EP1942989A1

EP1942989A1 - Viscous remineralising oral and dental care agents and dental cleaning agents

Info

Publication number: EP1942989A1
Application number: EP06806499A
Authority: EP
Inventors: Tech Gmbh&Co. Kg Sus; Ulllrich Bernecker; Adolf Peter Barth; Christiane SCHÜLE; Tilo Poth; Holger Franke
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2005-10-31
Filing date: 2006-10-24
Publication date: 2008-07-16
Also published as: WO2007051543A1

Abstract

The invention relates to oral and dental care agents and dental cleaning agents comprising > 0.005 % by weight of calcium salt(s) in the form of individual crystallites or particles comprising a plurality of said crystallites, an individual crystallite having a thickness ranging between 2 and 50 nm and a length ranging between 10 and 150 nm. The particles are rod and/or plate-shaped, preferably predominantly plate-shaped and the agent has a viscosity, (after 7 days of storage at 20 °C, measured at 20 °C and an air pressure of 1 bar, Brookfield viscosimeter RVDV II+, with Helipath at a shear rate of 4 U/min), of 450,000 to 1,000,000 mPas, preferably from 500,000 to 700,000 mPas and in particular from 550,000 to 650,000 mPas. Said oral and dental care agents and dental cleaning agents remineralise the teeth, making them less sensitive to external influences.

Description

"Viscose remineralizing oral and dental care and cleaning products"

The invention relates to preparations for oral and dental care and cleaning, which have a remineralizing effect due to special ingredients, have a high cleaning performance, without scratching the tooth surface or to be very abrasive and beyond the Disease of halitosis and reduce bad breath.

Dentifrices are available in various forms on the market and are primarily used to clean the tooth surface and to prevent tooth and gum disease. They usually contain a combination of polishes, humectants, surfactants, binders, flavorings and fluoride-containing and antimicrobial agents. In addition to toothpowder, which play a minor role because of their increased abrasiveness, dentifrices are mainly offered in paste, cream and translucent or transparent gel form. Liquid or liquid toothpastes and mouthwashes have also become increasingly important in recent years.

In addition to the cleaning of the teeth, the consumer of the generic products also expected a care of the teeth and the oral cavity. In particular, a "clean" feel, ie a smooth and shiny tooth surface as well as a fresh mouthfeel are essential aspects for the buying incentive of oral and dental care and cleaning preparations. A successful remedy of the generic type should therefore thoroughly clean the teeth without damaging the tooth or tooth surface while reducing and / or preventing bad breath.

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). But calcium fluoride has been described several times as part of dentifrices and as a component for strengthening the enamel and for caries prophylaxis.

The availability of these substances for the desired remineralization crucially depends on the particle size of these sparingly water-soluble and dispersed in the dentifrice components. It has therefore been proposed to use these sparingly soluble calcium salts in the finest distribution.

From DE-A-21 34 862, for example, a dentifrice for hypersensitive teeth was known, the ultrafine hydroxyapatite (Ca ₅ [(PO ₄ ) ₃ OH]), the particle size of 6-8 microns (microns) is given because by grinding hardly higher subtleties can be achieved. In EP 1 139 995 A1 it is proposed to stabilize suspensions of calcium salts which are sparingly soluble in water in very finely divided form during precipitation or shortly thereafter by carrying out the precipitation in the presence of an agglomeration inhibitor or redispersing the dispersion in the presence of the agglomeration inhibitor. These suspensions can be used in toothpastes, amounts above 0.1% by weight (based on the total composition and calculated as calcium salt) being disclosed.

It was the task of solving the above-mentioned problems without having to incorporate high levels of possibly more expensive ingredients in the formulations. In addition, the object of the present invention was to provide oral and dental care and cleaning agents that remineralize the teeth and make them less sensitive to external influences.

It has now been found that nanoparticulate calcium salts are effective also and in particular in small amounts, in particular when the viscosity of the agents is adjusted to specific values.

