R. Z. Wang et al. described composites of hydroxyapatite and collagen insoluble Collagen handled and distributed in very large amounts of solvent be, which is technically complicated. This method also raises problems in terms of disposal of incurred in the production sewerage on.

It has now been found that overcoming certain materials from the above-mentioned disadvantages of the prior art are.

task the present invention is to provide an opportunity whereby the remineralization and / or neomineralization of bone, in particular tooth material, preferably dentin and / or enamel, as well as the stratification on the enamel and / or dentin, accelerates becomes.

These Task is solved by a composition containing sparingly water-soluble calcium salts and / or their composite materials in an amount of 1 to 99 wt .-% based on the amount of the composition.

The Invention relates to this In addition, kits containing at least one composition according to the invention and additionally a suitable applicator for the composition and / or another component B, the use the kits of the invention.

The Invention also relates to a system, characterized that it contains at least one composition according to the invention and one aqueous solution a soluble Calcium salt and / or a soluble Phosphate salt includes.

Farther The invention relates to methods of using the inventive compositions, kits and systems.

mainly rod- and / or platelet means, that at least 50%, preferably at least 70%, is particularly preferred at least 80% of the particles are in the form of platelets and / or rods. Predominantly platelet-shaped, that at least 50%, preferably at least 70%, is particularly preferred at least 80% of the particles are in the form of platelets.

Especially Preferably, the particles have a substantially platelet-shaped form on.

Advantageously, the calcium salts or composite materials according to the invention comprising these, with the predominantly platelet-shaped calcium particles of the structure of the bone substance in vivo, the also made of plates, very similar. This has the particular advantage that they have a particularly good ability to re-and neomineralization due to the similarity of the form with the biological Apatiten (eg bone or Dentinapatit), so that the process of biomineralization can take place even faster and better.

One Another advantage of the invention is that the poorly water-soluble Calcium salts or composite materials, including these, with a predominantly platelet-shaped structure the calcium salts have improved biocompatibility.

When Particle diameter is here the diameter of the particles in the direction their greatest length extension be understood. Below the average particle diameter is an over the Total composite value to understand average value. He is lying according to the invention 1000 nm, preferably below 300 nm.

Preferably the average particle diameter of the crystallites is in the range from 10 to 150 nm, and most preferably are the crystallites with a thickness in the range of 2 to 50 nm and a length in the range from 10 to 150 nm. Under thickness here is the smallest diameter the crystallites understand, by length their largest diameter.

The Determination of the particle diameter of the crystallites can by the Specialist familiar Methods are determined, in particular by the evaluation of the in X-ray diffraction observed broadening of the reflexes. Preferably takes place the evaluation by Fit method for example, the Rietveld method.

According to one particularly preferred embodiment the crystallites preferably have a thickness of 2 to 15 nm and a length from 10 to 50 nm; particularly preferably a thickness of 3 to 11 nm and a length from 15 to 25 nm, up.

According to one another preferred embodiment The invention relates to the calcium salts of the invention and / or the Composite materials comprising these having an average particle diameter of Particles in the range of below 1000 nm, preferably below 300 nm before.

The Determination of the particle diameter of the particles can be carried out by a person skilled in the art common Methods are determined, in particular by the evaluation of Imaging methods, in particular transmission electron microscopy.

According to one particular embodiment have the inventive heavy water-soluble calcium salts and / or the composite materials comprising these, predominantly platelet-shaped particles with a width in the range of 5 to 150 nm and a length in the range from 10 to 150 nm and a height (thickness) from 2 to 50 nm.

Under Height (thickness) Here is the smallest diameter of the particles in relation to the three to understand mutually perpendicular spatial directions, under Length her largest diameter. The width of the particles is therefore the other perpendicular to the length Diameter equal to or smaller than the length dimension of the particle, but bigger or at least equal to its height dimension is.

The platelet-shaped particles lie as more or less irregularly shaped particles, partly as rather round particles, partly rather angular particles with rounded edges Edges in front.

This is particularly noticeable in the pictures that stand in the way can be recorded by transmission electron microscopy.

The platelet-shaped particles are common in such samples also overlapping several times in front. Overlapping Particles are typically imaged at the points of overlap with greater blackening as non-overlapping Particle. The specified lengths, Widths and heights are preferably not overlapping per se Particles of the sample determined (measured).

The height of the platelet-shaped particles can preferably be obtained from such images by determining the dimensions of the particles having their largest surface perpendicular to the image plane. The perpendicular to the image plane particles are characterized by a particularly high contrast (high density) and appear rather rod-shaped. These are perpendicular to the image plane platelet-shaped particles can be identified as actually standing perpendicular to the image plane if they show a broadening of the dimension (at least in one spatial direction) and a decrease in the density of the image when tilting the image plane.

to Determination of height it is particularly suitable for the particle, the image plane of the sample several times in different positions to tilt and the dimensions the particle in the setting to determine by the highest contrast / highest darkness and the smallest extent of the particles is characterized. The shortest extent then corresponds to the height the particle.

According to one preferred embodiment is the average length the particle preferably 30 to 100 nm.

Prefers The width of these particles is in the range between 3 to 100 nm, preferably between 5 to 80 nm, in particular between 10 and 60 nm.

According to one particular embodiment is in the case of the particles of the sparingly water-soluble invention Calcium salts and / or composite materials, including these, the relationship of length to width between 1 and 4, preferably from 1 to 3, particularly preferred between 1 and 2, for example, 1.2 (length 60 nm, width 50 nm) or 1.5 (length 80, width 40 nm).

The platelike shape the particle is affected by the ratio of length formed to width. Is that relationship between lengths and width significantly larger than 4, are more rod-shaped particles in front.

Of the Advantage of the platelet-shaped particles with a relationship of preferably 1 to 2 is that these particles are natural Bone material very similar Length too Wide ratio and therefore a particularly good and biocompatible or neomineralization of the dental material (dentin and enamel).

According to a further particular embodiment, the particles have an area of 0.1 × 10 ^-15 m ² to 90 × 10 ^-15 m ² , preferably an area of 0.5 × 10 ^-15 m ² to 50 × 10 ^-15 m ² , particularly preferably 1.0 × 10 ^-15 m ² to 30 × 10 ¹⁵ m ² , very particularly preferably 1.5 × 10 ^-15 m ² to 15 × 10 ^-15 m ^2, for example 2 × 10 ^-15 m ² .

When area the particle becomes the surface the plane, spanned by the length and the vertical Width, according to the usual determined by geometric calculation methods.

Surprisingly succeeded with the present invention, the calcium salts of the invention or composite materials, including these, in the form of crystalline to produce inorganic nanoparticles, which is a particular effective neomineralization of dental material (dentin and enamel) and bone tissue.

As slightly sparingly soluble in water calcium salt should be understood as those salts which are soluble in water at 20 ° C to less than 0.1 wt .-% (1g / l). Such suitable salts are, for example, calcium hydroxyphosphate (Ca ₅ [OH (PO ₄ ) ₃ ]) or hydroxylapatite, calcium fluorophosphate (Ca ₅ [F (PO ₄ ) ₃ ]) or fluoroapatite, fluorine-doped hydroxylapatite having the composition Ca ₅ (PO ₄ ) ₃ (OH, F) and calcium fluoride (CaF ₂ ) or fluorite or fluorspar and other calcium phosphates such as di-, tri- or tetracalcium phosphate (Ca ₂ P ₂ O ₇ , Ca ₃ (PO ₄ ) ₂ , Ca ₄ P ₂ O ₉ , Oxyapatite (Ca ₁₀ (PO ₄ ) ₆ O) or non-stoichiometric hydroxyapatite (Ca _{5-1 / 2 (x + y)} (PO ₄ ) _3-x (HPO ₄ ) _x (OH) _1-y ) Calcium phosphates (eg Ca _{5-1 / 2 (x + y + z)} (PO ₄ ) _3-xz (HPO ₄ ) _x (CO ₃ ) _z (OH) _1-y ), calcium hydrogen phosphate (eg CaH (PO ₄ ) · 2H ₂ O) and octacalcium phosphate (e.g., Ca ₈ H ₂ (PO ₄ ) ₆ · 5H ₂ O).

When Calcium salt can be used in the composite materials of the invention or also several salts in the mixture, selected from the group of phosphates, Fluorides and fluorophosphates optionally containing additional hydroxyl and / or contain carbonate groups, preferably be included. Particularly preferred are hydroxyapatite and fluoroapatite.

According to one another embodiment of the invention the crystallites and / or particles of calcium salts which are free or in the composite materials according to the invention be enveloped by one or more surface modifiers.

As a result, for example, the production of composite materials can be facilitated in such cases, in which the calcium salts can be difficult to disperse. The surface modifier is adsorbed on the surface of the crystallites and / or particles and changes them so that the dispersibility of the calcium salt increases and the agglomeration of the crystallites and / or particles is reduced or substantially prevented.

Furthermore can by a surface modification the structure of the sparingly water-soluble Calcium salts and in particular the composite materials and the Loading the polymer component can be influenced with the calcium salt. This is the case when using the composite materials possible in remineralization processes, Influence on the course and speed of the remineralization process to take.

Under Surface modifiers are substances to be understood which are on the surface of the finely divided particles physically adhere, but not chemically react with these. The individual on the surface adsorbed molecules the surface modifier are essentially free of intermolecular bonds with each other. Under surface modifiers are to be understood in particular dispersants. dispersants are the expert, for example, under the terms emulsifiers, protective colloids, Wetting agents, detergents, etc. known.

• – Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe;
• – C_12/18-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin;
• – Glycerinmono- und -diester und Sorbitanmono- und -diester von gesättigten und ungesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen und deren Ethylenoxidanlagerungsprodukte;
• – Alkylmono- und -oligoglycoside mit 8 bis 22 Kohlenstoffatomen im Alkylrest und deren ethoxylierte Analoga;
• – Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• – Polyol- und insbesondere Polyglycerinester, wie z. B. Polyglycerinpolyricinoleat, Polyglycerinpoly-12-hydroxystearat oder Polyglycerindimerat. Ebenfalls geeignet sind Gemische von Verbindungen aus mehreren dieser Substanzklassen;
• – Anlagerungsprodukte von 2 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• – Partialester auf Basis linearer, verzweigter, ungesättigter bzw. gesättigter C_6/22-Fettsäuren, Ricinolsäure sowie 12-Hydroxystearinsäure und Glycerin, Polyglycerin, Pentaerythrit, Dipentaerythrit, Zuckeralkohole (z. B. Sorbit), Alkylglucoside (z. B. Methylglucosid, Butylglucosid, Lauryl-glucosid) sowie Polyglucoside (z. B. Cellulose);
• – Mono-, Di- und Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEG-alkylphosphate und deren Salze;
• – Wollwachsalkohole;
• – Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;
• – Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol gemäß DE-PS 11 65 574 und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin oder Polyglycerin sowie
• – Polyalkylenglycole.

Suitable surface modifiers are, for example, emulsifiers of the nonionic surfactant type from at least one of the following groups:

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group;
• C _12/18 fatty acid _mono- and diesters of addition products 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 having 6 to 22 carbon atoms and their ethylene oxide addition products;
• - Alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs;
• - Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• - Polyol and in particular polyglycerol esters, such as. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxy stearate or polyglycerol dimerate. Also suitable are mixtures of compounds of several of these classes of substances;
• - addition products 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 _6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, Butylglucoside, lauryl glucoside) and polyglucosides (eg, cellulose);
• - Mono-, di- and trialkyl phosphates and 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 11 65 574 and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol and
• - Polyalkylene glycols.

The Addition products of ethylene oxide and / or of propylene oxide Fatty alcohols, fatty acids, Alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil known, commercially available Products. These are mixtures of homologues whose middle Alkoxylation degree the ratio the molar amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out corresponds.

C _8/18 alkyl mono- and oligoglycosides, their preparation and their use are known in the art. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With regard to the glycoside radical, both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of preferably approximately 8 are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.

Typical examples of anionic emulsifiers are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, Alkyl ether sulfates such as, for example, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfo-succinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as acylglutamates and acylaspartates, alkyl oligoglucoside sulphates, protein fatty acid condensates (especially wheat-based vegetable products), and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution.

Furthermore, zwitterionic surfactants can be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry 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 N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylamino-propyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3 carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. Particularly preferred is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine. Also suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C _8/18 -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group 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-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12/18 acylsarcosine. In addition to the ampholytic, quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

When Surface modifier suitable protective colloids are z. B. natural water-soluble polymers such as Gum arabic, starch, water-soluble Derivatives of water-insoluble polymeric natural products such. Cellulose ethers such as methyl cellulose, Hydroxyethylcellulose, carboxymethylcellulose or modified Carboxymethyl cellulose, hydroxyethyl starch or hydroxypropyl guar, as well as synthetic water-soluble Polymers, such as. Polyvinyl alcohol, polyvinylpyrrolidone, polyalkylene glycols, polyaspartic and polyacrylates.

In usually the surface modifiers become in a concentration of 0.1 to 50, but preferably 1 to 20 wt .-%, based on the calcium salts used.

When Surface modifier Especially preferred are the nonionic surfactants in in an amount of 1 to 20% by weight, based on the weight of the calcium salt. To be particularly effective, the nonionic surfactants of Type of the alkyl C8-C16 (oligo) glucosides and the ethoxylates of the hardened castor oil.

• a. in Wasser schwerlösliche Calciumsalze, wobei die Calciumsalze in Form von einzelnen Kristalliten oder in Form von Partikeln, umfassend eine Mehrzahl besagter Kristallite, mit einem mittleren Teilchendurchmesser im Bereich von unter 1000 nm, bevorzugt unter 300 nm vorliegen, und
• b. eine Polymerkomponente,

wobei die Partikel im Kompositmaterial vorwiegend stäbchen- und/oder plättchenförmig, bevorzugt vorwiegend plättchenförmig sind.According to a particular embodiment, the composite materials according to the invention comprises

• a. sparingly soluble calcium salts in water, wherein the calcium salts in the form of individual crystallites or in the form of particles comprising a plurality of said crystallites having an average particle diameter in the range of less than 1000 nm, preferably less than 300 nm, and
• b. a polymer component,

wherein the particles in the composite material predominantly rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped.

Under Composite materials are understood to be composites which the comprising components mentioned under a) and b) and microscopically represent heterogeneous, but macroscopically appearing aggregates, and in which the crystallites or particles of the calcium salts the scaffolding the polymer component associated. The proportion of polymer components in the composite materials is between 0.1 in the composite material and 80% by weight, preferably between 10 and 60, especially between 30 and 50 wt .-% based on the total weight of the composite material.

The composite materials according to the invention are therefore structured composite materials in the counter to the RZ Wang et al. described composite of hydroxyapatite and collagen, 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 methods described in RZ Wang et al. Hydroxylapatite particles present in the described hydroxyapatite-collagen composite have a size of 2-10 nm. Hydroxylapatite particles in this size range are assigned to the range of amorphous or partially X-ray amorphous substances.

One Another advantage of composite materials is that they are not tend to strong aggregation, so that they are in the production process better process. In particular, an improved dispersibility of the composite.

According to one particular embodiment the polymer component is selected from a protein component, polyelectrolytes and polysaccharides.

• – Alginsäuren
• – Pektinen
• – Carrageenan
• – Polygalakturonsäuren
• – Amino- und Aminosäurederivaten von Alginsäuren, Pektinen, Carrageenan und Polygalakturonsäuren
• – Polyaminosäuren, wie z. B. Polyasparaginsäuren
• – Polyaspartamiden
• – Nucleinsäuren, wie z. B. DNA und RNA
• – Ligninsulfonaten
• – Carboxymethylcellulosen
• – Amino- und/oder Carboxylgruppen-haltigen Cyclodextrin-, Cellulose- oder Dextran-Derivaten
• – Polyacrylsäuren
• – Polymethacrylsäuren
• – Polymaleinaten
• – Polyvinylsulfonsäuren
• – Polyvinylphosphonsäuren
• – Polyethyleniminen
• – Polyvinylaminen

sowie Derivaten der vorstehend genannten Stoffe, insbesondere Amino- und/oder Carboxyl-Derivaten. Bevorzugt werden im Rahmen der vorliegenden Erfindung Polyelektrolyte eingesetzt, die zur Salzbildung mit zweiwertigen Kationen geeignete Gruppen tragen. Insbesondere eignen sich Carboxylat-Gruppen tragende Polymere.A preferred embodiment of the invention is that polyelectrolytes are used as the polymer component. Suitable polyelectrolytes for the purposes of the invention are polyacids and polybases, it being possible for the polyelectrolytes to be biopolymers or else synthetic polymers. Thus, the inventive compositions contain, for example, one or more polyelectrolytes selected from

• - Alginic acids
• - pectins
• - carrageenan
• - Polygalacturonic acids
• Amino and amino acid derivatives of alginic acids, pectins, carrageenan and polygalacturonic acids
• - Polyamino acids, such as. B. polyaspartic acids
• - polyaspartamides
• - Nucleic acids, such as. B. DNA and RNA
• - lignosulfonates
• - carboxymethylcelluloses
• - Amino- and / or carboxyl-containing cyclodextrin, cellulose or dextran derivatives
• - polyacrylic acids
• - polymethacrylic acids
• - polymaleinates
• - Polyvinylsulfonic acids
• - Polyvinylphosphonic
• - Polyethyleneimines
• - Polyvinylamines

and derivatives of the abovementioned substances, in particular amino and / or carboxyl derivatives. In the context of the present invention, preference is given to using polyelectrolytes which carry suitable groups for salt formation with divalent cations. In particular, polymers bearing carboxylate groups are suitable.

in the Particularly preferred polyelectrolytes according to the invention are polyaspartic acids, alginic acids, pectins, deoxyribonucleic acids, ribonucleic acids, polyacrylic and polymethacrylic acids.

All particularly preferred are polyaspartic acids having a molecular weight in the range between about 500 and 10,000 daltons, in particular 1000 up to 5000 daltons.

Another preferred embodiment of the invention is that polysaccharides are selected as the polymer component. In particular, these polysaccharides are selected from glucuronic acid and / or iduronic acid-containing polysaccharides. These are to be understood as meaning those polysaccharides which are composed inter alia of glucuronic acid, preferably D-glucuronic acid, and / or iduronic acid, in particular L-iduronic acid. A constituent of the carbohydrate skeleton is formed by glucuronic acid or iduronic acid. The iduronic acid isomeric to glucuronic acid has the other configuration at the C5 carbon atom of the ring. Glucuronic acid and / or iduronic acid-containing polysaccharides are preferably to be understood as meaning those polysaccharides which contain glucuronic acid and / or iduronic acid in a molar ratio of from 1:10 to 10: 1, in particular from 1: 5 to 5: 1, particularly preferably 1: 3 to 2: 1, based on the sum of the other monosaccharide building blocks of the polysaccharide. Advantageously, by the anionic carboxyl groups of the glucuronic acid and / or iduronic acid-containing polysaccharides a particularly good change be achieved with the calcium salt, which lead to a particularly stable and at the same time particularly good biomineralizing composite material. Examples of suitable polysaccharides are the glucuronic acid and / or iduronic acid-containing glycosaminoglycans (also referred to as mucopolysaccharides), microbially produced xanthan gum or welan or gum arabic, which is obtained from acacia.

One Advantage of the composite materials according to the invention is the special stability in aqueous Systems without the addition of dispersing aids such as, for example, polyvalent Alcohols (such as glycerol or polyethylene glycols).

According to one particularly preferred embodiment the polymer component is selected from a protein component, preferably from proteins, protein hydrolysates and their derivatives.

