WO2008061816A2 - Homogeneous, storage-resistant dispersions - Google Patents

Abstract

The invention relates to homogeneous, storage-resistant dispersions of calcium salts that are poorly soluble in water and/or polymers with at least one surfactant.

Description

 "Homogeneous storage-stable dispersions"

The invention relates to homogeneous, storage-stable dispersions of poorly water-soluble calcium salts and / or of polymers with at least one surfactant.

Calcium phosphate salts have long been added to the dentifrice and dentifrice formulations both as abrasive components and to promote remineralization of the enamel. This is especially true for hydroxyapatite and fluorapatite as well as for amorphous calcium phosphates and for brushite (dicalcium phosphate dihydrate). Also calcium fluoride has been described several times as a component of dentifrices and as a component for strengthening the enamel and for caries prophylaxis.

For these and many more applications, among other things the use as

Bone replacement materials require liquid formulations. Unfortunately, the currently known formulations show disadvantages in terms of application technology, in particular lack of dispersibility of the solid constituents.

The same applies to formulations based on hydroxylapatite and collagen composites. These composites of natural bone composition also suffer greatly from the lack of difficult dispersibility.

By way of example, a major disadvantage of the composite materials known from the prior art is that unfavorable dispersibility exists in many solvents, especially in water. This often means that these composite materials are poorly incorporated into the formulations required for their commercial application or have unsatisfactory dispersion stability in the preparations used for their use.

For example, it may be that an approximately 10 percent dispersion of an apatite gelatin composite containing as dispersing aids based on the total dispersion more than 10 wt.% Mono- or polyhydric alcohols (such as glycerol or polyethylene glycols), depending on the storage conditions sedimented within a few days.

Incidentally, the storage stability of such dispersions also depends on the raw materials provided. For example, a comparable dispersion in which the same raw materials - only from other batches - were used, within a few days lead to an increase in viscosity, up to a cut-resistant mass. It is very tedious to impossible to get the dependence on the raw materials used by suitable specifications for the raw materials under control.

It has now been found that it is possible to overcome the abovementioned disadvantages of the prior art by means of certain dispersions. Accordingly, the invention provides a homogeneous, storage-stable dispersion comprising a) at least one sparingly soluble in water calcium salt and / or b) at least one polymer component, preferably from the group of

Polyelectrolytes, and / or polysaccharides, and / or protein components c) more than 10 wt.% Of at least one surfactant, and wherein it is very particularly preferred that in the dispersion according to the invention the weight percentage of i) total amount of said surfactant c ) based on the j) total amount of the components mentioned under a) and b) makes up more than 60% and in particular the ratio of said total quantities according to i) to j) at 0.8: 1 to 5: 1, preferably at 1: 1 to 4: 1, and most preferably from 1: 1 to 3: 1.

Storage stability in the context of the present invention is intended to mean that the rheological properties of the dispersion over a storage time of 4, preferably 6 and in particular 8 weeks under various climatic conditions (at constant storage temperatures of -1 ^{0 0} C to + 4O ⁰ C or in alternating climate: each for 12 h 4O ⁰ C, 32.5 ⁰ C, 25 ⁰ C, 32.5 ⁰ C, 4O ⁰ C, 32.5 ⁰ C, etc.) does not change significantly. Furthermore, the solid should not sediment visible. In particular, the final viscosity of the resulting dispersions after a storage period of 4 weeks, preferably 6 and especially 8 weeks at the above climatic conditions measured at shear rates of 30 s ^"1 and at 2O ⁰ C at a value of one 20stel to 20 times and preferred a 10th to 10 times, especially a 5th to δfachen and in particular a 4tel to 4 times the viscosity starting value (at the beginning of the storage period) assume.

As sparingly soluble in water calcium salt should be understood as those salts which are soluble at 2O ⁰ C to less than 0.1 wt .-% (1 g / l) in water. 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 -y _{2 (x + y)} (PO ₄ ) _{3. X} (HPO ₄ ) _X (OH) ₁ ). Also suitable are carbonate-containing calcium phosphates (eg Ca ₅ _y _{2 (x + y + z)} (PO ₄ ) _{3 X. Z} (HPO ₄ ) _X (CO ₃ ) _Z (OH) _Ly ), calcium hydrogen phosphate (eg CaH (PO ₄ ) ^* 2 H ₂ O) and octacalcium phosphate (eg, Ca ₈ H ₂ (PO _{4) 6} ^* 5 H ₂ O). As the calcium salt may particularly preferably one or several salts in a mixture, selected from the group of phosphates, fluorides and fluorophosphates, which optionally additionally hydroxyl and / or carbonate groups contain k can be understood. Particularly preferred are hydroxyapatite and fluoroapatite. As stated in the foregoing, a preferred embodiment of the invention is that polyelectrolytes are used as the said polymer component. Suitable polyelectrolytes for the purposes of the present invention are polyacids and polybases, it being possible for the polyelectrolytes to be biopolymers or else synthetic polymers. For example, the compositions according to the invention preferably contain one or more polyelectrolytes selected from

alginic

pectins

carrageenan

polygalacturonic

Amino and amino acid derivatives of alginic acids, pectins, carrageenan and

polygalacturonic

Polyamino acids, such as. B. polyaspartic acids

Polyaspartamiden

Nucleic acids, such as. B. DNA and RNA

lignosulfonates

carboxymethyl

Amino- and / or carboxyl-containing cyclodextrin, cellulose or dextran derivatives

polyacrylic

polymethacrylic

Polymaleinaten

polyvinylsulfonic

polyvinylphosphonic

polyethyleneimines

Polyvinylamines and derivatives of the abovementioned substances, in particular amino and / or carboxyl

Derivatives. Very particular preference is given in the context of the present invention

Polyelectrolytes are used, which carry suitable groups for salt formation with divalent cations. In particular, polymers bearing carboxylate groups are suitable.

Polyelectrolytes preferred in the context of the invention are polyaspartic acids, alginic acids, pectins, deoxyribonucleic acids, ribonucleic acids, polyacrylic acids and polymethacrylic acids.

Very particularly preferred are polyaspartic acids having a molecular weight in the range between about 500 and 10,000 daltons, in particular 1000 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. Below are to understand such 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 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. 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.

In a likewise preferred embodiment, the polymer component is selected from a protein component, preferably from proteins, protein hydrolysates and their derivatives. In the context of the present invention, proteins are basically all proteins, irrespective of their origin or their production. Examples of proteins of animal origin are keratin, elastin, collagen, fibroin, albumin, casein, whey protein, placental protein. Preferred according to the invention from these are collagen, keratin, casein, whey protein, proteins of plant origin such as wheat and wheat germ protein, rice protein, soy protein, oat protein, pea protein, potato protein, almond protein and yeast protein may also be preferred according to the invention.

In the context of the present invention, protein hydrolysates are degradation products of proteins such as, for example, collagen, elastin, casein, keratin, 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 K. Drauz and H. Waldmann, Enzyme Catalysis in Organic Synthesis, VCH Verlag, Weinheim 1975. In the degradation, the proteins are cleaved into smaller subunits, the degradation via the stages of the polypeptides can go beyond 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, the protein hydrolysates used in cosmetics are preferably those having 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 hydrolyzates are described, for example, by G. Schuster and A. Domsch in soaps oils Fette Wachse 108, (1982) 177 and Cosm.Toil. 99, (1984) 63, by HW Steisslinger in Parf.Kosm. 72, (1991) 556 and F. Aurich et al. in Tens.Surf.Det. 29, (1992) 389 appeared. Preferably, according to the invention, protein hydrolysates of collagen, keratin, casein and vegetable proteins are used, for example those based on wheat gluten or rice protein, the production of which is described in German Patent DE 19502167 C1 and DE 19502168 C1 (Henkel).

In the context of the present invention, protein hydrolyzate derivatives are to be understood as meaning chemically and / or chemoenzymatically modified protein hydrolysates such as, for example, 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 derivatives of protein hydrolysates of collagen, keratin and casein and vegetable protein hydrolysates are used according to the invention such. B. Sodium Cocoyl Hydrolyzed Wheat Protein or Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein.

Further examples of protein hydrolysates and protein hydrolyzate derivatives falling 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 can be formed in each of the dispersions of the invention by one or more substances selected from the group of proteins, protein hydrolysates and protein hydrolyzate derivatives.

Preferred protein components are all structure-forming proteins, protein hydrolyzates and protein hydrolyzate derivatives, which are understood as meaning protein components which due to their chemical constitution form specific three-dimensional spatial structures familiar to the person skilled in the art of protein chemistry under the terms secondary, tertiary or even quaternary structure are.

According to a particularly preferred embodiment of the dispersion according to the invention, the protein component is selected from collagen, gelatin, casein and their hydrolysates, preferably gelatin, more preferably gelatin of type A, B or AB, in particular gelatin of the acid bone type (AB) which are also called "acid-bone" or "acid Process osseiiϊ'-gelatin are known, and be prepared from Ossein by highly acidic process conditions.

Ossein, as a collagen-containing starting material for the preparation of gelatin of type AB "acid bone" or "acid process Ossein", is prepared as an extract from minced bones, especially bovine bone, possibly after degreasing and drying for one or more days (preferably at least one Week and more) in aqueous solution, preferably cold acid, preferably dilute acid (eg hydrochloric acid), are incorporated to remove the inorganic bone components, especially hydroxyapatite and calcium carbonate. The result is a spongy demineralized bone material, the Ossein.

The collagen in the ossein is denatured by a digestion process and released by treating the material under strongly acidic conditions.

The preparation of the gelatin from said raw materials takes place by multiple extraction with aqueous solutions. Preferably, the pH of the solution can be adjusted before the extraction process. Particularly preferred are several extraction steps with water or aqueous solutions with increasing solvent temperature.