The present invention is in a first embodiment, an oral and dental care and cleaning agent containing ≥ 0.005 wt .-% calcium salt (s) in the form of individual crystallites or in the form of particles, comprising a plurality of said crystallites, wherein a single Crystallite having a thickness in the range of 2 to 50 nm and a length in the range of 10 to 150 nm, wherein the particles are rod and / or platelet-shaped, preferably predominantly platelet-shaped and wherein the agent has a viscosity (after 7 days storage at 20 ⁰ C, measured at 20 ° C and an air pressure of 1 bar, Brookfield RVDV II + viscometer, with Helipath at a shear rate of 4 U / min) from 450,000 to 1,000,000 mPas, preferably from 500,000 to 700,000 mPas and in particular from 550,000 to 650,000 mPas.

Oral and dental care products as well as mouth and tooth cleaning agents in the sense of the invention are mouthwashes and toothpowder, oral and toothpastes, liquid mouthwashes and toothpastes as well as oral and dental gels. Preferably, toothpastes and liquid dentifrices are suitable. For this purpose, the oral and dental care and cleaning agents, e.g. in the form of toothpastes, liquid toothpastes, toothpowder, mouthwashes or possibly also as gum, e.g. B. as chewing gum, present. Preferably, however, they are present as more or less flowable or plastic toothpastes, as they are used for cleaning the teeth using a toothbrush.

The compositions according to the invention have a remineralizing effect. In addition, the sparingly soluble calcium salt, and in particular its composites, is additionally capable of In the natural saliva of humans to deposit in supersaturated concentrations calcium and phosphate ions. This nucleation effect thus leads to the construction of new tooth material (neomineralization), in particular of the enamel and / or of the dentin, from the body's own reservoirs. In particular, this achieves a closure of the dentinal tubules.

Particular preference is given to using sparingly water-soluble calcium salts according to the invention, which are more preferably selected from phosphates, fluorides and fluorophosphates.

As slightly soluble or sparingly soluble in water (hereinafter also referred to as sparingly soluble, poorly soluble in water or sparingly soluble), those salts are to be understood which are soluble in water or in the liquid suspension medium to less than 1 g / l (20 ° C) , Preferred salts are calcium hydroxyphosphate (Ca ₅ [OH (PO ₄ ) ₃ ]) or hydroxylapatite, calcium fluorophosphate (Ca ₅ [F (PO ₄ J ₃ ]) or fluoroapatite, F-doped hydroxyapatite of the general composition Ca ₅ (PO ₄ J ₃ (OH ₁ F) and calcium fluoride (Ca F ₂ ) or fluorite (fluorspar).

According to the invention, particularly preferred oral and dental care and cleaning compositions contain, based on their weight, from 0.01 to 0.5% by weight, preferably from 0.02 to 0.4% by weight, particularly preferably from 0.03 to 0.25 wt .-%, more preferably 0.04 to 0.2 wt .-% and in particular 0.05 to 0.15 wt .-% calcium salt (s) in the form of individual crystallites or in the form of rod and or platelet-shaped, preferably predominantly platelet-shaped particles comprising a plurality of said crystallites, wherein 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 from 10 to 50 nm; particularly preferably has a thickness of 3 to 7 nm and a length of 15 to 25 nm.

In addition, oral and dental care and cleaning preparations according to the invention are preferred in which the calcium salt (s) in the form of individual crystallites or in the form of rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped particles comprising a plurality of said crystallites, wherein 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, is selected from the group hydroxyapatite, fluoroapatite and calcium fluoride.

The oral and dental care and cleaning agents according to the invention may additionally contain carboxymethylcellulose; this is desirable in view of the theological properties of the agents, moreover, an enhancement of the calcium salt (e) in the form of individual predominantly crystallites or in the form of particles comprising a plurality of said crystallites, wherein 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, found when the compositions of the invention contain carboxymethylcellulose. The carboxymethyl cellulose (CMC for short) is generally the sodium salt of the glycolic acid ether of cellulose. CMC can be described by the following formula in which the radicals R are selected from H, CH ₂ -COONa:

CMC is technically produced by reacting alkali cellulose with monochloroacetic acid or its sodium salt. The resulting CMC contains due to production of common salt and sodium glycolate and diglycolate. Commercially available CMC is a colorless powder or granules and is offered with degrees of substitution of about 0.5-1.5 and a wide range of solution viscosities.