When In principle, proteins all come within the scope of the present invention Proteins independent of their origin or production. Examples of proteins of animal origin are kerstin, elastin, collagen, fibroin, albumin, Casein, whey protein, placental protein. According to the invention preferred out of these are collagen, kerstin, casein, whey protein, proteins of vegetable origin such as wheat and wheat germ protein, Rice protein, soy protein, oat protein, pea protein, potato protein, Almond protein and yeast protein can according to the invention also be preferred.

Within the scope of the present invention, protein hydrolysates are degradation products of proteins such as, for example, collagen, elastin, casein, kerstin, almond, potato, wheat, rice and soy protein, which are formed by acidic, alkaline and / or enzymatic hydrolysis of the proteins themselves or their degradation products such as gelatin. For the enzymatic degradation all hydrolytic enzymes are suitable, such as. B. alkaline proteases. Further suitable enzymes and enzymatic hydrolysis processes are described, for example, in US Pat K. Drauz and H. Waldmann, Enzymes Catalysis in Organic Synthesis, VCH-Verlag, Weinheim 1975 , In the degradation of the proteins are cleaved into smaller subunits, the degradation can go through the stages of the polypeptides on the oligopeptides to the individual amino acids. Among the less degraded protein hydrolysates is, for example, the preferred within the context of the present invention gelatin, which may have molecular weights in the range of 15000 to 250000 D. Gelatin is a polypeptide obtained primarily 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, that is, a more hydrolyzed gelatin gives a lower viscosity solution. The gel strength of the gelatin is given in Bloom numbers. In the enzymatic cleavage of the gelatin, the polymer size is greatly reduced, resulting in very low Bloom numbers.

Furthermore, in the context of the present invention, preference is given to protein hydrolyzates which are customary in cosmetics and have an average molecular weight in the range from 600 to 4000, particularly preferably from 2000 to 3500. Overviews of the preparation and use of protein hydrolysates are, for example, from G. Schuster and A. Domsch in soaps oils Fette Wachse 108, (1982) 177 and Cosm.Toil. 99, (1984) 63 , from HW Steisslinger in Parf.Kosm. 72, (1991) 556 and F. Aurich et al. in Tens.Surf.Det. 29, (1992) 389 published. Preferably, protein hydrolysates of collagen, kerstin, casein and vegetable proteins are used according to the invention, for example those based on wheat gluten or rice protein, their preparation in the two German patents DE 195 02 167 C1 and DE 195 02 168 C1 (Henkel) is described.

Under Protein hydrolyzate derivatives are within the scope of the present invention chemically and / or chemoenzymatically modified protein hydrolysates to understand such as those under the INCI names Sodium Cocoyl Hydrolyzed Wheat Protein, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein, Potassium Cocoyl Hydrolyzed Collagen, Potassium Undecylenoyl Hydrolyzed Collagen and Laurdimonium Hydroxypropyl Hydrolyzed collagen known compounds. Preferably according to the invention derivatives from protein hydrolysates of collagen, Kerstins and casein as well vegetable protein hydrolysates used such. B. Sodium Cocoyl Hydrolyzed Wheat Protein or Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein.

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

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

When Protein components preferred are all structure-forming proteins, Protein hydrolysates and protein hydrolyzate derivatives, among which such Protein components are understood to be due to their chemical Constitution to form certain three-dimensional spatial structures, those skilled in protein chemistry under the terms secondary, tertiary or also quaternary structure common are.

According to one Particularly preferred use is the protein component of the composite materials selected from collagen, gelatin, casein and their hydrolysates Gelatin, more preferably gelatin of type A, B or AB, in particular Gelatin of the type Acid bone.

According to one particularly preferred embodiment can Gelatins of type AB are used, which also under the name "acid-bone" - or "acid process ossein "-Gelatin and from ossein due to highly acidic process conditions getting produced.

ossein, as a collagen-containing starting material for the production of gelatin of type AB "acid bone "or" acid process ossein "is made as an extract of minced bones, especially bovine bone, possibly after degreasing and drying for one or more days (preferred at least one week and more) in aqueous solution, preferably cold acid diluted Acid (e.g. Hydrochloric acid), be incorporated to the inorganic bone components, in particular Hydroxyapatite and calcium carbonate. It results a sponge-like demineralized bone material, the Ossein.

The Collagen in the ossein is broken down by a digestion process denatured and released, in which the material is strongly acidic Conditions is treated.

The Production of gelatin from the raw materials mentioned finds by multiple extraction with aqueous solutions instead of. Preferably, before the extraction process, the pH of the solution be set. Especially preferred are several extraction steps with water or aqueous solutions with increasing solvent temperature.

composite materials those made of a slightly water-soluble Calcium salt can be obtained with gelatin of type AB (acid-bone) can, are particularly suitable for use in uses according to the invention.

Surprisingly has now been found that the composite materials, the gelatin of Type AB, "acid contain bone, have a particularly strong neomineralization. composite materials those made of a slightly water-soluble Calcium salt can be obtained with gelatin of type AB (acid-bone) can, are thus particularly suitable for use in bones and teeth (see. Examples). The composite materials according to the invention are therefore preferred for use in comparison to the said composites in particular for rapid closure of dentinal tubules, for Remineralization of the tooth material, for use in teeth and Bones for prevention and / or therapy of damage, the on external influences, in particular of body-related, chemical, physical and / or microbiological nature, e.g. in erosion, primary lesions and Initial caries and caries prophylaxis, to improve resistance to mechanical stress and generally to improve the cleaning properties the teeth and dental health in general.

The difficult according to the invention water-soluble Calcium salts and composite materials, including these, can by precipitation reactions from aqueous solutions water-soluble calcium salts and aqueous solutions water Phosphate and / or fluoride salts are prepared, wherein the precipitation in Case of the composite materials according to the invention in the presence of polymer components.

The Production of the composite materials according to the invention is preferably carried out in such a way that the polymer components in pure, dissolved or colloidal form of the neutral or alkaline aqueous phosphate and / or fluoride salt solution or the neutral or alkaline solution of the calcium salt the precipitation reaction enclosed become. Alternatively you can the polymer components in pure, dissolved or colloidal form submitted and subsequently successively in any order or simultaneously with the neutral or alkaline calcium salt solution as well as the neutral or alkaline phosphate and / or fluoride salt solution are added. Under neutral solutions should solutions with a pH between about 6.5 and about 7.5.

at the production process according to the invention can the merge the individual components in principle in all possible Sequences take place. The alkalizing agent used is preferably ammonia.

A another variant of the invention the manufacturing process is that one from the precipitation an acid solution a water-soluble Calcium salt together with a stoichiometric amount of a water-soluble Phosphate and / or fluoride salt or from an acidic solution of Hydroxylapatite with a pH below 5, preferably at a pH below of 3, by raising the pH with aqueous alkali or ammonia in the presence of the polymer components.

A Another method variant is that one nanoparticulate calcium salts in pure or dispersed form or by precipitation reactions from aqueous solutions water Calcium salts and aqueous solutions water Dispersions of nanoparticulate calcium salts prepared phosphate and / or fluoride salts with the polymer components, the latter preferably in dissolved or dispersed form, with the addition of any Order selected can be.

Prefers becomes the solution or dispersion of the polymer component and a dispersion of the nanoparticulate Added calcium salt.

at All said production process, the resulting dispersion of the composite material as required by methods known to those skilled in the art such as B. filtration or centrifugation of the solvent and the other ingredients the reaction mixture and separated by subsequent drying, z. B. by freeze-drying, isolated in solvent-free form become.

When solvent Water is used in all manufacturing processes, however, in individual steps of the production also organic solvents such as B. mono- or polyhydric alcohols having 1 to 4 carbon atoms or Glycerin can be used.

The Preparation of the calcium salts according to the invention or composite materials, including these, and especially those Composite materials with a protein component selected from Collagen, casein or gelatin, preferably gelatin of type AB, with surface-modified Crystallites and / or particles of calcium salts, may be analogous precipitation method as described above, but the precipitation of the nanoparticulate Calcium salts or composite materials in the presence of one or several surface modifiers he follows.

Prefers be first by a precipitation reaction between aqueous solutions of calcium salts and aqueous solutions of phosphate and / or fluoride salts in the presence of surface modifiers the surface modified nanoparticulate Calcium salts generated. these can subsequently be purified from by-products of the reaction mixture, for. B. by concentration under reduced pressure and subsequent dialysis. By stripping off the solvent can additionally a dispersion of the surface-modified Calcium salt with a solids content produced as desired become. Subsequently By adding the polymer components in pure, dissolved or colloidal form, again the order of addition is not critical and, if necessary, afterreaction at elevated temperature, preferably in the range between 50 and 100 ° C and for a duration of 1 to 100 Minutes, the composite material of surface-coated calcium salt and polymer components formed.

Especially suitable for the preparation of a calcium salt or composite material according to the invention, which predominantly platelet-shaped particles contains will the precipitation the calcium salt or the composite material at a pH between 5 and 9, preferably between 6 and 8, more preferably performed by 7.

Especially suitable for the preparation of a calcium salt or composite material according to the invention, which is predominantly rod-shaped particles contains will the precipitation the calcium salt or the composite material at a pH of greater or equal 9, preferably, between 9.5 and 14, especially preferably around 11 carried out.

A solution of a calcium salt with the polymer component is preferably initially introduced to form the preferred composite material according to the invention, and a phosphate solution is slowly added, the pH being between 5 and 9, preferably between 6 and 8, particularly preferably around 7. In a particularly preferred manner, the pH is corresponding to the addition of the phosphate solution by addition constant amounts of aqueous base kept constant.

For the preparation of dispersions of surface-modified calcium salts, other methods can be used, such as those in the German application DE 198 58 662.0 described.

The calcium salts according to the invention or composite materials, including these, and especially those Composite materials with a protein component selected from Collagen, casein or gelatin, more preferably gelatin from Type A, B or AB, in particular gelatin of the type acid bone, in particular the of hydroxyapatite, fluorapatite and calcium fluoride are suitable as a mineralizing component for the preparation of compositions for cleaning and / or care of the teeth.