A preferred embodiment of the present invention is also a composite of the sparingly water-soluble calcium salt described in the previous embodiments together with the at least one polymer component mentioned.

By composite materials, the present invention preferably means composites comprising the water-sparingly soluble calcium salt according to the invention contained in the previous embodiments together with the at least one polymer component mentioned according to the invention. The composite materials according to the invention preferably represent microscopically heterogeneous, macroscopically but homogeneously appearing aggregates in which the primary particles of the calcium salts are present at the framework of the polymer component mentioned in accordance with said polymer component.

It is known that the availability of calcium compounds and / or composites containing them for the desired in various applications neo and / or remineralization very crucially depends on the particle size of these sparingly soluble in water and dispersed in the dentifrice components. It has therefore been proposed in the prior art to use these sparingly soluble calcium salts and / or composites containing them in the finest distribution.

In general, therefore, it is preferred in the dispersion according to the invention that the said sparingly water-soluble calcium salt and / or the said composite be 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 below 1000 nm, preferably below 300 nm, wherein it is particularly preferred that the particles are rod-shaped and / or platelet-shaped, in particular predominantly platelet-shaped are. Predominantly platelet-shaped means that at least 50%, preferably at least 70%, particularly preferably at least 80% of the particles are present in the form of platelets. Particularly preferably, the particles have a substantially platelet-like form.

The particle diameter is to be understood here as the diameter of the particles in the direction of their greatest length expansion. The mean particle diameter is to be understood as a value which is averaged over the total amount of the composite.

It should be noted that it is preferable that a single crystallite has a thickness in the range of 2 to 50 nm and a length in the range of 10 to 150 nm, in particular, a thickness of 2 to 15 nm and a length of 10 to 50 nm; most preferably has a thickness of 3 to 1 1 nm and a length of 15 to 25 nm.

The determination of the particle diameter of the crystallites can be determined by the methods familiar to the person skilled in the art, in particular by the evaluation of the broadening of the reflections observed in X-ray diffraction. Preferably, the evaluation by Fit method, for example, the Rietveld method.

The determination of the particle diameter of the particles can be determined by the methods familiar to the person skilled in the art, in particular by the evaluation of imaging methods, in particular transmission electron microscopy.

If platelet-shaped particles are present in the dispersion according to the invention, it is furthermore preferred for these to have a length of from 10 to 150 nm and a width of from 5 to 150 nm and a height (thickness) of from 2 to 50 nm. Under height (thickness) here is the smallest diameter of the particles based on the three mutually perpendicular spatial directions to understand under length their largest diameter. The width of the particles is therefore the further perpendicular to the length diameter which is equal to or smaller than the length dimension of the particle, but greater than or at least equal to its height dimension. The platelet-shaped particles are present as more or less irregularly shaped particles, sometimes as rather round particles, in some cases more angular particles with rounded edges. This is particularly noticeable in images that can be recorded by transmission electron microscopy. The platelet-shaped particles often also overlap several times in such samples. Overlapping particles are typically imaged at the points of overlap with greater blackening than non-overlapping particles. The specified Lengths, widths and heights are preferably determined (measured) on non-overlapping particles of the sample.

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 standing particles are characterized by a particularly high contrast (high density) and appear rather rod-like. These platelet-shaped particles, which are perpendicular to the image plane, 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 the image plane is tilted.

In order to determine the height of the particles, it is particularly suitable to tilt the image plane of the sample several times in different positions and to determine the dimensions of the particles in the setting which is characterized by the highest contrast / highest density and the smallest dimension of the particles. The shortest extent then corresponds to the height of the particles.

According to a preferred embodiment, the average length of the particles is preferably 30 to 100 nm.

In principle, if particles are present in the dispersion according to the invention, it is preferred for these particles to have a ratio of length to width of from 1 to 4, particularly preferably from 1 to 3, very particularly preferably from 1 to 2.

It is also a preferred embodiment of the dispersion according to the invention, if in the presence of particles, these particles at least one side with an area of 0.1 ^* 10 ^{~ 15} m ² to 90 ^* 10 ^'15 m ² , preferably from 0.5 ^* 10 ^'15 m ² to 50 ^* 10 ^{' 15} m ² , more preferably 1, 0 ^* 10 ^{" 15} m ² to 30 ^* 10 ^{~ 15} m ² , most preferably 1, 5 ^* 10 ^{~ 15} m ² to 15 ^* 10 ^{~ 15} m ² have.

As area of the particles, the area of the plane, spanned by the length and the vertical width, is determined according to the usual geometric calculation methods.

It is also preferred for the purposes of the present invention if, in the presence of crystallites and / or particles, the crystallites and / or particles of said calcium salts are enveloped by one or more surface modifiers.

In a further preferred embodiment of the present invention, said sparingly water-soluble calcium salt and said polymer component are in the form of a composite in which the polymer component is a protein component whose proportion 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.

Depending on the embodiment, the sparingly water-soluble calcium salts and / or composite materials contained in the dispersion according to the invention, comprising these, can be prepared by precipitation reactions from aqueous solutions of water-soluble calcium salts and aqueous solutions of water-soluble phosphate and / or fluoride salts, the precipitation in the case of the composite materials in the presence is carried out by polymer components.

The precipitation of the water-soluble calcium salt or of the corresponding composite material at a pH of between 5 and 9, preferably between 6 and 8, is particularly suitable for the preparation of a calcium salt and / or composite material which is preferably present in the dispersion according to the invention and contains predominantly platelet-shaped particles. more preferably around 7.

Preferably, a solution of a water-soluble calcium salt with the polymer component is initially charged to form the composite material preferably contained in the dispersion 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 kept constant during the addition of the phosphate solution by adding appropriate amounts of aqueous base.

It is also preferred that the dispersion of the invention at 20 ⁰ C using a rotary rheometer (TA Instruments AR 1000) at shear rates of 30 sec ^{"1 has} a viscosity between 100 mPa s and 30,000 mPa s, preferably between 200 mPa s and 10,000 mPa s and especially between 250 mPa.s and 5000 mPa.s .. An embodiment in which the corresponding viscosity values are in the range between 300 and 1700 mPa.s is especially preferred.

Incidentally, it is preferable that the dispersion of the invention at 20 ⁰ C is readily pumpable in the commonly used in production plants pumps. This is for example for the handling of the production, as well as for the filling and transport to the users and of course for the simple further advantage.

It is also a preferred embodiment of the dispersion of the invention, if the viscosity of said dispersion after storage over a period of 4, preferably 6 and especially 8 weeks at a constant storage temperature between ^{0 0} C and

40 ⁰ C between 100 mPa s and 30,000 mPa s, preferably between 200 mPa s and 10,000 mPa s and in particular between 250 mPa s and 5000 mPa s, wherein the measurement at 20 ⁰ C below Using a rotary rheometer (TA Instruments AR 1000) at shear rates of 30 sec ^{"1 was} performed.

Furthermore, a dispersion is preferred in which a composite referred to in a preferred embodiment is present, wherein said at least one polymer component, in the composite material between 0.5 and 70 wt .-%, preferably between 8 and 60 wt .-% based on the Total weight of the composite material.

It is likewise a preferred embodiment of the dispersion according to the invention if the liquid phase of the dispersion comprises an organic solvent, preferably from the group of hydroxy group-, in particular polyhydroxy-group-containing, solvents and / or derivatives thereof, it being very particularly preferred when said organic solvent is selected from the group of monohydric or polyhydric alcohols having preferably 1 to 4 C atoms and / or derivatives thereof and in particular is selected from ethanol, 1, 2-propanediol, glycerol, hexanediol and mixtures thereof.

Insofar as the organic solvents referred to as preferred are organic ethers, it is preferred that the organic solvent preferably contained in the dispersion according to the invention is selected from diisopropyl monomethyl ether, dipropylene glycol monomethyl ether, butyl diglycol ether.

It is further preferred that the surfactant contained in the dispersion according to the invention is selected from the groups of anionic, cationic, nonionic and amphoteric, zwitterionic surfactants (amphoteric / betaines), the alkylamine oxides, the silicone compounds and the phosphoric acid esters and their salts. As a selected surfactant from the group of nonionic surfactants, for example, the following groups are suitable:

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 alkylphenols having 8 to 15 carbon atoms in the alkyl group;

₁₂ C _/ i ₈ fatty acid monoesters and diesters of addition products of 1 to 30 mol ethylene oxide onto 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; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil; Polyol and especially polyglycerol esters, e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate 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, dipenta erythritol, sugar alcohols (eg sorbitol), 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 Th-PEG-alkyl phosphates and their

salts;

Lanolin alcohol;

Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1 165574 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. These are homolog mixtures, whose average 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.

Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, fatty acid fatty acids, alkyl sulfates, alkyl ether sulfates such as 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 aurides, N-acylamino acids such as acylglutamates and acylaspartates, alkyloligoglucoside sulphates, protein fatty acid condensates (in particular 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 / ampholytes / betaines can be used. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and optionally 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 are ampholytic surfactants. Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C _{8 /} iβ-alkyl or acyl group in the molecule, are at least contain a 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-alkyltauzenes, 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 /} iβ-acylsarcosine. In addition to the ampholytic tenides, quaternary surfactants are to be considered, preferably methyl-quaternized difatty acid triethanolamine ester salts.

In principle, it is preferred that said surfactant is selected from the groups of a) alkyl sulfates having a saturated or unsaturated, branched or linear alkyl group having 8 to 22 carbon atoms, preferably having 10 to 16 carbon atoms, the alkyl sulfate being particularly preferably sodium lauryl sulfate, b) alkyl glucosides having a saturated or unsaturated, branched or linear alkyl group having 8 to 22 carbon atoms, preferably having 10 to 16 carbon atoms and their ethoxylated analogs, particularly preferably containing as alkyl glucoside lauryl glucoside which, in a very particularly preferred embodiment, provides additional antimicrobial protection for the dispersion according to the invention, c) fatty acid ethanolamides having a saturated or unsaturated, branched or linear alkyl group having 8 to 22 C atoms, preferably having 10 to 16 C atoms, the fatty acid ethanolamide being particularly preferably lauryl ethanolamide, d) betaines and e) Ether sulfates.