Preferred oral and dental care and cleaning agents according to the invention are characterized in that they contain, based on their weight, from 0.25 to 2.0% by weight, preferably from 0.5 to 1, 75% by weight and in particular 0, Containing 75 to 1, 5 wt .-% carboxymethycellulose (CMC).

Particularly preferred is the use of CMC grades with specific Theological properties. Here are the oral and dental care and cleaning according to the invention bsonders preferably containing a Na-CMC, the 2 wt .-% - solution in water has a viscosity (after 7 days of storage at 2O ⁰ C, measured at 2O ⁰ C and an air pressure of 1 bar, Brookfield RVDV II + viscometer, with helipath at a shear rate of 4 rpm) of from 200 to 1000 mPas, preferably from 300 to 800 mPas and in particular from 350 to 700 mPas.

In addition to the stated calcium salts in nanoparticulate form, the oral and dental care and cleaning compositions according to the invention may contain further Ca salts, which need not necessarily be nanoparticulate. Here, in particular, calcium glycerophosphate has proven that is marketed under the trade name Furdentyl ^®.

Oral and dental care and cleaning agents which are particularly preferred according to the invention are characterized in that they contain, in addition to the calcium salt (s) in the form of individual crystallites or in the form of rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped particles comprising A plurality of said crystallites, wherein 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, contain further calcium salt (s), preferably calcium glycerophosphate. The oral and dental care and cleaning agents according to the invention may contain the nanoparticulate calcium salts in different forms. Preferably, the calcium salts are stabilized against agglomeration. In a first preferred embodiment of the present invention, the oral and dental care of the invention contain the calcium salt (s) in the form of individual crystallites or in the form of rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped particles comprising a plurality of said crystallites , wherein 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 the form of a suspension, which - based on the weight of the suspension - a) 0.01 to 15 wt. %, preferably 0.1 to 10 wt .-% and in particular 0.5 to 7.5 wt .-% of at least one water-soluble surfactant and / or at least one water-soluble polymeric protective colloid; b) 0.01 to 15 wt .-%, preferably 0.1 to 10 wt .-% and in particular 0.5 to 7.5 wt .-% of the or the calcium salts (s) in the form of individual crystallites or in A form of rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped, particles comprising a plurality of said crystallites, wherein 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 this embodiment, as the liquid medium in which the calcium salts may be dispersed, water is primarily suitable. Those made from an aqueous suspension, e.g. However, calcium salt particles isolated by filtration or centrifugation can also be redispersed in organic solvents and likewise yield suspensions of the primary particles in the nanometer range, which hardly tend to agglomerate. Suitable organic liquid media are e.g. water-soluble, lower alcohols and glycols, polyethylene glycols, glycerol or mixtures thereof with each other or with water.

Among primary particles, the crystallites, i. H. understood the single crystals of said calcium salts. The term "length" is to be understood here as meaning the diameter of the particles in the direction of their greatest length extension. Thickness here is to be understood as the smallest diameter of the crystallites (primary particles). The determination of the corresponding different diameters of the crystallites can be determined by 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.

According to a particularly preferred embodiment, the shape of a single crystallite is rather rod-shaped. According to a particularly preferred embodiment, the crystallites preferably have a thickness of 2 to 15 nm and a length of 10 to 50 nm; more preferably, a thickness of 3 to 11 nm and a length of 15 to 25 nm, on.

Surprisingly, it has been possible to provide calcium salts or composite materials comprising these, which have a predominantly platelet-like structure of the particles.

The particles of the calcium salts, which are composed of individual crystallites according to the invention, can be present in the form of platelets and / or rods depending on the conditions of the production process.