By the structured form, in particular of the preferred composites and the particle size of the contained therein Calcium compounds may have the effect of strengthening the enamel and the closure of lesions and dentin tubules especially fast and complete respectively.

Farther can calcium salts according to the invention or composite materials, including these, and especially those Composite materials with a protein component selected from Collagen, casein or gelatin, more preferably gelatin from Type A, B or AB, in particular gelatin of the acid bone type, as neo- or remineralizing components in compositions for strengthening of the enamel are used.

A further use of the calcium salts or composite materials, comprising these, and in particular such composite materials with a protein component selected from collagen, casein or gelatin, more preferably gelatin type A, B or AB, in particular gelatin of the type Acid bone, takes place as the biomineralisation inducing or promoting component for the treatment of tooth or bone defects.

The calcium salts according to the invention or composite materials, including these, and especially those Composite materials with a protein component selected from Collagen, casein or gelatin, more preferably gelatin from Type A, B or AB, in particular gelatin of the type Acid bone, or Compositions containing these are also for coating of implants.

A Use of the calcium salts according to the invention or composite materials, including these, and especially those Composite materials with a protein component selected from Collagen, casein or gelatin, more preferably gelatin from Type A, B or AB, in particular gelatin of the type Acid bone, or Compositions containing at least these, for smoothing the surface of teeth and / or Bone is also preferred.

The calcium salts according to the invention or composite materials, including these, and especially those Composite materials with a protein component selected from Collagen, casein or gelatin, more preferably gelatin from Type A, B or AB, in particular gelatin of the type acid bone, in particular the of hydroxyapatite and fluorapatite, may be the biomineralization induce or promote bone tissue. They are therefore suitable furthermore as a biomineralizing component for the production of Compositions for the recovery or regeneration of bone material, such as B. of compositions for the treatment of bone defects and bone burs as well as for promotion ingrowth of implants.

The Compositions of the invention contain the poorly water-soluble Calcium salts and / or their composite materials in an amount of 1 to 99 wt .-%, preferably in an amount of 2 to 70 wt .-%, especially preferably 3 to 50 wt .-%, particularly preferably in an amount from 5 to 20% by weight, based on the amount of the composition. Dependent on of the specific application and the associated requirements For consistency, processability, etc., it may be preferable that the composition the sparingly soluble Calcium salts and / or their composite materials in an amount of For example, 5, 6, 7, 8, 9, 10 12, or 15 wt .-%.

In a preferred embodiment, the composition according to the invention may additionally contain 0.1 to 70% by weight of calcium hydroxide and / or 0.01 to 10% by weight of clove oil. Particularly preferred are compositions containing both calcium hydroxide and clove oil in said concentrations. Such compositions are particularly suitable for preparing surfaces of the tooth for a filling, an inlay or the like and thus the adhesion of the fillings, the inlays or the like to improve on the tooth. The clove oil serves in particular as an antibacterial agent that can complicate or prevent the formation of decay under the filling or inlay.

According to the invention preferred are compositions that support the remineralization process by the hardly soluble in water Calcium salt and / or the composite materials comprising these, in addition 0.1 to 10 wt .-%, preferably 0.1 to 5 wt .-% and in particular 0.1 to 3% by weight of a remineralization promoting component, respectively based on the total weight of the agent.

The Remineralization promotion component promotes in the inventive compositions the remineralization of the enamel and the closure of dental lesions and is selected from fluorides, microparticulate Phosphate salts of calcium such. Calcium glycerol phosphate, Calcium hydrogenphosphate, hydroxyapatite, fluorapatite, F-doped Hydroxyapatite, dicalcium phosphate dihydrate and calcium fluoride. But also magnesium salts such. For example, magnesium sulfate, magnesium fluoride or magnesium monofluorophosphate have a remineralizing effect.

According to the invention preferred Remineralization components are magnesium salts.

suitable embodiments of the compositions according to the invention are solid, liquid or semi-liquid Compositions The compositions according to the invention contain according to another preferred embodiment additional Ingredients such as emulsifiers (or surfactants), humectants, Binders, thickeners, flavorings, buffer substances, Dyes, preservatives and active ingredients against dental and Gum disease.

For an improvement the cleaning effect and the foaming and in particular the Aufziehverhaltens of the compositions of the invention are usually surfactants Surfactants or surfactant mixtures used. They promote fast and complete resolution and Distribution of toothpastes in the oral cavity and support at the same time mechanical plaque removal, especially at the sites with a toothbrush difficult to access are. About that favor they are water insoluble Substances, for example of aromatic oils, stabilize the polish dispersion and support the Anticaries effect of fluorides.

in principle can anionic surfactants, zwitterionic and ampholytic surfactants, nonionic surfactants, cationic surfactants or mixtures thereof Compounds can be used as surfactants in toothpaste formulations. Included in the invention Toothpastes preferably at least one surfactant from the group of anionic surfactants.

The Surfactant or the surfactant mixture is customary in the compositions according to the invention in an amount of 0.1-10 Wt .-%, preferably 0.3-7 Wt .-% and in particular 1-5 Wt .-%, based on the total weight of the composition used.

Anionic surfactants

suitable Surfactants with good foaming action are anionic surfactants, too a certain enzyme-inhibiting effect on the bacterial metabolism the plaque have.

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

Preference is given to the use of at least one anionic surfactant, in particular a sodium lauryl alkyl sulfate having 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 may be preferred according to the invention to use zwitterionic and / or ampholytic surfactants, preferably in combination with anionic surfactants. As zwitterionic surfactants such oberflä denotes chenaktiven compounds which carry in the molecule at least one quaternary ammonium group and at least one carboxylate and a sulfonate group. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammoniumglycinate, for example the Trimethylammoniumglycinat, Kokosalkyldimethylammoniumglycinat, N-acylamino-propyl-N, N-dimethyl-ammoniumglycinate, for example Kokosacylaminopropyldimethyl-ammoniumglycinat, and 2-alkyl 3-carboxymethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethylglycinate. Particularly preferred is the known under the CTFA name Cocamidopropyl Betaine fatty acid amide derivative. Such products are available, for example under the name Tego betaine ^® BL 215 and ZF 50 and Genagen ^® CAB commercially.

Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C ₈ -C ₁₈ -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodiopropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine. In addition to the ampholytic, quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

Nonionic surfactants

• – Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe;
• – C₁₂-C₁₈-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin;
• – Glycerinmono- und -diester und Sorbitanmono- und -diester von gesättigten und ungesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen und deren Ethylenoxidanlagerungsprodukte;
• – Alkylmono- und -oligoglycoside mit 8 bis 22 Kohlenstoffatomen im Alkylrest und deren ethoxylierte Analogas;
• – Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• – Polyol- und insbesondere Polyglycerinester, wie z.B. Polyglycerinpolyricinoleat, Polyglycerinpoly-12-hydroxystearat oder Polyglycerindimerat.

Nonionic surfactants are particularly suitable according to the invention for promoting the cleaning action. Particular preference is given to those nonionic surfactants which are selected from at least one of the following groups:

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group;
• - C ₁₂ -C ₁₈ fatty acid mono- and diesters of addition products 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 having 6 to 22 carbon atoms and their ethylene oxide addition products;
• - Alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogues;
• - Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• Polyol and in particular polyglycerol esters, such as, for example, polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate.

• – Anlagerungsprodukte von 2 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• – Partialester auf Basis linearer, verzweigter, ungesättigter bzw. gesättigter C₈-C₂₂-Fettsäuren, Ricinolsäure sowie 12-Hydroxystearinsäure und Glycerin, Polyglycerin, Pentaerythrit, Dipentaerythrit, Zuckeralkohole (z.B. Sorbit), Sucrose, Alkylglucoside (z.B. Methylglucosid, Butylglucosid, Laurylglucosid) sowie Polyglucoside (z.B. Cellulose);
• – Mono-, Di- und Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEGalkylphosphate und deren Salze;
• – Wollwachsalkohole;
• – Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;
• – Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol gemäß DE-PS 11 65 574 und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin oder Polyglycerin sowie
• – Polyalkylenglycole.

Also suitable are mixtures of compounds of several of these classes of substances;

• - addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• - Partial ester based on linear, branched, unsaturated or saturated C ₈ -C ₂₂ fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (eg sorbitol), sucrose, alkyl glucosides (eg methyl glucoside, butyl glucoside, lauryl glucoside ) as well as polyglucosides (eg cellulose);
• - Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEGalkylphosphate 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 11 65 574 and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol and
• - Polyalkylene glycols.

The addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products and are preferred according to the invention. These are homolog mixtures whose mean degree of alkoxylation corresponds to the ratio of the molar amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C ₁₂ -C ₁₈ fatty acid mono- and diesters of addition products of ethylene oxide with glycerol are made DE-PS 20 24 051 known as a refatting agent for cosmetic preparations.

C ₈ -C ₁₈ -Alkylmono- and -oligoglycoside, their preparation and their use are known from the prior art, for example US-A-3,839,318 . DE-A-20 36 472 . EP-A-77 167 or WO-A-93/10132 known. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With regard to the glycoside radical, both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of preferably approximately 8 are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products. An alkyl (oligo) glycoside of the formula RO (C ₆ H ₁₀ O) _x -H in which R is an alkyl group having 12 to 14 C atoms and x is preferably suitable as the alkyl (oligo) glycoside Mean value of 1 to 4 has.

A particularly preferred example of a according to invention, the nonionic surfactant may be mentioned, for example, PEG-glyceryl stearate, sold under the name Tagat ^® S commercially.

Humectants become common in dental cosmetics for protection against dehydration and for consistency control and cold stability of the products used. You can but also for suspension and flavoring or gloss influence.

Usually will as humectants toxicologically harmless polyols, such as sorbitol, Xylitol, glycerol, mannitol, 1,2-propylene glycol or mixtures thereof used, but also polyethylene glycols having molecular weights of 400-2000 can serve as humectant components in toothpastes.

Prefers is the combination of several humectant components, wherein the combination of glycerin and sorbitol containing 1,2-propylene glycol or polyethylene glycol is to be regarded as particularly preferred.