Another variant of the dispersion of the invention contains as additional components one or more antimicrobial components, preferably selected from the groups of alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and Formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores, peroxides , Parabens, in particular the p-hydroxybenzoic acid esters, preferably selected from the methyl, ethyl and propyl esters, with methyl and ethyl esters being particularly preferred.

It is further preferred that the dispersion according to the invention comprises both the solvent to be used in a preferred embodiment of the present invention, in particular glycerol, and the antimicrobial component to be used in a preferred embodiment of the present invention, preferably at least one p-hydroxybenzoic acid ester preferably selected from the methyl, ethyl and propyl esters, in particular from methyl and ethyl esters, wherein it is likewise preferred that the dispersion contains at least one further antimicrobial component with fungistatic and / or fungicidal activity.

In the abovementioned preferred embodiment of the dispersion according to the invention, it is advantageous if the weight percent ratio of the amount of solvent to be used in a preferred embodiment of the present invention, in particular glycerol, to the amount of the surfactant present in the dispersion according to the invention is 5: 1 to 1 : 100, preferably from 4: 1 to 1:10, in particular from 3: 1 to 1: 3.

These formulations have shown advantages in terms of the performance of the combinations, especially in conjunction with a synergistic increase in antimicrobial performance, most notably in bacteria.

In this context, another object of the present invention is directed to an antimicrobial combination or an antimicrobial system comprising a solvent to be used according to a preferred embodiment of the present invention, in particular glycerol and a surfactant present according to the invention, especially sodium lauryl sulfate, wherein the weight percent ratio of Solvent to surfactant 5: 1 to 1: 100, more preferably from 4: 1 to 1: 10, and in particular from 3: 1 to 1: 3, and an antimicrobial component, most preferably the solvent at least glycerol and the surfactant at least sodium lauryl sulfate. In a very particularly preferred embodiment, at least glycerol is present as solvent and at least sodium laurysulfate as surfactant and at least one p-type as antimicrobial component.

Hydroxybenzoic acid esters selected from the methyl, ethyl and propyl esters, with methyl and ethyl esters being particularly preferred. The weight percent ratio of glycerol to sodium lauryl sulfate in this combination is preferably 4: 1 to 1: 100, more preferably 4: 1 to 1:10, and in particular from 3: 1 to 1: 3, with a ratio of 2: 1 to 1: 1.

Likewise provided by the present invention is a dispersion obtainable by combining a calcium salt according to the invention, preferably present as glycerinic dispersion, and / or a polymer component according to the invention with one or further components selected from the surfactants contained according to the invention.

It is preferred for the present invention available dispersion that said, preferably glycerinsche dispersion before, during, or is heated after contacting with said one or another component to 30 to 8O ⁰ C, preferably at 35 to 65 ⁰ C, and in particular 40 up to 6O ⁰ C, especially to a maximum of 5O ⁰ C. Another object of the present invention is a process for preparing a dispersion according to the invention wherein a, preferably glycerinic dispersion of the sparingly sparingly water-soluble calcium salt according to the invention and / or the polymer component according to the invention with one or further components selected from the present invention as surfactants.

It is preferred in the context of the process according to the invention that the said, preferably glycerin dispersion before, during or after contacting with said one or more components is heated to 30 to 8O ⁰ C, preferably to 35 to 65 ⁰ C, in particular to 40 up to 6O ⁰ C, especially to a maximum of 5O ⁰ C.

In addition, the present invention relates to compositions which contain a combination of a dispersion according to the invention with other active ingredients and ingredients or are obtainable by a combination of a dispersion according to the invention with other active ingredients and ingredients.

Another object of the present invention is the use of a dispersion of the invention or a composition according to the invention for cleaning and / or care of the teeth, in particular to achieve a neo and / or remineralizing effect. For the purposes of the present invention, preference is given to largely suppressing agglomeration in the dispersions of the present invention and more preferably to increase the monodispersity of the dispersion. The dispersion according to the invention particularly preferably exhibits a high proportion of single crystals. For the purposes of the present invention, it is very particularly advantageous that a rapid, equal or regular growth results on the substrates, for example the teeth.

It is also an object of the present invention oral and dental care and - cleaning agent, preferably toothpastes containing a dispersion of the invention or a composition of the invention.

The compositions for cleaning and / or care of the teeth can be present for example in the form of pastes, liquid creams, gels or mouthwashes. Even in liquid preparations, the dispersions or compositions according to the invention are readily dispersed, remain stably dispersed and do not tend to sediment.

The content of the dispersions or compositions according to the invention in the oral and dental care preparations according to the invention is from 0.01 to 10% by weight, preferably from 0.01 to 5% by weight, very particularly preferably less than 3% by weight and in particular less than 2 % By weight based on the total weight of the composition. The oral and dental care compositions according to the invention can furthermore contain 0.1 to 9% by weight, in particular 2 to 8% by weight, of at least one cleaning agent.

Cleaning agents are among the essential ingredients of a toothpaste and, depending on their intended function, are present alone or in combination with other cleansers or polishes. They are used for the mechanical removal of the uncalcified plaque and should ideally lead to the gloss of the tooth surface (polishing effect) with minimal abrasion (abrasion effect) and damage to the enamel and the dentin. The abrasion behavior of the polishing agents and cleaning bodies is essentially determined by their hardness, particle size distribution and surface structure. When selecting suitable cleaning bodies, those which have a minimum abrasion effect, in particular, are therefore preferably selected.

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

Usually, water-insoluble inorganic substances are used as cleaning or polishing agents. Particularly advantageous is the use of very finely divided polishing agent having an average particle size of 1 to 200 .mu.m, preferably 1 to 50 .mu.m and in particular 1 to 10 microns.

In principle, the polishing agents according to the invention may be selected from silicic acids, aluminum hydroxide, aluminum oxide, silicates, organic polymers or mixtures thereof. However, it is also possible for so-called metaphosphates, alkaline earth metal carbonates or bicarbonates and also calcium-containing polishing components to be present in the compositions according to the invention.

It may be preferred according to the invention to use silicas as polishing agents in toothpastes or liquid dentifrices. Among the silicic acid polishing agents, a distinction is generally made between gel silicic acids, hydrogel silicic acids and precipitated silicas. Precipitated and gel silicas are particularly preferred according to the invention, since they can be widely varied in their preparation and are particularly well tolerated with fluoride active ingredients. They are also particularly suitable for the production of gel or liquid toothpastes.

Gel silicas are produced by the reaction of sodium silicate solutions with strong, aqueous mineral acids to form a hydrosol, aging to the hydrogel, washing and subsequent drying. If the drying takes place under mild conditions to water contents of 15 to 35 wt .-%, so-called hydrogel silicic acids are obtained, as described for example in US 4,153,680. By drying this Hydrogel silicic acids to water contents below 15 wt .-% occurs irreversible shrinkage of the previously loose structure to the dense structure of the so-called xerogel. Such Xerogelkieselsäuren are known for example from US 3,538,230.

A second, preferably suitable group of silica polishing agents are the precipitated silicas. These are obtained by precipitation of silica from dilute alkali silicate solutions by addition of strong acids under conditions where aggregation to the sol and gel can not occur. Suitable processes for the preparation of precipitated silicas are described, for example, in DE-OS 25 22 586 and in DE-OS 31 14 493. Particularly suitable according to the invention is a precipitated silica prepared according to DE-OS 31 14 493 with a BET surface area of 15 to 110 m ² / g, a particle size of 0.5 to 20 .mu.m, wherein at least 80 wt .-% of the primary particles under 5 microns, and a viscosity in 30% glycerol-water (1: 1) dispersion of 30 to 60 Pa s (2O ⁰ C) in an amount of 10 to 20 wt .-% of the toothpaste. Particularly suitable precipitated silicas of this type have rounded corners and edges and are commercially available for example under the trade name of Sident 12 DS ^® from Degussa.

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

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

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

As the alumina polishing agent is preferably a weakly calcined alumina having a content of α and γ-alumina in an amount of about 0.01 to 5 wt .-%, preferably 0.1 to 2 wt .-%, based on the Total weight of the agent. Suitable weakly calcined clays are prepared by calcination from aluminum hydroxide. Aluminum hydroxide is converted into the thermodynamically stable Ct-Al ₂ O ₃ at temperatures above 1200 ° C. by calcination. The thermodynamically unstable Al ₂ O ₃ modifications occurring at temperatures between 400 and 1000 ° C. are referred to as gamma forms (compare Ullmann, Enzyclopädie der technischen Chemie, 4th Edition (1974), Volume 7, page 298). By selecting the temperature and the time during the calcination, one can set the degree of calcination, ie the conversion into the thermodynamically stable Ct-Al ₂ O _3, to any desired level. Low calcination gives an alumina containing γ-Al ₂ O ₃ , which is lower the higher the calcination temperature and the longer the calcination time. Slightly calcined clays are distinguished from pure Ct-Al ₂ O ₃ by lower agglomerate hardness, larger specific surface area, and larger pore volumes.

The dentin abrasion (RDA) of the invention to be used weaker calcined clays with a proportion of 10 to 50 wt .-% γ-Al ₂ O ₃ is only 30 to 60% of dentin abrasion of a highly calcined, pure Ct-Al ₂ O ₃ (measured in a standard toothpaste with 20% by weight of alumina as the sole polishing agent).