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.

Advantageously, the calcium salts or composite materials according to the invention comprising these, with the predominantly platelet-like calcium particles of the structure of the bone substance in vivo, which is also composed of plates, are particularly similar. This has the particular advantage that, because of the similarity of the form with the biological apatites (for example bone or dentin apatite), they have a particularly good ability for re-mineralization and neo-mineralization, so that the process of biomineralization can take place even faster and better.

A further advantage of the invention is that the sparingly water-soluble calcium salts or composite materials comprising these having a predominantly platelet-like structure of the calcium salts have improved biocompatibility.

According to a further preferred embodiment of the invention, the calcium salts used according to the invention and / or the composite materials comprising these with an average particle diameter of the particles in the range of less than 1000 nm, preferably less than 300 nm.

The particle diameter is to be understood here as the diameter of the particles in the direction of their greatest length expansion (= length of the particles). The mean particle diameter is to be understood as a value which is averaged over the total amount of the composite. It is according to the invention below 1000 nm, preferably below 300 nm.

The determination of the particle diameter of the particles can be determined by methods familiar to the person skilled in the art, in particular by the evaluation of imaging methods, in particular transmission electron microscopy. According to a particular embodiment, the sparingly water-soluble calcium salts according to the invention and / or the composite materials comprising these, platelet-shaped particles having a width in the range of 5 to 150 nm and a length in the range of 10 to 150 nm and a height (thickness) of 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 can be observed in particular in the images which can be recorded by means of 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. The width of these particles is preferably in the range between 10 and 100 nm.

According to a particular embodiment, in the case of the particles of the sparingly water-soluble calcium salts and / or composite materials according to the invention comprising these, the ratio of length to width is between 1 and 4, preferably from 1 to 3, more preferably between 1 and 2, for example 1, 2 (Length 60 nm, width 50 nm) or 1, 5 (length 80, width 40 nm).

The platelet-like shape of the particles is formed by the ratio of length to width. If the ratio between length and width is significantly greater than 4, rod-shaped particles are more likely.

The advantage of the platelet-shaped particles with a ratio of preferably 1 to 2 is that these particles have a natural bone material particularly similar length to width ratio and therefore a particularly good and biocompatible Re- or neomineralization of the tooth material (dentin and enamel ) exhibit.

According to a further particular embodiment, the particles have a surface area of 0.1 * ¹⁰ ¹⁵ m ² to 90 * 10 ^"15 m ^2, preferably an area of 0.5 * ^{10" 15} m ² to 50 ^* 10 ^'15 m ² , more preferably 1, 0 ^* 10 ^"15 m ² to 30 ^* 10 ^" 1 ^S m ² , very particularly preferably 1, 5 * 10 ^"15 m ² to 15 * 10 ^{" 15} m ^2, for example 2 ^* 10 ^'15 m ² , 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.

The suspensions used in this preferred embodiment of the present invention contain (based on the weight of the suspension) 0.01 to 15 wt .-%, preferably 0.1 to 10 wt .-% and in particular 0.5 to 7.5 wt. -% of the calcium salt (s) in the form of individual crystallites or in the form of rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped particles comprising a plurality of said crystallites, having a thickness in the range of 2 to 50 nm and a length in the range of 10 to 150 nm. As a further ingredient of the suspension are (based on the suspension) 0.01 to 15 wt .-%, preferably 0.1 to 10 wt .-% and in particular 0.5 to 7.5 wt % of at least one water-soluble surfactant and / or at least one water-soluble polymeric protective colloid.

The term "surfactants" is understood as meaning surface-active substances which form adsorption layers on the upper and boundary surfaces or which can aggregate in volume phases to give micelle colloids or lyotropic mesophases. A distinction is made between anionic surfactants consisting of a hydrophobic radical and a negatively charged hydrophilic head group, amphoteric surfactants which carry both a negative and a compensating positive charge, cationic surfactants which have a hydrophilic group in addition to a positively charged hydrophilic group, and nonionic surfactants which have no charges but strong dipole moments and are highly hydrated in aqueous solution.