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

The Compositions of the invention additionally contain at least in a preferred embodiment a binder or thickener. These have a consistency-regulating effect and continue to prevent the separation of the liquid and solid components.

Your Use amounts in the compositions of the invention 0.1-5 Wt .-%, preferably 0.1-3 Wt .-% and in particular 0.5-2 Wt .-%.

used become according to the invention for example natural and / or synthetic water-soluble polymers such as alginates, carrageenans, agar-agar, guar gum, gum arabic, Succinoglycan gum, guar gum, locust bean gum, tragacanth, karaya gum, Xanthan, pectins, cellulose and their ionic and non-ionic Derivatives such as carboxymethylcellulose, hydroxyethylcellulose or methylhydroxypropyl cellulose, hydrophobically modified celluloses, Strength- and starch ethers.

And water-soluble carboxyvinyl polymers (for example Carbopol ^® types), polyvinyl alcohol, polyvinylpyrrolidone, and higher molecular weight polyethylene glycols (particularly those having molecular weights from 10 ² -10 ⁶ D) are suitable as binder or thickener. Similarly, phyllosilicates and finely divided silicas (Aerogelkieselsäuren and fumed silicas) fulfill this function.

In a particularly preferred embodiment contains the composition according to the invention 0.001 to 50% by weight of a salt of carboxymethylcellulose, in particular a sodium salt.

In a further preferred embodiment contains the inventive composition a or more buffer substances. These substances serve to pH during the application and the effect of the composition of the invention largely to keep constant. Particularly preferred are buffer systems, the have their buffer range in the range between pH = 5 and 10, in particular phosphate buffer systems.

In a further preferred embodiment, the compositions according to the invention contain additional active substances against tooth and gum diseases. Among such agents are inventions According to the anticaries agents, antimicrobial agents, tartar inhibitors, flavorings or any combination of these substances.

Anti-caries agents

Fluorine compounds, preferably from the group of fluorides or monofluorophosphates in an amount of 0.1-0.5% by weight of fluorine, are especially suitable for controlling and preventing caries. Suitable fluorine compounds are, for. For example, sodium fluoride, potassium fluoride, stannous fluoride, disodium monofluorophosphate (Na ₂ PO ₃ F), dipotassium monofluorophosphate or the fluoride of an organic amino compound. Monofluorophosphates are compounds which do not release the fluoride directly to a predominant extent, but only in combination with activators, for example the enzymes contained in the healthy saliva, which release fluoride. Accordingly, such compounds can be referred to as precursors for water-soluble fluoride.

Anti-plaque agents

According to the invention preferred Preparations, in particular oral and dental care and cleaning preparations, are characterized in that they additionally Antiplaque agents, preferably methyl p-hydroxybenzoate, ethyl or propyl ester, sodium sorbate, sodium benzoate, bromochlorophen, Triclosan, phenyl salicylic acid ester, Biguanids z. As chlorhexidine, thymol, preferably in amounts of 0.1 to 5 wt .-%, preferably from 0.25 to 2.5 wt .-% and in particular from 0.5 to 1.5% by weight, based in each case on the total agent, contain.

Antimicrobial agents

When antimicrobial component are suitable for. Phenols, resorcinols, Bisphenols, salicylanilides and -amides and their halogenated derivatives, halogenated carbanilides and p-hydroxybenzoic acid esters.

Under the antimicrobial components are particularly suitable which inhibit the growth of plaque bacteria. 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'-trichloro-2'-hydroxydiphenyl ether (Triclosan) are 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 (hexetidine) Zinc and copper ions also act antimicrobial, with synergistic Effects especially in combination with hexetidine and triclosan occur. Also quaternary Ammonium compounds, such as. Cetylpyridinium chloride, benzalkonium chloride, Domiphen bromide and dequalinium chloride can be used. As antimicrobial octapinol, octenidine and sanguinarine have also been effective.

The antimicrobial agents are preferably used in amounts of 0.01-1 wt .-% in the inventive compositions. Irgacare ^® MP is particularly preferably used in an amount of 0.01-0.3 wt .-%.

Tartar inhibitors

Tartar is mineral deposits that are very similar to natural tooth enamel. In order to inhibit calculus formation, substances are added to the dentifrices according to the invention which specifically intervene in crystal nucleation and prevent existing germs from growing on. These are, for example, condensed phosphates, which are preferably selected from the group of tripolyphosphates, pyrophosphates, trimetaphosphates or mixtures thereof. They are used in the form of their alkali metal or ammonium salts, preferably in the form of their sodium or potassium salts. Aqueous solutions of these phosphates typically react alkaline, so that the pH value of the dentifrice according to the invention is adjusted to values of 7.5-9, if appropriate by addition of acid. As acids can be z. As citric acid, phosphoric acid or acid salts, for. B. NaH ₂ PO ₄ can be used. The desired pH of the dentifrice can also by addition of acidic salts of the condensed phosphates, ie z. B. K ₂ H ₂ P ₂ O ₇ , can be adjusted.

Also Mixtures of various condensed phosphates and / or hydrated Salts of the condensed phosphates can be used according to the invention. Tartar inhibitors usually become in amounts of 0.1-5 Wt .-%, preferably 0.1-3 Wt .-% and in particular 0.1-2 % By weight used in the compositions according to the invention.

Further suitable tartar inhibitors are organophosphonates such as 1-azacycloheptane-2,2-diphosphonate (Na salt), 1-hydroxyethane-1,1-diphosphonate (Na salt) and zinc citrate.

Agents against hypersensitive teeth

Preferably contain the compositions of the invention continue active 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.

The Eugenol can with aromatic oils may be included mixed in the compositions. It is preferred in the form of clove bud oil contained in the compositions.

Preferably contain the compositions of the invention 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 Form of clove bud oil.

flavorings

Preferably contain the compositions of the invention Flavors to which z. Sweetening and / or flavoring oils.

When sweeteners For example, saccharinates (especially sodium saccharinate) are suitable, Cyclamates (especially sodium cyclamate) and sucrose, lactose, Maltose or fructose.

When aromatic oils come all for composition SPMS natural and synthetic flavors in question. Natural flavors can be both in the form of the essential oils isolated from the drugs (mixture) as well as in the form of the individual components isolated therefrom become. Preferably at least one aromatic oil from the group of peppermint oil, curly mint oil, aniseed oil, star anise oil, caraway oil, eucalyptus oil, fennel oil, cinnamon oil, clove oil, geranium oil, sage oil, pimento oil, thyme oil, marjoram oil, basil oil, citrus oil, Gaultheria oil or one / more containing isolated or synthetically produced components of these oils be. The most important components of the oils mentioned are z. Menthol, carvone, Anethole, cineole, eugenol, cinnamaldehyde, caryophyllene, geraniol, citronellol, Linalool, salves, thymol, terpinene, terpinol, methylchavicol and Methyl salicylate. Other suitable flavors are z. For example, menthyl acetate, Vanillin, ionone, linalyl acetate, rhodinol and piperitone.

• • Vitamine, z. B. Retinol, Biotin, Tocopherol, Ascorbinsäure und deren Derivate (z. B. Ester, Salze);
• • Pigmente, z. B. Titandioxid oder Zinkoxid;
• • Gefärbte Pigmentpartikel, beispielsweise gefärbte Kieselsäurepartikel, wie sie z. B. unter der Verkaufsbezeichnung Sorbosil^®BFG 51, BFG 52 und BFG 53 oder Sorbosil^®2352 im Handel sind. Es können auch Gemische unterschiedlich gefärbter Pigmentpartikel verwendet werden. Solche, z. B. kräftig orange, rot oder blau gefärbten Gelkieselsäure-Partikel können in Mengen von 0,1–1,0 Gew.-% in den erfindungsgemäßen Mitteln enthalten sein;
• • Bleichmittel wie beispielsweise Wasserstoffperoxid und Wasserstoffperoxid-Vorstufen;
• • Farbstoffe;
• • pH-Stellmittel und Puffersubstanzen, z. B. Natriumcitrat, Natriumbicarbonat oder Kalium- und Natriumphosphate,
• • Konservierungsmittel, z.B. p-Hydroxybenzoesäuremethyl-, ethyl- oder -propylester, Natriumsorbat, Natriumbenzoat, Bromchlorophen oder Triclosan;
• • wundheilende und entzündungshemmende Stoffe wie z. B. Allantoin, Harnstoff, Panthenol, Azulen oder Kamillenextrakt, Acetylsalicylsäure-Derivate, Alkali-Rhodanide;
• • Mineralsalze wie Zink-, Magnesium- und Mangansalze, beispielsweise -sulfate.

Finally, other common adjuvants may be included to improve the stability and sensory properties of the compositions. Such aids are, for example:

• • vitamins, eg. Retinol, biotin, tocopherol, ascorbic acid and their derivatives (eg, esters, salts);
• • pigments, eg. For example, titanium dioxide or zinc oxide;
• Colored pigment particles, for example colored silica particles, as described e.g. B. under the sales name Sorbosil ^® BFG 51, BFG 52 and BFG 53 or Sorbosil ^® 2352 are commercially available. Mixtures of differently colored pigment particles can also be used. Such, z. B. strongly orange, red or blue colored gel silica particles may be present in amounts of 0.1-1.0 wt .-% in the inventive compositions;
• Bleaching agents such as hydrogen peroxide and hydrogen peroxide precursors;
• • dyes;
• • pH adjusting agents and buffer substances, eg. Sodium citrate, sodium bicarbonate or potassium and sodium phosphates,
• Preservatives, eg methyl, ethyl or propyl p-hydroxybenzoate, sodium sorbate, sodium benzoate, bromochlorophene or triclosan;
• • wound healing and anti-inflammatory substances such. Allantoin, urea, panthenol, azulene or chamomile extract, acetylsalicylic acid derivatives, alkali rhodanides;
• Mineral salts such as zinc, magnesium and manganese salts, for example sulphates.