In contrast to Ct-Al ₂ O _3, the γ-Al ₂ O ₃ can be with an aqueous ammoniacal solution of Alizarin S (1, 2-dihydroxy-9,10-anthraquinone-4-sulfonic acid) stain red. The degree of dyeability can be selected as a measure of the degree of calcination or of the proportion of 5-Al ₂ O ₃ in a calcined alumina:

Approximately 1 g of Al ₂ O ₃ , 10 ml of a solution of 2 g / l Alzarin S in water and 3 drops of an aqueous, 10 wt .-% solution of NH 3 are placed in a test tube and boiled briefly. The Al ₂ O ₃ is then filtered off, washed, dried and evaluated under the microscope or evaluated colorimetrically.

Suitable, slightly calcined clays containing from 10 to 50% by weight of γ-Al ₂ O ₃ can be colored pale to deep pink by this process.

Alumina abrasives of various degrees of calcination, fineness and bulk densities are commercially available, e.g. the "Poliertonerden" of the company Giulini-Chemie or ALCOA.

A preferred suitable quality "Poliantonerde P10 feinst" has an agglomerate size of less than 20 microns, a mean primary crystal size of 0.5 to 1, 5 microns and a bulk density of 500 to 600 g / l.

The use of silicates as polishing agent components may also be preferred according to the invention. They are used in particular in modern practice as a cleaning body. Examples of silicates which can be used according to the invention are aluminum silicates and zirconium silicates. In particular, the sodium aluminum silicate of the empirical formula Na ₁₂ (AlO _{2) I2} (SiO _{2) I2} x 7H ₂ O may be suitable as a polishing agent, such as the synthetic zeolite A.

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

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

Another polish suitable for use in the oral and dental care compositions of the present invention is calcium phosphate dihydrate (CaHPO ₄ X 2H ₂ O). Calcium phosphate dihydrate occurs in nature as brushite and is available as a polishing agent commercially in suitable particle sizes of 1 to 50 microns.

According to the invention, oral and dental care preparations are preferred which, in support of the remineralization process by the dispersions or compositions according to the invention, additionally contain 0.1 to 10% by weight, preferably 0.1 to 5% by weight and in particular 0.1 to 3% by weight. -% of a Remineralisationsförderungs component, each based on the total weight of the agent included.

The Remineralisationsförderungs component promotes remineralization of the enamel and the closure of dental lesions in the compositions of the invention and is selected from fluorides, microparticulate phosphate salts of calcium such. Calcium glycerophosphate, calcium hydrogen phosphate, hydroxyapatite, fluoroapatite, F-doped hydroxyapatite, dicalcium phosphate dihydrate and calcium fluoride. But also magnesium salts such. As magnesium sulfate, magnesium fluoride or magnesium monofluorophosphate have remineralizing.

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

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

According to a further preferred embodiment, the oral and dental care products according to the invention contain additional toothpaste ingredients, such as surfactants, humectants, binders, flavorings and active substances against tooth and gum diseases. For improving the cleaning effect and foaming of the oral and dental care compositions of the invention, surface-active surfactants or surfactant mixtures are usually used. They promote the rapid and complete dissolution and distribution of dental creams in the oral cavity and at the same time support the removal of mechanical plaque, especially in those places that are difficult to access with a toothbrush. In addition, they promote the incorporation of water-insoluble substances, such as aromatic oils, stabilize the polishing agent dispersion and support the Antikarieswirkung of fluorides.

Humectants are usually used in dental cosmetics to protect against dehydration and for consistency control and cold stability of the products. However, they can also serve for suspension mediation and to influence the taste or gloss.

Commonly used as humectants are toxicologically acceptable polyols such as sorbitol, xylitol, glycerol, mannitol, 1,2-propylene glycol, or mixtures thereof, but also polyethylene glycols having molecular weights of 400 to 2,000 can serve as humectant components in dentifrices.

Preferred is the combination of several humectant components, wherein the combination of glycerol and sorbitol with a content of 1, 2-propylene glycol or polyethylene glycol is to be regarded as particularly preferred.

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

In a further preferred embodiment, the oral and dental cleaning agent according to the invention contains additional active ingredients against tooth and gum diseases. According to the invention, such active substances are 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 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. Anti-plaque agents

Preparations preferred according to the invention, in particular oral and dental care and cleansing compositions, are characterized in that they additionally have antiplaque active ingredients, preferably methyl, ethyl or propyl p-hydroxybenzoate, sodium sorbate, sodium benzoate, bromochlorophene, triclosan, phenyl salicylic acid ester, Biguanids z. For example, 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 wt .-%, respectively on the entire remedy, included.

Antimicrobial agents

As antimicrobial component z. As phenols, resorcinols, bisphenols, salicylanilides and amides and their halogenated derivatives, halogenated carbanilides and p-hydroxybenzoic acid esters.

Among the antimicrobial components, those which inhibit the growth of plaque bacteria are particularly suitable. Examples are halogenated diphenyl ethers, such as 2,4-dichloro-2'-hydroxydiphenyl ether, 4,4'-dichloro-2'-hydroxydiphenyl ether, 2,4,4'-TNbromo-2'-hydroxydiphenyl ether, 2,4,4'-dichloro-2'-hydroxydiphenyl ether. Thchloro-2'-hydroxydiphenyl ether (Triclosan) suitable as antimicrobial agents. In addition to bromochlorophene, bisbiguanides such as chlorhexidine and alexidine, phenylsalicylic acid esters and 5-amino-1,3-bis (2-ethylhexyl) hexahydro-5-methylpyhmidine (hexetidine), zinc and copper ions also have an antimicrobial effect, with synergistic effects in particular in combination with hexetidine and triclosan occur. Also quaternary ammonium compounds, such as. As cetylpyridinium chloride, benzalkonium chloride, domiphen bromide and dequalinium chloride are used. Octapinol, octenidine and sanguinarine have also proven to be effective as antimicrobial agents.

The antimicrobial agents are preferably used in amounts of 0.01 to 1 wt .-% in the inventive compositions. Irgacare ^® MP is particularly preferably used in an amount of 0.01 to 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 in the form of their alkali or Ammonium salts, preferably used 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 to 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.

It is also possible to use mixtures of different condensed phosphates and / or hydrated salts of the condensed phosphates according to the invention. Tartar inhibitors are usually used in amounts of 0.1 to 5 wt .-%, preferably 0.1 to 3 wt .-% and in particular 0.1 to 2 wt .-% in the inventive compositions.

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

Active ingredients against hypersensitive teeth

Preferably, the agents of the invention further contain hypersensitive tooth active agents 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 may be mixed with aromatic oils in the oral and dental care products. Preferably, it is included in the compositions in the form of clove bud oil.

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

flavorings

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

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

Aromatic oils are all natural and synthetic flavors used for oral and dental care. Natural flavors can be found both in the form of the essential oils isolated from the drugs (mixture) and in the form of the individual components isolated therefrom be used. Preferably at least one aromatic oil should be selected from the group of peppermint oil, spearmint oil, aniseed oil, star aniseed 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 or more thereof or synthetic be produced components of these oils. The most important components of the oils mentioned are z. Menthol, carvone, anethole, cineole, eugenol, cinnamaldehyde, caryophyllene, geraniol, citronellol, linalool, salvos, thymol, terpinene, terpinol, methylchavicol and methyl salicylate. Other suitable flavors are z. For example, menthyl acetate, vanillin, ionone, linalyl acetate, rhodinol and piperitone.

Finally, other common adjuvants may be included to improve the stability and sensory properties of the oral and dental care products. 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 to 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, sodium bicarbonate or potassium and sodium phosphates,

Preservatives, e.g. 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 wt .-%, based on the total weight, in the inventive compositions. 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. Oral and dental care and cleaning agents which are preferred according to the invention are characterized in that they increase the insensitivity of the teeth-increasing substances, preferably potassium salts, particularly 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 wt .-%, more preferably from 2.5 to 10 wt .-% and in particular from 4.0 to 8.0 wt .-%, each based on the total agent included.

Also preferred are preparations, in particular oral and dental care and - cleansing, 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.

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

The oral and dental care and cleaning agents of this embodiment to be used in the present invention include bioactive glass or glass powder or glass ceramic powder or composite materials comprising such a bioactive glass. For the purposes of the present application, glass powders are also understood as meaning granules and glass beads.

Due to the requirements for the toxicological safety of the glass and its suitability for consumption, the glass powder should be particularly pure. The burden of heavy metals is preferably low. Thus, the maximum concentration in the range of cosmetic formulations is preferably for Pb <20 ppm, Cd <5 ppm, As <5 ppm, Sb <10 ppm, Hg <1 ppm, Ni <10 ppm.

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. About the P ₂ O ₅ content may be in silicate glasses, glass ceramics, or Composites the chemical resistance of the glass and thus the ion delivery in aqueous media can be adjusted. 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 enhance the antimicrobial, in particular the antibacterial properties of the glass-ceramic antimicrobial acting ions such. B. Ag, Au, I, Ce, Cu, Zn in concentrations less than 5 wt .-% may be included.

Coloring ions such. As Mn, Cu, Fe, Cr, Co, V, may be contained individually or in combination, preferably in a total concentration less than 1 wt .-%.

Usually, the glass or the glass ceramic is used in powder form. The ceramization can be done either with a glass block or Glasribbons or with glass powder. After ceramization, the glass ceramic blocks or ribbons must be ground to powder. If the powder has been ceramified, it may also be necessary to re-mill to remove agglomerates formed during the ceramification step. The grinding can be carried out both dry and in aqueous or non-aqueous grinding media. Usually, the particle sizes are less than 500 microns. As appropriate, particle sizes <100 microns or <20 microns have been found. Particularly suitable are particle sizes <10 microns and less than 5 microns and less than 2 microns, 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 35 to 60% by weight, preferably 40 to 60% by weight,

Na ₂ OO to 35 wt .-%, preferably 5 to 30 wt .-%,

K ₂ OO to 35 wt .-%, preferably O to 20 wt .-%,

P ₂ O ₅ O to 10 wt .-%, preferably 2 to 10 wt .-%,

MgO 0 to 10% by weight, preferably 0 to 5% by weight,

CaO O to 35% by weight, preferably 5 to 30% by weight,

Al ₂ O ₃ O to 25 wt .-%, preferably O to 5 wt .-%,

B ₂ O ₃ O to 25% by weight, preferably from 0 to 5% by weight,

TiO ₂ O to 10 wt .-%, preferably 0.1 to 5 wt .-%.