Suitable anionic surfactants (E1) in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, linear and branched fatty acids having 8 to 30 C atoms (Soap),

Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 16,

Acylsarcosides having 8 to 24 C atoms in the acyl group,

Acyltaurides having 8 to 24 carbon atoms in the acyl group,

Acyl isethionates having 8 to 24 C atoms in the acyl group,

Sulfobemsteinsäuremono- and dialkyl esters having 8 to 24 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester having 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 8 to 24 carbon atoms, linear alpha-olefinsulfonates with 8 to 24 carbon atoms,

Alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 C atoms,

Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -OSO ₃ H, in which R is a preferably linear alkyl group having 8 to 30 C atoms and x = O or 1 to 12, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ether

Sulfonates of unsaturated fatty acids having 8 to 24 carbon atoms and 1 to 6 double bonds

Esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15

Represent molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms,

Alkyl and / or alkenyl ether phosphates of the formula (E1-I),

R ¹ (OCH ₂ CH ₂ ) _n -OP (O) (OX) -OR ² (E1-I)

in the R ^{1 is} preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R ^{2 is} hydrogen, a radical (CH ₂ CH ₂ O) _n R ² or X, n is from 1 to 10 and X is hydrogen, an alkali metal radical or alkaline earth metal or NR ³ R ⁴ R ⁵ R ⁶ , where R ³ to R ⁶ independently of one another represents hydrogen or a C ₁ to C ₄ hydrocarbon radical, is, sulfated fatty acid alkylene glycol ester of the formula (E1-II) R ⁷ CO (AlkO) _n SO ₃ M (E1-II) in the R ⁷ CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, Alk for CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , n for numbers from 0.5 to 5 and M for a cation, monoglyceride sulfates and monoglyceride ether sulfates of the formula (E1-III)

CH ₂ O (CH ₂ CH ₂ O) _x -COR ⁸

I CHO (CH ₂ CH ₂ O) _y H (E1-III)

I CH ₂ O (CH ₂ CH ₂ O) ₂ SO ₃ X

in which R ⁸ CO is a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z are in total O or numbers from 1 to 30, preferably 2 to 10, and X is an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. Preferably, monoglyceride sulfates of the formula (E1-III) are used in which R ⁸ CO is a linear acyl radical having 8 to 18 carbon atoms, amide-ether carboxylic acids,

Condensation products of C ₈ - C ₃₀ - fatty alcohols with protein hydrolysates and / or amino acids and their derivatives, which are known to the skilled person as protein fatty acid condensates, such as Lamepon ^® - types Gluadin ^® - types Hostapon ^® KCG or Amisoft ^® - types.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethylester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, Monoglycerdisulfate, alkyl and Alkenyletherphosphate and protein fatty acid condensates.

Zwitterionic surfactants (E2) are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -C00 ^H or -SO ₃ ^H group. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyldimethylammonium niumglycinat, N-acyl-aminopropyl-N, N-dimethylammoniumglycinate, for example, the cocoacylaminopropyl-dimethylammoniumglycinat, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazoline having in each case 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants (E3) are understood as meaning those surface-active compounds which contain, in addition to a C ₈ -C ₂₄ -alkyl or -acyl group, at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and for forming internal Salts are capable. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidoproylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids with each about 8 to 24 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine.