All of these optional dentifrice ingredients are contained together in an amount of about 2 to 10% by weight, based on the total weight, in the compositions of the invention. Preparations to be used according to the invention, preferably oral and dental care products, in particular the toothpastes, may also contain the insensitivity of the teeth-enhancing substances, for example potassium salts such. As potassium nitrate, potassium citrate, potassium chloride, potassium bicarbonate and potassium oxalate. OF INVENTION According to preferred oral and dental care and cleaning agents are characterized in that they the insensitivity of the teeth-enhancing substances, preferably potassium salts, more preferably potassium nitrate and / or potassium citrate and / or potassium chloride and / or potassium bicarbonate and / or potassium oxalate, preferably in amounts of From 0.5 to 20% by weight, particularly preferably from 1.0 to 15% by weight, more preferably from 2.5 to 10% by weight and in particular from 4.0 to 8.0% by weight, in each case based on the total agent included.

Prefers continue to be preparations, in particular oral and dental hygiene and cleanser that enhances the insensitivity of the teeth Substances, preferably potassium salts, more preferably potassium nitrate and / or potassium citrate and / or potassium chloride and / or potassium bicarbonate and / or potassium oxalate, preferably in amounts of 0.5 to 20 wt .-%, particularly preferably from 1.0 to 15% by weight, more preferably from 2.5 to 10% by weight, and in particular from 4.0 to 8.0 wt .-%, each based on the total Means, included.

Particularly according to the invention preferred oral and dental care and cleaning agents are characterized in that they 0.2 to 20 wt .-%, preferably 0.4 to 14 wt .-%, particularly preferably 0.5 to 3 wt .-% and in particular 0.6 to 2 wt .-% of at least one contain bioactive glass.

The to be used according to the invention Oral and dental care and cleaning agent of this embodiment contain bioactive glass or glass powder or glass ceramic powder or composite materials comprising such a bioactive glass. Among glass powders are in the context of the present application also Granules and glass beads Understood.

by virtue of the requirements for the toxicological safety of the glass as well as their suitability for consumption the glass powder should be particularly pure be. The burden of heavy metals is preferably low. So is the maximum concentration in the field of cosmetic formulations preferably for Pb <20ppm, Cd <5ppm, As <5ppm, Sb <10ppm, Hg <1ppm, Ni <10ppm.

The unfused starting glass, which is contained directly in the preferred compositions according to the invention or is optionally used for the production of a glass ceramic which can be used according to the invention, contains SiO ₂ as a network former, preferably between 35-80% by weight. At lower concentrations, the spontaneous tendency to crystallize increases greatly and the chemical resistance decreases sharply. At higher SiO ₂ values, the crystallization stability may decrease and the processing temperature is significantly increased, so that the hot-forming properties deteriorate. Na ₂ O is used as a flux during melting of the glass. At concentrations of less than 5%, the melting behavior is adversely affected. Sodium is a constituent of the phases which form during the ceramization and, if high crystalline phase proportions are to be set by the ceramization, must be present in the glass in correspondingly high concentrations. K ₂ O acts as a flux when melting the glass. In addition, potassium is released in aqueous systems. If high potassium concentrations are present in the glass, potassium-containing phases such as calcium silicates are also eliminated. The P ₂ O ₅ content of silicate glasses, glass ceramics or composites can be used to adjust the chemical resistance of the glass and thus the ion emission in aqueous media. For phosphate glasses, P ₂ O _{5 is} network images. The P ₂ O ₅ content is preferably between 0 and 80 wt .-%. In order to improve the meltability, the glass may contain up to 25% by weight of B ₂ O ₃ . Al ₂ O ₃ is used to adjust the chemical resistance of the glass.

to reinforcement the antimicrobial, especially the antibacterial properties the glass ceramic can antimicrobial ions such. B. Ag, Au, I, Ce, Cu, Zn in Be contained concentrations of less than 5 wt .-%.

coloring Ions such. Mn, Cu, Fe, Cr, Co, V, may be used singly or in combination, preferably in a total concentration of less than 1% by weight be.

Usually the glass or the glass ceramic is used in powder form. The Ceramization can either be done with a glass block or glass ribbons done or with glass powder. After ceramization, the Glass ceramic blocks or ribbons are ground into powder. Was the powder ceramified, must if necessary be ground again to agglomerates, which during the Keramierungenschrittes arise are to remove. The grindings can be both dry as well in aqueous or non-aqueous Grinding media carried out become. Usually the particle sizes are smaller 500 μm. As appropriate Particles sizes <100 microns and <20 microns proved. Particularly suitable are particle sizes <10 microns as well as smaller 5 μm as well as less than 2 μm, see below.

The bioactive glasses or glass powder or glass ceramic powder or composite compositions contained in the preferred compositions according to the invention comprise glasses which preferably comprise the following components: SiO ₂ : 35-80% by weight, Na ₂ O: 0-35% by weight, P ₂ O ₅ : 0-80 wt%, MgO: 0-5 wt%, Ag ₂ O: 0-0.5 wt%, AgJ: 0-0.5 wt%, NaJ : 0-5 wt%, TiO ₂ : 0-5 wt%, K ₂ O: 0-35 wt%, ZnO: 0-10 wt%, Al ₂ O ₃ : 0-25 Wt .-% and B ₂ O ₃ : 0-25 wt .-%.

Furthermore, the base glass according to the above composition to achieve further effects such as color or UV filtering ions such as Fe, Co, Cr, V, Ce, Cu, Mn, Ni, Bi, Sn, Ag, Au, J individually or in total to be added to 10 wt .-%. A further glass composition may be as follows: SiO ₂ : 35-80 wt%, Na ₂ O: 0-35 wt%, P ₂ O ₅ : 0-80 wt%, MgO: 0-5 wt %, Ag ₂ O: 0-0.5 wt%, AgJ: 0-0.5 wt%, NaJ: 0-5 wt%, TiO ₂ : 0-5 wt% , K ₂ O: 0-35 wt .-%, ZnO: 0-10 wt .-%, Al ₂ O ₃ : 0-25 wt .-%, B ₂ O ₃ : 0-25 wt .-%, SnO : 0-5 wt%, CeO ₂ : 0-3 wt%, and Au: 0.001-0.1 wt%.

Particularly preferred oral and dental care and cleaning agents according to the invention are characterized in that the bioactive glass - based on its weight - has the following composition: SiO ₂ From 35 to 60% by weight, preferably 40 to 60% by weight, Na ₂ O 0 to 35% by weight, preferably From 5 to 30% by weight, K ₂ O 0 to 35% by weight, preferably 0 to 20% by weight, P ₂ O ₅ 0 to 10% by weight, preferably From 2 to 10% by weight, MgO 0 to 10% by weight, preferably 0 to 5% by weight, CaO 0 to 35% by weight, preferably From 5 to 30% by weight, Al ₂ O ₃ 0 to 25% by weight, preferably 0 to 5% by weight, B ₂ O ₃ 0 to 25% by weight, preferably 0 to 5% by weight, TiO ₂ 0 to 10% by weight, preferably 0.1 to 5 wt .-%.

As already mentioned above, the bioactive glass is preferably used in particulate form. Here are Particularly preferred oral and Zahnpflege- invention and detergent characterized in that the antimicrobial Glass particle sizes <10 microns, preferably from 0.5 to 4 μm, more preferably from 1 to 2 μm, having.

Especially when using the composite material according to the invention in products for the daily oral and dental care, especially in toothpaste, it is desirable that the process of remineralization as well as neomineralization particularly effective and fast.

to Coating of implants can the composite materials according to the invention for example, according to the standard method known in the art the dip coating or the plasma spraying are applied.

to Use as injectable bone replacement materials may be composite materials according to the invention be combined with suitable other substances, such. B. glycosaminoglycans or proteins, and with suitable solvents and auxiliaries such as z. B. a diluted aqueous Formulated phosphate buffer.

Next Synthetic organic thickeners are especially natural organic Thickener, in particular agar-agar, carrageenan, tragacanth, gum arabic, Alginates, pectins, polyoses, guar flour, carob kernel, Strength, Dextrins, gelatin and casein suitable. Of which modified natural substances are also preferred, especially carboxymethylcellulose and other cellulose ethers, hydroxyethyl cellulose and hydroxypropyl cellulose as well as core flour ethers. Synthetic organic thickeners, e.g. Polyether or inorganic thickeners such as polysilicic acids and / or Clay minerals (e.g., montmorillonites, zeolites or silicas) may also be used used according to the invention become.

According to one another preferred embodiment contain the compositions of the invention in addition to the calcium salt according to the invention and / or the composite materials comprising these, in addition at least a fluoride salt. Surprisingly It has been found that the addition of fluoride to a synergistic reinforcement the nucleating effect of the composite materials according to the invention lead. Especially preferred is the addition of sodium and / or potassium fluoride. at simultaneous addition of active compounds according to the invention and low Quantities of fluoride show an approximately five-fold synergistic amplification.

Prefers are amounts according to the invention from 0.01 to 1.2% by weight, in particular from 0.1 to 0.90% by weight of fluoride salt, dependent from the fluoride salt used (e.g., sodium fluoride). This corresponds an amount of fluoride ion used of 0.05 to 0.15% by weight, in particular from 0.08 to 0.12 wt .-%.

Prefers are amounts according to the invention from 0.05 to 0.15% by weight, in particular from 0.08 to 0.12% by weight Fluoride based on the amount of fluoride ions.

The The invention also includes kits containing at least one composition according to the invention and additionally a suitable applicator for the composition and / or a further component B and the Use of the kits according to the invention.

preferred Application forms are polishing devices, trays, brushes, sponges or other porous Application elements.

With a polishing facility, it is possible one or more of the compositions of the invention on a To polish the place to be treated on the tooth, that is, the Composition intimately in depressions, fissures, cracks, scratches, Dentintubuli, primary lesions, etc. contribute. This results in a seal of depressions, fissures, Cracks, scratches, dentinal tubules, fillings, shrink fillings and inlays possible. By sealing, the formation or the progression of erosive and / or carious Processes on the tooth reduced, or even prevented. Another Advantage is that it also eases inlays, fillings etc. effectively combated can be, as these are common is due to that by erosive and / or carious degradation of dental material Columns between the filling or form the inlay and the tooth base. This will increase the liability of fillings and inlays increasingly worse, which can eventually lead to a loss.