As already mentioned above, the bioactive glass is preferably used in particulate form. Here, particularly preferred oral and dental care and cleaning compositions according to the invention are characterized in that the antimicrobial glass particle sizes <10 .mu.m, preferably from 0.5 to 4 .mu.m, more preferably from 1 to 2 microns having.

The content of the dispersions or compositions according to the invention in the oral and dental care preparations according to the invention is from 0.01 to 10% by weight, preferably from 0.01 to 2% by weight, very particularly preferably less than 2% by weight and in particular less than 1 % By weight based on the total weight of the composition.

A preferred embodiment is toothpastes with a content of silica, polishing agents, humectants, binders and flavors which are 0.00001 to 10, in particular 0.01 to 4,% by weight, preferably 0.01 to 2,% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight, based on the total weight of the composition, of dispersions or compositions according to the invention.

Furthermore, dispersions or compositions according to the invention can be used as neo- or remineralizing components in compositions for strengthening the enamel.

Further use of the dispersion or the composition according to the invention takes place as the biomineralization-inducing or promoting component for the treatment of tooth or bone defects.

The dispersion or composition according to the invention or compositions containing them are also suitable for being used for coating implants.

Use of the dispersion or composition of the invention, or compositions containing at least these, for smoothing the surface of teeth and / or bones is also preferred. The dispersion or composition of the invention can induce or promote biomineralization in bone tissue. They are therefore further suitable as a biomineralizing component for the preparation of compositions for the recovery or new formation of bone material, such as. B. of compositions for the treatment of bone defects and bone burs as well as to promote the ingrowth of implants.

For coating implants, the dispersions of the invention or the compositions according to the invention can be applied, for example, by the standard methods of dip coating or plasma spraying known to those skilled in the art.

For use as injectable bone replacement materials, the dispersions of the invention or the compositions according to the invention may be combined with suitable further substances, such as e.g. As glycosaminoglycans or proteins, and with suitable solvents and auxiliaries such. B. formulated into a dilute aqueous phosphate buffer.

Another object of the invention relates to the use of the dispersion according to the invention or the composition according to the invention for the protection and / or therapeutic and / or preventive treatment of teeth and / or bones before or in case of damage due to external influences, in particular body-related, chemical, physical and / or microbiological nature, in particular for the prevention and repair of erosions on bones and teeth, in particular enamel, care of the enamel, and for the protection of the teeth against attack by acids, in particular by bacterial activity or by the action of acids from food, for Protection against demineralization of the teeth, sealing of fissures, protection and / or repair of primary lesions and / or initial caries in the enamel, as well as for smoothing the tooth surface, caries prevention, improving cleanability, mechanical resists z of teeth and dental health in general.

According to a preferred embodiment, the dispersion according to the invention or the composition according to the invention are used against attacks by acids.

The term acids is to be understood here as meaning both the intrinsic acids and the extrinsic acids. The damage caused by intrinsic acids relates in particular to medical conditions associated with contact of gastric acid with the oral region, in particular in belching, regurgitation, heartburn or vomiting, also in connection with pathological eating disorders, in particular bulimia.

Particularly suitable is the use in attack by extrinsic acids, in particular due to bacterial activity or the action of acids from food. Furthermore, it has been observed that in addition to the prevention, erosion of teeth (dentin and enamel) and bone, especially enamel, repair of erosions on tooth and bone, in particular the enamel, takes place by the dispersion according to the invention or the composition according to the invention.

The dispersion according to the invention or the composition according to the invention are therefore also to be used therapeutically in the repair of damage, in particular erosions, on bones and teeth, in particular on the enamel.

The dispersion according to the invention or the composition according to the invention are preferably used to protect against and / or repair primary lesions and / or initial caries in enamel and to seal fissures. According to the invention, fissures (i.e., the crevasse-like recesses on the chewing surfaces of the molars and molars) can be sealed by the use according to the invention and thus their cariousness can be reduced.

Furthermore, the use of the dispersion according to the invention or of the composition according to the invention leads to a better mechanical resistance, in particular that the extent of micro-scratches, craters or mechanical abrasion is reduced.

The use of the invention leads to a better resistance to mechanical stress of the teeth, which can be caused in addition to chewing in particular by vigorous brushing. Damage or erosion of softened enamel can thus be avoided.

Because of the said positive properties of the dispersion according to the invention or of the composition according to the invention, these are themselves or compositions containing them, thus generally used for improving the cleanability of the teeth and the dental health.

In addition, an object of the present invention is directed to the use of a dispersion according to the invention or a composition according to the invention for coating implants.

Moreover, the present invention comprises the use of a dispersion according to the invention or a composition according to the invention as a food additive.

Also sweets having a total candy content of preferably at least 0.000001% by weight of a dispersion of the invention or of a composition of the invention are within the scope of the present invention in particular, when the sweets are selected from chewing gum, hard and soft caramels, gumdrops, jelly products, marshmallows, licorice, dragées, pastilles and candied fruit.

In a preferred embodiment, the candy is selected from the group of sugar confectionery. Sugar confectionery is a diverse group of foods that usually have a distinctly sweet taste due to sugar and / or other common sugars, sugar or other sweeteners or other sweet ingredients, according to the Confectionery Directive of the Federation of the German Confectionery Industry. Sweets are also filling, glaze or confectionery masses, as well as layers, coatings or fillings of confectionery or pastry. Sugar confectionery also includes sugar-free sugar confectionery. In these, the sweet taste is achieved by sugar alcohols and / or sweeteners.

Preferred confectionery products are, in particular, hard and soft caramels, gumdrops, jelly products, marshmallows, licorice products, dragees, lozenges and candied fruits.

Caramels (also called candies) generally obtain their character by boiling a solution of sugars and / or sugar alcohols and are prepared using odorous and flavoring substances, coloring and / or texture affecting substances with or without filling in various forms. The texture of the caramel ranges from hard caramels, e.g. Drops up to the soft caramels, which differ in particular by their residual water content. This can be up to about 5% by weight for hard caramels and up to about 15% by weight for soft caramels. Soft caramels are, for example, the elastic-chewing gum-like chewy candy or the soft, easily chewable, z.T. sticky toffees. Depending on the method of production, e.g. distinguished sliced, embossed, cast and laminated candies.

Jelly products in the spirit of the present invention are elastic-soft confectionery confections (e.g., jelly fruits). Likewise sweets according to the invention are gumdrops, e.g. Fruit gums, gummy bears, wine gums or gum pastilles. They are tough-elastic and chewable-firm and, like the jelly products, are made from sugars and / or sugar alcohols, gelling agents (such as agar, pectin or gum arabic), gelatin and / or starch (modified if necessary). Waxes or vegetable oils can also be used as a release and shine agent.

Licorice products are made from a mixture of sugars and / or sugar alcohols, gelatin and / or (also modified) starch and / or flour and / or gelling and thickening agents as well as various flavors. In addition, licorice products contain as a characteristic ingredient at least 3% licorice juice (Succhus liquiritiae, in the commercial dry form). The addition of up to 8 wt .-%, in particular up to 2 wt .-% Salmiaksalz leads to so-called Starklakritzen. Dragees consist of a smooth or curly top made with sugar types and / or sugar alcohols, chocolate types and / or other glazes in a coating process and a liquid, soft or firm core. In the coating process, for example, a saturated sugar solution is finely distributed from a nozzle to the rotating in Dragierkesseln core sprayed. The sugar crystallizes through the simultaneously injected warm air and gradually forms many thin layers around the core. If the sugar layer does not contain any residual moisture, the candy is referred to as a harddrage; in the case of softdries, on the other hand, about 6 to 12, in particular 8 to 10,% by weight of residual moisture can be present. Dragees are externally often provided with a thin release and gloss layer, the gloss layer by treatment with waxy substances, such as carnauba wax, arises. In particular, the nature of influencing substances such as starch and coloring, odor and flavoring substances are used.

Compresses or pastilles are produced by the tableting or powder casting or extrusion process and may contain, in addition to the sugars and / or sugar alcohols, small amounts of binders and lubricants.

According to a particularly preferred embodiment, the candy is a hard or soft caramel or a dragee. These sweets have the advantage that they are kept in the mouth for a long time and the active ingredients and auxiliaries incorporated in the sweetener in the form of the dispersion or inventive composition are released only gradually. The mineralizing, and in particular the neomineralizing effect is thereby particularly promoted.

Particularly in the case of sweets made from melts of sugar and / or sugar alcohols, such as, for example, caramel, the dispersion according to the invention or the composition according to the invention can advantageously be incorporated directly into the melt. Surprisingly, this does not lead to a crystallization of the sugar in the melts, which leads to the addition of conventional, ground apatite to a polycrystalline, difficult to process mass. The gritty taste of coarse-grained apatite could not be determined either.

Especially preferred are the hard caramels such as e.g. Sweets, drops, candy canes or lollipops, which remain in the mouth for a particularly long time, whereby the stepwise release of the calcium salt or the composite material according to the invention is optimally given.

In spite of the partially tooth-damaged ingredients (sugar), the consumption of the candy according to the invention leads, in addition to the enjoyment experience, to dental care and tooth preservation as well as, in addition, to the mineralization of the enamel and / or of the dentin. On the, not always possible after the consumption of sweets, but for the health of the teeth so far Necessary dental care, usually with a toothbrush, toothpaste and / or mouthwash, can thus be dispensed with without damaging the teeth due to the consumption of sweets.