Nonionic surfactants (E4) contain as hydrophilic group e.g. a polyol group, a polyalkylene glycol ether group, or a combination of polyol and polyglycol ether groups. Such compounds are, for example

- Addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the Alkyl group, with a methyl or C ₂ - C ₆ - alkyl radical end-capped addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 C. -atoms and with alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as the type available under the commercial names Dehydol ^® LS, Dehydol ^® LT (Cognis),

C ₁₂ -C ₃₀ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,

- addition products of 5 to 60 mol ethylene oxide onto castor oil and hydrogenated castor oil, polyol fatty acid esters, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol - types (Cognis),

- alkoxylated triglycerides,

alkoxylated fatty acid alkyl esters of the formula (E4-I)

R ¹ CO- (OCH ₂ CHR ² ) _W OR ³ (E4-I) in the R ¹ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or methyl, R ^{3 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and w is a number from 1 to 20 stands,

- amine oxides, hydroxy mixed ethers,

Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,

Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters,

Addition products of ethylene oxide onto fatty acid alkanolamides and fatty amines, sugar surfactants of the alkyl and alkenyl oligoglycoside type according to formula (E4-II),

in which R ^{4 is} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. The alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (E4-II) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides and stands for a number between 1 and 10. While p in the individual molecule must always be integer and here before For all given values p = 1 to 6, the value p for a given alkyloligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R ⁴ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl oligoglucosides of chain length C ₈ -C ₀ (DP = 1 to 3), which are obtained as first runnings in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol with a content of less than 6 wt .-% C ₁₂ - Alcohol can be contaminated and alkyl oligoglucosides based on technical Cg _/ n-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹⁵ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, Petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated _{C12 /} i ₄ coconut alcohol with a DP of 1 to 3

Sugar surfactants of the fatty acid N-alkyl polyhydroxyalkylamide type, a nonionic surfactant of the formula (E4-III),

R ⁵ CO-NR ⁶ - [Z] (E4-III)

R ^{5 is} CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{6 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands. The fatty acid N-alkyl polyhydroxyalkylamides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. Preferably, the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars having 5 or 6 carbon atoms, especially glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (E4-IV):

R ⁷ CO-N R ⁸ -CH ₂ - (C HOH) ₄ -CH ₂ OH (E4-I V)

The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (E4-IV) in which R ^{8 is} hydrogen or an alkyl group and R ⁷ CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or those technical mixtures. Particular preference is given to fatty acid N-alkylglucamides of the formula (E4-IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C 12/14 coconut fatty acid or a corresponding derivative. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

The preferred nonionic surfactants are the alkylene oxide addition products of saturated linear fatty alcohols and fatty acids having in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations having excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants. These connections are identified by the following parameters. The alkyl radical R contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When using so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

Furthermore, very particularly preferred nonionic surfactants are the sugar surfactants. These may preferably be present in the agents used according to the invention in amounts of from 0.1 to 20% by weight, based on the total agent. Amounts of 0.5-15% by weight are preferred, and most preferred are amounts of 0.5-7.5% by weight.

The compounds used as surfactant with alkyl groups may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides are used as catalysts. The use of products with narrow homolog distribution may be preferred.

Cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines can be used according to the invention. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names quaternium-27 and quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms. According to the invention, preference is given to using QAV with behenyl radicals, in particular those known as behentrimonium chloride or bromide (docosanyltrimethylammonium chloride or bromide). Other preferred QAV's have at least two behenyl residues, with QAV being particularly preferred, which are two behenyl residues on an imidazolinium backbone. Commercially available, these substances are, for example, under the names Genamin ^® KDMP (Clariant) and Crodazosoft ^® DBQ (Crodauza).

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^®, ^® and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N ₁ N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® L80 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group is that available under the name Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine.

Water-soluble polymeric protective colloids are understood as meaning high-molecular compounds which are adsorbed onto the surface of the nanoparticles and modify them in such a way that they are prevented from coagulating and agglomerating. Suitable polymeric protective colloids are e.g. natural water-soluble polymers such as e.g. Gelatin, casein, albumin, starch, vegetable gums and water-soluble derivatives of water-insoluble polymeric natural products, e.g. Cellulose ethers (methylcellulose, hydroxyethylcellulose, carboxymethylcellulose), hydroxyethyl starch or hydroxypropyl guar.

Synthetic water-soluble polymers useful as protective colloids are e.g. Polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, polyaspartic acid and others.