In a particularly preferred embodiment the kit according to the invention, used in particular when using a polishing device be, the composition of the invention deep, that is several microns to push into dentinal tubules. Here is the composition then act in the way that the dentinal tubules permanently closed become. Preferably, this may interact with the saliva, or another, calcium and / or phosphate ions containing solution expire. By doing so in this way the dentinal tubules not only on the dentin surface be closed by a protective layer, but the tubules are also closed to a depth of several microns, holds the Closure of the dentinal tubules and thus the desensitizing effect the treatment much longer, as previously known from the prior art.

In a likewise preferred embodiment The kit may contain a tray as an application form. Under a Tray becomes according to this Invention understood a device that at any point in the Mouth is attached, in the way that a tub or rail-like Storage area for the composition of the invention around one or more teeth is formed around, and the composition of the invention over a longer Period, for example 1 minute to 1 week, in contact with the tooth can be held. This makes it possible, the composition of the invention adapted to the desired Result controlled to act on the tooth.

From The invention also includes kits other than include the previously described application forms. These include, for example Brush, sponges or other, in any case, porous application forms.

The inventive kits can another component B include. These are preferred an etchant, a bleach, a water-soluble Calcium salt and / or a water-soluble phosphate salt.

In a particularly preferred embodiment, the kit contains as component B an acid etchant based on a phosphoric acid and / or an acidic polymer and / or an acidic gel. The pH of the acidic etchant is preferably in the range between 0 and 6. It has surprisingly been found that in the treatment of teeth with an acidic etchant and the composition according to the invention a particularly rapid neo- or remineralization of teeth is possible. This has the advantage that the desired effect can be observed after a short time and / or after only a few applications even after only a single application. Without wishing to be bound by this theory, the etching step possibly serves to form a particularly active tooth surface on which the composition according to the invention is particularly strong for the controlled formation of a mineral layer leads.

In a further preferred embodiment contains Component B is an alkaline etchant, preferably an aqueous alkaline solution of alkali metal and / or alkaline earth metal hydroxides having a pH between 8 and 14. Particular preference is given to solutions of sodium hydroxide, Potassium hydroxide and calcium hydroxide. It was found that one Treatment of tooth surfaces with an alkaline caustic and a composition of the invention to a particularly strong orderly formation of mineral Material on the tooth surface leads. This is a special protection and sealing of dentinal tubules, Fissures, scratches, primary lesions, Columns, fillings, shrink fillings and inlays possible.

The The invention therefore also encompasses the use of a kit according to the invention for the sealing of dentinal tubules, fissures, scratches, primary lesions, Columns, fillings, shrink fillings and inlays.

The Invention encompasses this also a method for sealing dentinal tubules, fissures, scratches, Primary lesions, Columns, fillings, shrink fillings and inlays, characterized in that a composition according to the invention on the tooth, the fillings or applying the inlays.

In a further preferred embodiment of the invention Component B of the kit is a bleach. The treatment of teeth with Bleach can cause disorder lead to the mineral structure of the tooth. It was found that one the injury the mineral structure by a treatment with a bleach This can be mitigated by bleaching treated teeth as well with a composition according to the invention treated. The order of the two treatments is arbitrary, this means, the treatment of the teeth with the composition of the invention can before, while or after treatment with the bleach. Prefers is an application of the composition according to the invention before or after the bleaching step.

The The invention therefore also encompasses a method for bleaching teeth, thereby characterized in that before, during or after applying the bleaching agent to the teeth before or after application, a composition according to the invention according to the Teeth interact leaves.

A likewise preferred embodiment includes kits containing in component B a solution of at least one soluble Calcium salt and / or a soluble Phosphate salt includes. Preference is given to components which have a solution both salts dissolved Form include.

The soluble calcium and / or phosphate salt should be understood as meaning those salts which are soluble in water at 20 ° C. to more than 0.1% by weight (1 g / l). Such suitable calcium salts are, for example, calcium chloride, calcium sulfate, calcium lactate, calcium malate, calcium citrate and calcium nitrate. The soluble phosphate salts are preferably selected from ammonium, alkali and / or alkaline earth metal salts, in particular Na ₃ PO ₄ , NaH ₂ PO ₄ , Na ₂ HPO ₄ , K ₃ PO ₄ , K ₂ HPO ₄ , KH ₂ PO ₄ , (NH ₄ ) ₃ PO ₄ and their mixed salts.

It has been found that a treatment of teeth with the composition according to the invention and a solution of soluble calcium salts and / or phosphate salts, preferably soluble calcium and phosphate salts, leads to a particularly rapid and effective orderly formation of mineral material on the tooth surface. Particularly preferred are so-called supersaturated solutions of calcium salts and phosphate salts, so such solutions are available for the product P = [Ca ^{2+] 5} x [PO4 ^{3-] 3} x [OH ^-] is greater than the solubility of hydroxyapatite, indicated on base the empirical formula is Ca ₅ (PO 4) ₃ (OH) for hydroxyapatite.

It has been shown to treat the tooth surface with the composition of the invention and the watery solution calcium and / or phosphate salts simultaneously or in any desired Order performed can be. With simultaneous use of both components is However, it is advantageous that the two components to immediately be stored separately from each other before use and only be mixed together immediately before use.

Especially it is preferred if initially a surface with the composition according to the invention and then with a supersaturated or near saturation limit concentrated solution a soluble Calcium and / or a soluble Phosphate salt is treated.

When wearing braces, dental braces and dental brackets, it can cause problems with tooth come over. Under dental braces and braces are understood according to this invention, devices for adjusting the tooth position, which are mechanically in the oral cavity, preferably attached to one or more teeth. These can be worn permanently or only temporarily. So-called brackets are devices with the same purpose understood, which are not only mechanically, but for example, partially or completely fixed by sticking to one or more teeth, and which are usually worn permanently.

Especially in brackets, but also in braces and braces it can through the deposition of plaque at the contact points between the devices and the tooth surface as well as in the immediate environment therefore to local demineralization and thus to a tooth damage come. The cause in particular, is that when wearing such devices the plaque by the usual Cleaning the teeth often not completely remove.

It it has been found that a treatment of these sites with a composition according to the invention, preferably when using one of the kits according to the invention, to a reduction or preventing demineralization at the contact points. An appropriate treatment may be before, during or after wearing the dental braces, braces or brackets are performed.

In a preferred embodiment the treatment is performed prior to the attachment of the device. hereby For example, a layer of mineralized material may be formed on the tooth surface so that the device is not on the tooth itself, but rather rests on the previously formed layer.

In a likewise preferred embodiment can the problems mentioned are reduced by having a Composition according to the invention on the parts of the braces or brackets, which after an attachment of the device rests on the tooth surface. The coating can then ganau in the places where the danger Demineralization is the greatest, for the formation of new mineral material or for a reduction contribute to the degradation of the tooth material.

Next the mentioned problems of degradation of dental material, for example caused by not removed plaque, wearing a Tooth clip or a bracket also to a non-pathological change the tooth surface to lead. Hereby changed itself the surface structure the tooth surface, without being harmed speak in the true sense. Nevertheless, such places often visible, for example caused by a change in the refractive index of the tooth material at these locations. It is therefore in many cases desired these visible, often white or brighter spots, for cosmetic reasons only remove or cover.

The The present invention therefore also encompasses a method of covering from non-carious changes the tooth surface, characterized in that the tooth with a composition according to the invention and / or a kit according to the invention is treated. As a result, the cover of the cosmetically undesirable Make possible so that the tooth surface again uniform acts.

The The following examples are intended to explain the subject matter of the invention in more detail:

Examples

1. Production of composite materials by precipitation reactions in the presence of the protein components

1.1 Preparation of an apatite-protein composite

For the preparation of the apatite-gelatin composite 2000 ml demineralized water is initially introduced into a thermostatically controlled at 25 ° C 4 l beaker in which 44.10 g (0.30 mol) CaCl ₂ .2H ₂ O (Fisher Chemicals pa) are dissolved. Separately, 35 g of gelatin (type AB, DGF-Stoess, Eberbach) are dissolved at about 50 ° C. in 350 ml of demineralized water. Both solutions are combined and stirred vigorously with a propeller stirrer. The pH is adjusted to 7.0 with dilute aqueous base.

300 ml of a 0.6 M (NH ₄ ) ₂ HPO ₄ solution previously adjusted to pH 7.0 are added to this gelatin and calcium salt solution with vigorous stirring over the course of 120 minutes. The pH is kept constant at pH 7.0 by the controlled addition of dilute aqueous base. After completion of the addition is stirred for a further 24 h.

Subsequently, will filled the dispersion in centrifuge cups and the solids content by centrifuging from the solution separated.

The dry composite material, contains 43 percent by weight organic, i. proteinaceous parts. This Proportion is by ashing the material at 800 ° C for 3 h or but by the expert Evaluation of a thermogravimetric measurement or by carbon combustion analysis (CHN) or determined by Kjeldal nitrogen analysis, in each case account for the proportion of ammonium chloride contamination.

It results in a predominantly platelet-shaped composite material.

2. Production of composite materials by incorporation of dispersions of surface-modified calcium salts in protein components

2.1 Composite material of hydroxyapatite and gelatin AB

At first were separate the solutions A and B produced.

solution A:

25.4 g calcium nitrate tetrahydrate and 8.50 g diammonium hydrogen phosphate were each dissolved in 100 g of deionized water. Both solutions were combined to form a white precipitate. After addition of 10 ml of 37% strength by weight HCl, a clear solution was obtained.

solution B:

200 ml of deionized water, 200 ml of 25 wt .-% aqueous ammonia solution and 20 g of Plantacare ^® 1200 were combined and cooled to 0 ° C in an ice bath. To form a hydroxyapatite precipitate, solution A was added to solution B with vigorous stirring. After removal of excess ammonia, the dispersion was purified by dialysis. The dispersion is then concentrated on a rotary evaporator by determination of the amount of water deposited so far that the solids content in the dispersion, calculated as hydroxylapatite, was 7.5% by weight.