Sugar alcohols which are preferred according to the invention are sorbitol or sorbitol syrup, mannitol, xylitol, lactitol, isomalt, maltitol or maltitol syrup. These substances have the advantage that they contain less calories per 100 g and, moreover, the degradation of the sugar alcohols to acids by some bacteria of the oral cavity takes place so slowly that they do not have a cariogenic effect. The addition according to the invention of dispersion according to the invention or composition according to the invention in sweeteners containing sugar substitutes causes a mineralization of the teeth during and / or after the consumption of the candy and thus contributes particularly to the maintenance of healthy teeth.

According to a further preferred embodiment, the candy according to the invention is filled. Sweets with a solid, gel or liquid core allows i.a. the addition of other flavor components in this core. Likewise, this can be introduced active ingredients that can not be incorporated in a direct manner (for example, by admixture) without loss of effect or loss. In candies u.a. Vitamins or alcohol are incorporated into such fillings.

It is particularly preferred that the filling contains the dispersion or composition according to the invention. The material according to the invention contained in the filling can thus also be incorporated into such sweets in which the risk of loss of effect by the properties of the candy or the production thereof consists. This filling may in particular be a suspension, a gel or a syrup. In particular, the suspensions or gels may be water-based to ensure good compatibility. An addition of further food-suitable dispersants or wetting agents can serve to keep the dispersion or composition according to the invention in suspension. Particularly suitable gel formers are organic thickeners and their derivatives.

In addition to synthetic organic thickeners, particularly natural organic thickeners, in particular agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein are suitable. Modified natural products are also preferred, in particular carboxymethylcellulose and other cellulose ethers, hydroxyethylcellulose and hydroxypropylcellulose, and gum ethers. Synthetic organic thickeners such as polyethers or inorganic thickeners such as polysilicic acids and / or clay minerals (eg montmorillonites, zeolites or silicic acids) can also be used according to the invention. According to another embodiment of the present invention, the candy is a filled chewing gum.

Chewing gums containing the inventive dispersion or composition according to the invention incorporated into the chewing gum and comprising the latter, however, release only small amounts of the active ingredient because of their sticky consistency. By biting on the filled chewing gum, the dispersion of the invention or the composition according to the invention comprising it, which is contained in the filling, are released directly in the mouth and can thus act better than in conventional chewing gums. The chewing gum additionally promotes the salivation by the executed chewing motion. The caries-causing acids are diluted, thus naturally supporting the health of the oral cavity. Particularly tooth-care and -supporting chewing gums contain sugar substitutes, in particular sugar alcohols.

Chewing gums consist of sugars and / or sugar alcohols, sweeteners, flavors, other odor and taste or consistency-giving ingredients, dyes and a water-insoluble gum that becomes plastically chewing. In addition, the chewing gums may also contain separating and coating agents (such as talcum).

Kaumassen are mixtures of consistency-giving substances, the natural gums, which are solidified juices (exudates) from tropical plants such as chicle, gum arabic, gutta-percha, karaya gum and tragacanth, rubber and the thermoplastics butadiene-styrene copolymers, isobutylene-isoprene copolymers, Polyethylene, polyisobutylene, polyvinyl esters of the unbranched fatty acids of C ₂ to C ₁₈ and polyvinyl ethers.

Plasticizers are resins and balsams. The natural substances include benzoin, dammar resin, rosin, mastic, myrrh, olibanum, balsam of Peru, Sandarrak, shellac and tolu balsam, the synthetic coumarone-indene resin, glycerol pentaerythritol ester of the rosin acid of the rosin and their hydrogenation products.

Paraffins (natural and synthetic) and waxes are used to influence the elasticity. In the waxes, there are those from the plant sector such as Carnabau wax and animal origin such as beeswax or wool wax, next to those from the mineral field such as microcrystalline waxes, as well as chemically modified or synthetic waxes. Plasticizers are emulsifiers (e.g., lecithins or mono- and diglycerides of fatty acids) and esters such as glycerol acetate as well as glycerine.

To regulate the chewy consistency, vegetable hydrocolloids such as agar-agar, alginic acid and alginates, guar gum, locust bean gum or pectin are added. For targeted adjustment of the chewing properties of chewing gums fillers are used, which are Carbonates of calcium or magnesium, oxides, for example, alumina, silica and silicates of calcium or magnesium. Stearic acid and its calcium and magnesium salts are used to reduce the adhesiveness of the chewing gum to enamel.

Before the remaining according to the recipe necessary for the production of chewing gum ingredients may be mixed, it is necessary for the gum base, (but at least 15%) of the final chewing gum constitutes about 20-35% to warm to 50-60 ⁰ C.

According to another preferred embodiment of the present invention, the candy comprises a dissolving component. This component or matrix dissolves in the mouth by contact with the saliva. The dissolution can also be achieved by a longer residence time in the mouth (in particular of over five minutes) and / or sucking. As a component or matrix is here, for example, the sugar matrix or the basic mass of a candy, a gummi candy or a filling to understand.

It is particularly preferred for the dissolving component or matrix to contain the dispersion or composition according to the invention contained in the candy, including the latter, in the candy. This advantageously leads to the fact that the dissolving component can release the active substance contained therein or contained in the mouth. In particular, this is important for such sweets in which the active ingredient is otherwise not released in large quantities.

This can be advantageous, for example, with a filled chewing gum. The dispersions or compositions of the present invention comprising these are incorporated into a solid, gelatinous or liquid filling which exits the chewing gum by biting on the chewing gum in the mouth and releases the active ingredient. In the case of a liquid filling this mixes with the saliva. It is also possible that the calcium salts of the invention and / or the composite materials comprising these, e.g. incorporated in granulated sugar pearls in a chewing gum. It is also possible for the material of the invention to be applied to the candy as a fine powdery dust, for example together with separating agents on chewing gums (for example with talcum) or acidic drops (which are often dusted with powdered sugar as protection against sticking, for example).

The active ingredient in the dissolving component or matrix does not remain, as when incorporated into the chewing gum of a chewing gum, largely trapped in or with a non-dissolving component. Thus, the necessary amount of active ingredient is made available in the mouth, which advantageously ensures effective mineralization of the teeth.

According to a particularly preferred embodiment of the invention, the candy consists essentially of at least one dissolving component or matrix. According to the invention It is particularly advantageous that there are no components of the candy to which the active ingredient, after sucking or melting, can still be bound in the mouth and thus not available for the mineralization of the tooth material. Corresponding sweets may be, for example, filled or unfilled caramels, gumdrops, jelly products, marshmallows, licorice, dragées or lozenges.

According to a further preferred embodiment, the candy contains flavorings, sweeteners, fillers and / or further auxiliaries (such as, for example, glycerol or mineral salts, for example Zn ²⁺ or Mg ²⁺ ). In principle, any natural or nature-identical flavorings, such as fruit flavors, can be used. These may be contained in particular in solid or liquid fruit preparations, fruit extracts or fruit powders. Preference is given to pineapple, apple, apricot, banana, blackberry, strawberry, grapefruit, blueberry, raspberry, passion fruit, orange, sour cherry, red and blackcurrant, woodruff and lemon. Also other flavors, in particular aroma oils such as peppermint oil, spearmint oil, eucalyptus oil, aniseed oil, fennel oil, caraway oil and synthetic flavor oils can be used. This is particularly preferably done in herbal and / or cough sweets and chewing gum.

Other flavoring additives may u.a. Milk, yoghurt, cream, butter, honey, malt, caramel, licorice, wine, almonds, pistachio, hazelnut or walnut kernels and other protein-rich oilseed and peanut kernels, coconut, cocoa, chocolate, cola or vanilla.

Also agents such as e.g. Menthol and / or vitamins to be included in the candy of the invention. Likewise, organophosphonates, e.g. 1-hydroxyethane-1, 1-diphosphonic acid, phosphono-propane-1, 2,3-thcarbonic acid (Na salt) or 1-azacycloheptane-2,2-diphosphonic acid (Na salt), and / or pyrophosphates are added that reduce the formation of tartar.

Sweeteners such as sodium saccharin, acesulfame-K, aspartame ^®, sodium cyclamate, stevioside, thaumatin, sucrose, lactose, maltose, fructose or glycyrrhizin are also preferably contained. This can reduce the amount of sugar and still obtain the predominantly sweet taste.

As preservatives it is possible to use all preservatives approved for foods, for example sorbic acid or benzoic acid and derivatives thereof, for example sodium benzoate and para-hydroxybenzoate (sodium salt), sulfur dioxide or sulfurous acid, sodium or potassium nitrite. Dyes and pigments to achieve a pleasing appearance may also be included. Another object of the present invention is the use of at least one dispersion of the invention or a composition according to the invention in sweets, in particular sugar confectionery, as an ingredient with a positive effect on dental health.

In particular, the dispersion according to the invention or the composition according to the invention or the candy containing it are used for dental care and tooth preservation as well as, in addition, for the mineralization of the enamel and / or of the dentin. A carious disease of the teeth can be counteracted by the use of materials according to the invention. In addition to the pleasure gratification so the candy according to the invention can be used in addition to the caries prophylaxis. According to a further preferred embodiment, in addition to the dispersion according to the invention or the composition according to the invention comprising these, the compositions according to the invention additionally comprise at least one fluoride salt. Surprisingly, it has been found that the addition of fluoride leads to a synergistic enhancement of the nucleating effect of the composite materials according to the invention. Particularly preferred is the addition of sodium and / or potassium fluoride. With the simultaneous addition of active compounds according to the invention and small amounts of fluoride, an approximately five-fold synergistic amplification is evident.

Preference is given in accordance with the invention to amounts of from 0.01 to 1.2% by weight, in particular from 0.1 to 0.90% by weight of fluoride salt, depending on the fluoride salt used (for example sodium fluoride). This corresponds to an amount of fluoride ions used from 0.05 to 0, 15 wt .-%, in particular from 0.08 to 0, 12 wt .-%.

Preference is given according to the invention amounts of 0.05 to 0.15 wt .-%, in particular from 0.08 to 0.12 wt .-% fluoride based on the amount of fluoride ions.

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

As a starting material for the examples, a sufficient amount of an apatite gelatin composite was initially made available.

For the preparation of said apatite gelatin composite 2000 ml of demineralized water were placed in a thermostated at 25 ⁰ C 4 I beaker and 44.10 g (0.30 mol) of CaCl ₂ -2H ₂ O (Fisher Chemicals pa) dissolved therein. Separately, 35 g of gelatin (type AB, DGF-Stoess, Eberbach) were dissolved at about 50 ^° C. in 350 ml of demineralized water. Both solutions were combined and stirred vigorously with a propeller stirrer. The pH was adjusted to 7.0 with dilute aqueous base.

With vigorous stirring, 300 ml of a 0.6 M (NH ₄ ) ₂ HPO ₄ solution, which had previously been adjusted to pH 7.0, were added uniformly to this gelatin and calcium salt solution over a period of 120 minutes. The pH was kept constant at pH 7.0 by the controlled addition of dilute aqueous base. After completion of the addition, stirring was continued for 24 h.

Subsequently, the dispersion was filled in centrifuge beakers and the solids content separated from the solution by centrifugation.

After drying, the composite material contained 43 percent by weight of organic, ie proteinaceous, portions. This proportion can be determined by ashing of the material at 800 ^° C. for 3 hours or by the expert evaluation of a thermogravimetric measurement or by carbon combustion analysis (CHN) or by Kjeldal nitrogen analysis, whereby the proportion of the ammonium chloride contamination can be excluded in each case. The procedure was continued with this dry composite material as follows: Several batches of a dispersion D consisting of

9.5% apatite / gelatin composite

15% glycerin

3% other additives such as preservatives, salts, etc. and water ad 100%

produced. All% data are by weight% with respect to the total amount of dispersion D.

When storing such a dispersion under different climatic conditions (at constant storage temperatures of -1 O ⁰ C to + 4O ⁰ C or alternating climate: each for 12 h 4O ⁰ C, 32.5 ⁰ C, 25 ⁰ C, 32.5 ⁰ C. , 4O ⁰ C, 32.5 ⁰ C, etc.) sediment these partially at room temperature and all other storage conditions described within a few days. Above that Sediment forms a clear, low-viscosity supernatant. In some cases, however, their viscosity also increases, in spite of the same chemical composition, so that a cut-resistant mass results.

Example 1 :

A formulation A according to the invention was prepared, consisting of

85% of dispersion D and 15% of Empicol LXSV / S (sodium dodecylsulfate) The% data are based on% by weight with respect to the total amount of formulation A. Dispersion D was initially charged and then the surfactant was added. The incorporation of the surfactant was carried out at an elevated temperature of about 5O ⁰ C. After one hour of stirring with a paddle was a dispersion with a viscosity in the range of 1 to 10 Pa.s at a shear rate of 30 s ^"1 measured at 2O ⁰ C before.

When storing such a dispersion under various climatic conditions (at constant storage temperatures of -10 ° C to + 4O ⁰ C or alternating climate: each for 12 h 4O ⁰ C, 32.5 ⁰ C, 25 ⁰ C, 32.5 ⁰ C, 4O ⁰ C, 32.5 ⁰ C, etc.) were still after a period of 4 weeks

Dispersions having a viscosity in the range 300-1700 mPa-s at a shear rate of 30 s ^"measured at 2O ⁰ C before ^{the first} addition, no phase separation was visually apparent, although the starting products not according to the invention shown a visible phase separation after a few days at room temperature had or were gelled.

In addition, the final viscosity of the dispersion according to the invention was even after a storage period of 4 weeks under the above climatic conditions measured at shear rates of 30 s ^"1 and at 2O ⁰ C still greater than one-third and less than 3 times the viscosity starting value (at the beginning of the storage period measured).

Example 2:

There have been combinations according to the invention of an investigation on their antimicrobial

Effectiveness.

The starting material for the examples was first a sufficient amount of an apatite

Gelatin composites provided.

For the preparation of said apatite gelatin composite 2000 ml of demineralized

Water in a thermostated at 25 ⁰ C 4 I beaker and 44.10 g (0.30

Mol) CaCl ₂ -2H ₂ O (Fisher Chemicals pa). Separately, 35 g of gelatin (type AB, DGF-Stoess, Eberbach) were dissolved at about 50 ^° C. in 350 ml of demineralized water.

Both solutions were combined and stirred vigorously with a propeller stirrer. The pH was adjusted to 7.0 with dilute aqueous base.

With vigorous stirring, 300 ml of a 0.6 M (NH ₄ ) ₂ HPO ₄ solution, which had previously been adjusted to pH 7.0, were added uniformly to this gelatin and calcium salt solution over a period of 120 minutes. The pH was kept constant at pH 7.0 by the controlled addition of dilute aqueous base. After completion of the addition, stirring was continued for 24 h. Subsequently, the dispersion was filled in centrifuge beakers and the solids content separated from the solution by centrifugation.

After drying, the composite material contained 43 percent by weight of organic, ie proteinaceous, portions. This proportion can be determined by ashing of the material at 800 ^° C. for 3 hours or by the expert evaluation of a thermogravimetric measurement or by carbon combustion analysis (CHN) or by Kjeldal nitrogen analysis, whereby the proportion of the ammonium chloride contamination can be excluded in each case. The procedure was continued with this dry composite material as follows: Several batches of a dispersion D consisting of

9.5% apatite / gelatin composite

19% Empicol LXSV / S (sodium dodecyl sulfate) and water ad 100%

produced. All% data are by weight% with respect to the total amount of dispersion D.

From the dispersion D, the following formulations were prepared, which have a pH of about 7:

A: 80% of dispersion D and 15% glycerol and water ad 100%

B: 80% of dispersion D and 16% glycerol and 3% ethyl p-hydroxybenzoate and water ad 100%

C: 80% of dispersion D and 21% glycerol and 1, 5% ethyl p-hydroxybenzoate and

Water ad 100%

About 30 g each of the formulations to be investigated were each containing about 0.3 ml of a bacterial inoculum suspension of about 1-5 × 10 ⁸ CFU / ml, comprising the germs Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, Enterobacter gergoviae, Pseudomonas aeruginosa, Burkolderia cepacia , charged. On the following days it was tested when the germs introduced into the formulation had died.

While in Formulation A living bacteria were still detected after 28 days, the germs in Formulation B were killed after 14 days and in Formulation C already after 7 days. In particular, the result with Formulation C shows that the combination of ideal ratios between solvent and surfactant can be used to optimize (reduce) the use of antimicrobial components.