These Dispersion was at room temperature to 100 ml of an analogous example 1.1 prepared 10 wt .-% aqueous solution of gelatin type AB (manufacturer: DGF Stoess) was added, then heated to 80 ° C and at this temperature Stirred for 5 minutes. Subsequently one left the mass to form the composite material at room temperature solidify.

Claims (52)

Composition, characterized in that it contains sparingly water-soluble calcium salts and / or their composite materials in an amount of 1 to 99 wt .-% based on the amount of the composition. Composition according to Claim 1, characterized that the calcium salts in the form of individual crystallites or in Form of particles comprising a plurality of said crystallites, with an average particle diameter in the range of less than 1000 nm, preferably below 300 nm. Composition according to one of the preceding claims, characterized characterized in that the said particles predominantly rod and / or platelet-shaped, preferred are predominantly platelet-shaped. Composition according to one of the preceding claims, characterized in that a single crystallite of the calcium salts and / or their composite materials have a thickness in the range of 2 to 50 nm and a length in the range of 10 to 150 nm, preferably a thickness of 2 to 15 nm and one length from 10 to 50 nm; particularly preferably a thickness of 3 to 11 nm and a length from 15 to 25 nm. Composition according to one of the preceding claims, characterized characterized in that the mean particle diameter of the particles in the range of less than 1000 nm, preferably less than 300 nm. Composition according to any one of the preceding claims, characterized in that the platelets chenförmigen particles have a length of 10 to 150 nm and a width of 5 to 150 nm. Composition according to one of the preceding claims, characterized characterized in that the particles have a length to width ratio of 1 to 4, preferably from 1 to 3, particularly preferably between 1 and 2. Composition according to one of the preceding claims, characterized in that the particles have an area of 0.1 × 10 ^-15 m ² to 90 × 10 ^-15 m ² , preferably an area of 0.5 × 10 ^-15 m ² to 50 × 10 ¹⁵ m ² , particularly preferably 1.0 × 10 ^-15 m ² to 30 × 10 ^-15 m ² , very particularly preferably 1.5 × 10 ^-15 m ² to 15 × 10 ^-15 m ² . Composition according to one of the preceding claims, characterized characterized in that the crystallites or particles of the present Calcium salts are coated by one or more surface modifiers. Composition according to one of the preceding claims, characterized characterized in that the calcium salts is selected from phosphates, fluorides and fluorophosphates optionally containing additional hydroxyl and / or carbonate groups can contain in particular from the group hydroxylapatite and fluorapatite. Composition according to one of the preceding claims, characterized characterized in that the composite material Calcium salts sparingly soluble in water, wherein the calcium salts in the form of individual crystallites or in the form of particles comprising a plurality of said crystallites a mean particle diameter in the range of less than 1000 nm, preferably below 300 nm, and A polymer component, includes, wherein the particles in the composite material predominantly rod and / or platelet-shaped, preferably predominantly platelet-shaped. Composition according to Claim 11, characterized that said polymer component of the composite material is selected from a protein component, polyelectrolytes and polysaccharides. Composition according to Claim 12, characterized that said polyelectrolytes are selected from the group consisting of is formed by polyaspartic acids, alginic acids, Pectins, deoxyribonucleic acids, ribonucleic acids, polyacrylic and polymethacrylic acids. Composition according to Claim 12, characterized that said polysaccharides are selected from glucuronic acid and / or iduronic Polysaccharides, preferably from Glykosaminoglykanen, in particular selected from chondroitin sulfates, heparin and hyaluronic acid, and xanthan. Composition according to Claim 12, characterized that said protein component is selected from proteins, protein hydrolysates and protein hydrolyzate derivatives. Composition according to Claim 15, characterized that said protein component is selected from collagen, gelatin, Kerstin, casein, wheat protein, rice protein, soy protein, almond protein and their hydrolyzates and hydrolyzate derivatives. Composition according to Claim 16, characterized that said protein component is selected from collagen, gelatin, Casein and its hydrolysates, preferably gelatin, more preferably Gelatin of the type A, B or AB, in particular gelatin of the acid type bone. A composition according to any one of claims 15 to 17, characterized in that the proportion of protein components in the composite material between 0.1 and 80 wt .-%, preferably between 10 and 60, in particular between 30 and 50 wt .-% based on the Total weight of the composite material is. Composition according to one of the preceding claims, characterized marked that in addition Fluoride are included. Composition according to one of the preceding claims, characterized in that it contains the sparingly water-soluble calcium salts and / or their composite materials in an amount of 2 to 70 Wt .-% based on the amount of the composition. A composition according to any one of the preceding claims characterized in that they are the sparingly water-soluble calcium salts and / or their composite materials in an amount of 3 to 50 wt .-% based included on the amount of the composition. Composition according to one of the preceding claims, characterized characterized in that they are the sparingly water-soluble calcium salts and / or their composite materials in an amount of 5 to 20 wt .-% based included on the amount of the composition. Composition according to one of the preceding claims, characterized that they additionally contains between 0.1 and 70 wt .-% calcium hydroxide. Composition according to one of the preceding claims, characterized that they additionally contains between 0.01 and 20 wt .-% clove oil. Composition according to one of the preceding claims, characterized characterized in that it contains between 0.1 and 70% by weight of calcium hydroxide and between 0.01 and 20% by weight of clove oil. Composition according to one of the preceding claims, characterized that they additionally at least one dampening solution, preferably glycerol and / or sorbitol contains. Composition according to one of the preceding claims, characterized that they additionally at least one polymer selected from alginates, carrageenans, agar-agarn, guar-gum, gum arabic, Succinoglycan gum, guar gum, locust bean gum, tragacanth, karaya gum, Xanthan, pectins, cellulose and their ionic and non-ionic Derivatives, starch and starch ethers contains. Composition according to one of the preceding claims, characterized characterized in that they contain from 0.001 to 50% by weight of a salt of Carboxymethylcellulose, preferably a sodium salt. Composition according to one of the preceding claims, characterized that they additionally one or more constituents selected from the group formed will be out - buffer substances, in particular phosphate buffer Water-soluble fluoride and / or a Preliminary stage for water-soluble fluoride - Dyes - Flavors - emulsifiers, especially PEG 40 - preservative - thickener contains. A composition according to any one of the preceding claims characterized in that they are substantially free of abrasives and cleaning agents is. A composition according to any one of claims 1 to 29, characterized in that they additionally 0 to 50 wt .-% at least of a particular Contains materials, preferably with particle sizes less than 5 ⧠m. A composition according to any one of claims 1 to 29 or 31, characterized in that particulate material selected is made of pumice stone, perlite and / or hydrated silica. Kit containing at least one composition according to one of the preceding claims and a suitable applicator for the composition and / or another component B. Kit according to claim 33, characterized in that the applicator a polishing device, a Trat, a sponge, a Brush or a porous one Is the order element. Kit according to one of claims 33 or 34, characterized that component B is an etchant, a bleach, a water-soluble Calcium salt and / or a water-soluble Phosphate salt includes. Kit according to one of claims 33 to 35, characterized that component B is selected from an acidic etchant Phosphoric acid, acidic polymers and acid gels. Kit according to one of claims 33 to 36, characterized that component B has a pH between 0 and 6. Kit according to one of claims 33 to 35, characterized that component B is an alkaline aqueous solution having a pH between 8 and 14. Kit according to one of Claims 33 to 38, characterized that component B is an aqueous solution a soluble Calcium salt and a soluble Phosphate salt includes. Use of the kit according to one of claims 33 to 39 for bleaching and / or whitening teeth. Use of the kit according to one of claims 33 to 39 for protecting the tooth from damage by wearing braces, Dental braces and dental brackets. Use of the kit according to one of claims 33 to 39 for the sealing of dentinal tubules, fissures, scratches, primary lesions, Columns, fillings, shrink fillings and / or inlays. Process for bleaching teeth, characterized that one before, while or after applying the bleaching agent to the teeth before or after application, a composition according to one the claims 1 to 32 on the teeth allow to act. Method for sealing dentinal tubules, fissures, Scratches, primary lesions, Columns, fillings, shrinkage fillings and inlays, characterized in that a composition according to one the claims 1 to 32 on the tooth, the fillings or applying the inlays. Method of protecting the tooth from damage and / or for reducing damage to the tooth by wearing braces, dental braces and dental brackets, characterized in that a composition according to one the claims 1 to 32 on the tooth and / or on the braces, Zahnklammer or Applying dental brackets. Method according to claim 45, characterized in that that the composition before attaching or after detachment of a Braces or a dental bracket is applied to the tooth. Method for covering non-carious changes the tooth surface, characterized in that the tooth with a composition according to one of the claims 1 to 32 and / or a kit according to any one of claims 33 to 39 is treated. Braces and brackets, characterized that they are in positions where they have direct contact with one tooth surface have, are coated with a composition according to one of claims 1 to 32. System, characterized in that it at least a composition according to a the claims 1 to 32 and an aqueous one solution a soluble Calcium salt and / or a soluble Phosphate salt includes. System according to claim 49, characterized that it is a water soluble Calcium salt and a water-soluble Phosphate salt contains. System according to one of claims 49 or 50, characterized in that the concentrations of the water-soluble calcium salt, of the water-soluble phosphate salt and of the hydroxydions present are so large that the product P = (Ca ²⁺ ) ⁵ × [PO 4 ^3- ] ³ × [ OH-] is greater than the solubility product of hydroxyapatite expressed on the basis of the empirical formula Ca ₅ (PO 4) ₃ (OH) for hydroxyapatite. System according to one of claims 49 to 51, characterized in that the composition according to any one of claims 1 to 32 and the calcium salts and / or phosphate salts containing solution ge separates from each other in different components.