Claims

claims: 1 . Homogeneous, storage-stable dispersion comprising a) at least one sparingly soluble in water calcium salt and / or b) at least one polymer component, and c) more than 10 wt.% Of at least one surfactant. 2. Dispersion according to claim 1, characterized in that a composite of said sparingly soluble in water calcium salt and said polymer component is present. 3. Dispersion according to one of claims 1 or 2, characterized in that said sparingly soluble in water calcium salt and / or said composite 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. 4. Dispersion according to claim 3, characterized in that the particles are rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped. 5. Dispersion according to one of claims 3 or 4, characterized in that a single crystallite has 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 a length of 10 to 50 nm; particularly preferably has a thickness of 3 to 1 1 nm and a length of 15 to 25 nm. 6. Dispersion according to one of claims 4 or 5, characterized in that the platelet-shaped particles have a length of 10 to 150 nm and a width of 5 to 150 nm. 7. Dispersion according to one of claims 3 to 6, characterized in that the particles have a ratio of length to width of 1 to 4, preferably from 1 to 3, particularly preferably from 1 to 2. 8. Dispersion according to one of claims 3 to 7, characterized in that the particles at least one side with an area of 0.1 ^* 10 ^{~ 15} m ² to 90 ^* 10 ^{~ 15} m ² , preferably of 0.5 ^* 10 ^{" 15} m ² to 50 ^* 10 ^"15 m ² , more preferably 1, 0 ^* 10 ^{" 15} m ² to 30 ^* 10 ^"15 m ² , most preferably 1, 5 ^* 10 ¹⁵ m ² to 15 ^* 10 ¹⁵ have m ² . 9. Dispersion according to one of claims 3 to 8, characterized in that the crystallites and / or particles of said calcium salts are coated by one or more surface modifiers. 10. Dispersion according to one of claims 1 to 9, characterized in that said polymer component is selected from the groups of protein components, polyelectrolytes and polysaccharides. 1 1. A dispersion according to claim 10, characterized in that said polyelectrolytes are selected from the group consisting of polyaspartic acids, alginic acids, pectins, deoxyribonucleic acids, ribonucleic acids, polyacrylic acids and polymethacrylic acids. 12. Dispersion according to claim 10, characterized in that said polysaccharides are selected from glucuronic acid and / or iduronic acid-containing polysaccharides, preferably from glycosaminoglycans, in particular selected from chondroitin sulfates, heparin and hyaluronic acid, and xanthan. 13. Dispersion according to claim 10, characterized in that said protein component is selected from proteins, protein hydrolysates and protein hydrolyzate derivatives. 14. Dispersion according to claim 10, characterized in that said protein component is selected from collagen, gelatin, keratin, casein, wheat protein, rice protein, soy protein, almond protein and their hydrolyzates and hydrolyzate derivatives. 15. Dispersion according to claim 14, characterized in that said protein component is selected from collagen, gelatin, casein and their hydrolysates, preferably gelatin, more preferably gelatin of the type A, B or AB, in particular gelatin of the acid bone type. 16. A dispersion according to any one of claims 2 to 15, characterized in that said sparingly soluble in water calcium salt and said polymer component in the form of a composite, wherein the polymer component is a protein component whose proportion 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. 17. A dispersion according to any one of claims 1 to 16, characterized in that in the dispersion of the weight percent of i) total amount of said surfactant more than 60% based on the j) total amount of claim 1 under a) and b) mentioned Components. 18. A dispersion according to claim 17, characterized in that the total amount referred to in i) in relation to the total amount according to j) at 0.8: 1 to 5: 1, preferably 1: 1 to 4: 1 and more preferably at 1: 1 to 3: 1. 19. A dispersion according to any one of claims 1 to 18, characterized in that said dispersion at 20 ⁰ C using a Rotationsrheometers (TA Instruments AR 1000) at Shear rates of 30 sec ^{1 has} a viscosity between 100 mPa s and 30,000 mPa s, preferably between 200 mPa s and 10,000 mPa s and in particular between 250 mPa s and 5000 mPa s. 20. Dispersion according to one of claims 1 to 19, characterized in that the viscosity of said dispersion after storage over a period of 4 weeks at a constant storage temperature between ^{0 0} C and 40 ⁰ C between 100 mPa-s and 30,000 mPa s, preferably between 200 mPa s and 10000 mPa s and in particular between 250 mPa s and 5000 mPa s, wherein the measurement at 20 ⁰ C using a rotary rheometer (TA Instruments AR 1000) at shear rates of 30 sec ^{"1 was} performed. 21. A dispersion according to any one of claims 2 to 20, that the proportion of the claimed in claim 1 b) component in the composite material between 0.5 and 70 wt .-%, preferably between 8 and 60 wt .-% based on the total weight of the composite material is. 22. Dispersion according to one of claims 1 to 21, characterized in that the liquid phase of the dispersion contains an organic solvent. 23. A dispersion according to claim 22, characterized in that said organic solvent is selected from the group of hydroxyl-containing solvents and / or derivatives thereof. 24. A dispersion according to claim 23, characterized in that said organic solvent is selected from polyhydroxy group-containing solvents and / or derivatives thereof. 25. A dispersion according to any one of claims 23 or 24, characterized in that said organic solvent is selected from the group of alcohols, preferably having 1 to 4 carbon atoms, and / or derivatives thereof. 26. A dispersion according to claim 25, characterized in that the group of alcohols is to be understood as the group of polyhydric alcohols. 27. A dispersion according to claim 25 or 26, characterized in that said organic solvent is selected from ethanol, 1, 2-propanediol, glycerol, hexanediol and mixtures thereof. 28. A dispersion according to any one of claims 25 to 27, characterized in that said organic solvent is selected from Diisopropylmonomethylether, Dipropylenglykolmonomethylether, Butyldiglycolether. 29. A dispersion according to any one of claims 1 to 28, characterized in that the surfactant mentioned in claim 1 according to c) is selected from the groups of anionic, cationic, nonionic, zwitterionic / amphoteric surfactants (amphoterics / betaines), the alkylamine oxides, the Silicone compounds and the phosphoric acid esters and their salts. 30. A dispersion according to claim 29, characterized in that said surfactant is selected from the groups of a) alkyl sulfates having a saturated or unsaturated, branched or linear alkyl kylgruppe having 8 to 22 carbon atoms, b) alkyl glucosides having a saturated or unsaturated, branched or linear alkyl group having 8 to 22 C atoms, c) fatty acid ethanolamides having a saturated or unsaturated, branched or linear alkyl group having 8 to 22 C atoms, d) betaines, e) ether sulfates. 31. A dispersion according to claim 30, characterized in that the group comprises a) alkyl sulfates having a saturated or unsaturated, branched or linear alkyl group having 10 to 16 carbon atoms, which is preferably contained as alkyl sulfate sodium lauryl sulfate. 32. A dispersion according to claim 31, characterized in that the group b) comprises alkylglucosides having a saturated or unsaturated, branched or linear alkyl group having 10 to 16 carbon atoms. 33. A dispersion according to claim 32, characterized in that is contained as the alkyl glucoside lauryl glucoside. 34. A dispersion according to claim 30, characterized in that the group c) fatty acid ethanolamides having a saturated or unsaturated, branched or linear alkyl group having 10 to 16 carbon atoms, particularly preferably lauryl-ethanolamide. 35. A dispersion according to any one of claims 1 to 34, characterized in that the dispersion additionally one or more antimicrobial components, preferably selected from the groups of alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives , Oxygen, nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl carbamate, iodine, iodophores, peroxides, p-hydroxybenzoic acid esters, preferably selected from the methyl, ethyl and propyl esters. A dispersion according to any one of claims 1 to 35, characterized in that the dispersion contains a solvent to be used according to claims 22 to 28 and an antimicrobial component to be used according to claim 35. 37. A dispersion according to claim 36, characterized in that the dispersion contains as solvent glycerol. 38. A dispersion according to claim 36 or 37, characterized in that the dispersion contains as antimicrobial component at least one p-hydroxy-benzoic acid ester, preferably selected from the methyl, ethyl and propyl ester. 39. Dispersion according to one of claims 36 to 38, characterized in that the dispersion contains at least one further antimicrobial component with fungistatic and / or fungicidal activity. 40. A dispersion according to any one of claims 36 to 39, characterized in that the weight percent ratio of the solvent to be used according to claims 22 to 28 to the surfactant according to the invention contained in the dispersion 5: 1 to 1: 100, preferably 4: 1 to 1: 10, in particular from 3: 1 to 1: 3. 41. Antimicrobial combination, comprising a according to claims 22 to 28 to be used solvent, in particular glycerol and an inventively present surfactant, in particular sodium lauryl sulfate, characterized in that the weight percent ratio of solvent to surfactant 5: 1 to 1: 100, preferably from 4: 1 to 1:10, in particular from 3: 1 to 1: 3. 42. Dispersion obtainable by combining a calcium salt according to the invention and / or a polymer component according to the invention with one or further components selected from the surfactants present invention. 43. A dispersion according to claim 42, characterized in that said, preferably glycerin dispersion before, during or after contacting with said one or more components is heated to 30 to 8O ⁰ C, preferably to 35 to 65 ⁰ C, in particular to 40 to 6O ⁰ C. 44. Compositions which contain a combination of a dispersion according to any one of claims 1 to 43 with other active ingredients and ingredients or by combination of a dispersion according to any one of claims 1 to 43 are available with further active ingredients and ingredients. 45. A process for the preparation of a dispersion according to any one of claims 1 to 43, characterized in that a preferably glycerin dispersion comprising the calcium salt mentioned in claim 1 according to a) and / or in claim 1 according to b) polymer component with one or more Components selected from the mentioned in claim 1 according to c) surfactant is brought together. 46. The method according to claim 435, characterized in that said, preferably glycerin dispersion before, during or after contacting with said one or more components is heated to 30 to 8O ⁰ C, preferably to 35 to 65 ⁰ C, in particular to 40 bis 6O ⁰ C. 47. Use of a dispersion according to any one of claims 1 to 43 or a composition according to claim 44 in compositions for cleaning and / or care of the teeth. 48. Use of a dispersion according to any one of claims 1 to 43 or a composition according to claim 44 for the preparation of compositions for strengthening the enamel. 49. Use of a dispersion according to any one of claims 1 to 43 or a composition according to claim 44 as the biomineralization inducing or promoting component for the preparation of compositions for the treatment of dental or bone defects. 50. Use of a dispersion according to any one of claims 1 to 43 or a composition according to claim 44 as a component for the protection and / or therapeutic and / or preventive treatment of teeth and / or bones before or in case of damage to external influences, in particular physical, chemical, physical and / or microbiological nature. 51. Use according to claim 50, characterized in that said external influences include attacks by acids, in particular due to bacterial activity or the action of acids from foodstuffs. Use according to claim 50, characterized in that said protection and / or said preventative treatment results in a reduction or inhibition of the demineralization of the teeth. 53. Use according to claim 50, characterized in that said protection and / or said preventive treatment results in sealing of fissures. 54. Use according to claim 50, characterized in that said protection and / or said preventive treatment leads to the protection and / or repair of primary lesions and / or initial caries in enamel. 55. Use according to claim 50, characterized in that said protection and / or said preventative treatment leads to the repair of erosions in bones and teeth, especially in enamel. 56. Use according to claim 50, characterized in that said protection and / or said preventive treatment leads to caries prophylaxis. 57. Use according to claim 50, characterized in that said protection and / or said preventive treatment leads to smoothing of the tooth surface. 58. Use according to claim 50, characterized in that said protection and / or said preventative treatment results in improving the cleanability of the teeth. Use according to claim 50, characterized in that said protection and / or said preventative treatment generally results in improving dental health. 60. Use according to claim 50, characterized in that said protection and / or said preventative treatment results in better mechanical resistance, in particular that the extent of micro-scratches, craters or mechanical abrasion is reduced. 61. Use of a dispersion according to any one of claims 1 to 43 or a composition according to claim 44 for coating implants. 62. Use of a dispersion according to any one of claims 1 to 43 or a composition according to claim 44 as an additive for food. 63. Oral and dental care and cleaning compositions containing a dispersion according to one of claims 1 to 43 or a composition according to claim 44. 64. Oral and dental care and cleaning agent according to claim 61, characterized in that it is toothpastes. 65. Sweets containing a dispersion according to any one of claims 1 to 43 or a composition according to claim 44. 66. Sweets according to claim 65, characterized in that they are selected from chewing gum, hard and soft caramels, gummi sweets, jelly products, marshmallows, liquorice, dragees, lozenges and candied fruits. 67. Compositions for inducing or promoting the regeneration of bone tissue containing a dispersion according to any one of claims 1 to 43 or a composition according to claim 44.