In preferred compositions of this embodiment of the invention, the suspension comprises one or more of polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and derivatives thereof, especially MC, HEC, HPC , HPMC and / or CMC, and / or copolymers and mixtures thereof. In the context of the present invention, polyvinyl alcohols are particularly preferred as water-soluble polymers. "Polyvinyl alcohols" (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure

in small proportions (about 2%) also structural units of the type

CH 2 CH CH CH 2 OH OH

contain.

Commercially available polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

In the context of the present invention preferred means of this embodiment are characterized in that the suspension comprises polyvinyl alcohols and / or PVAL copolymers whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

Preference is given to using polyvinyl alcohols of a specific molecular weight range, preference being given to compositions of this embodiment in which the suspension comprises polyvinyl alcohols and / or PVAL copolymers whose molecular weight is in the range from 3500 to 100,000 μmol ^"1 , preferably from 10,000 to 90,000 μmol ^{" 1} , particularly preferably from 12,000 to 80,000 gmol ^'1 and in particular from 13,000 to 70,000 gmol ^"1 .

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the context of the present invention especially suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

Further polyvinyl alcohols which are particularly suitable as protective colloid for the suspension are shown in the following table:

Further as protective colloid for the suspension suitable polyvinyl alcohols are ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C 500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK) , Also suitable are ERKOL types from Wacker.

A further preferred group of water-soluble polymers which can serve according to the invention as a protective colloid for the suspension are the polyvinylpyrrolidones. These are, for example, sold under the name Luviskol ^® (BASF). Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula (I)

which are prepared by free-radical polymerization of 1-vinylpyrrolidone by the method of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer provides only low molecular weight products. Commercially available polyvinylpyrrolidones have molar masses in the range of about 2500-750000 g / mol, which are characterized by the specification of the K values and - depending on the K value - have glass transition temperatures of 130-175 °. Also suitable are copolymers of vinylpyrrolidone with other monomers, in particular vinylpyrrolidone / Vinylester copolymers, as are marketed, for example under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers are particularly preferred non-ionic polymers.

The vinyl ester polymers are vinyl ester-accessible polymers having the moiety of the formula (II)

- CH ₉ - CH -

² I o

I

O ^ "R (M)

as a characteristic building block of the macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates by far the most important representatives of the greatest technical importance.

The polymerization of the vinyl esters is carried out free-radically by different processes (solution polymerization, suspension polymerization, emulsion polymerization,

Bulk polymerization.). Copolymers of vinyl acetate with vinylpyrrolidone contain monomer units of the formulas (I) and (II)

Further suitable water-soluble polymers are the polyethylene glycols (polyethylene oxides), which are referred to as PEG for short. PEG are polymers of ethylene glycol which are of the general formula (III)

H- (O-CH ₂ -CH ₂ ) _n -OH (III)

satisfy, where n can take values between 5 and> 100,000.

PEGs are prepared industrially by anionic ring-opening polymerization of ethylene oxide (oxirane), usually in the presence of small amounts of water. Depending on the reaction procedure, they have molar masses in the range of about 200-5,000,000 g / mol, corresponding to degrees of polymerization of about 5 to> 100,000.

The products with molecular weights <about 25 000 g / mol are liquid sore at room temperature are referred to as actual polyethylene glycols, abbreviated PEG. These short-chain PEGs can be added in particular to other water-soluble polymers, for example polyvinyl alcohols or cellulose ethers, as plasticizers. The polyethyleneglycols which can be used according to the invention and which are solid at room temperature are termed polyethylene oxides, abbreviated PEOX. High molecular weight polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and therefore show only weak glycol properties.

Also suitable as water-soluble coating material is also gelatine according to the invention, this preferably being used together with other polymers. Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as water-soluble coating material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.

Further water-soluble polymers which are suitable according to the invention in the suspension are described below:

Cellulose ethers, such as hydroxypropylcellulose, hydroxyethylcellulose and methylhydroxypropylcellulose, as sold, for example, under the trademarks Culminal ^® and Benecel ^® (AQUALON). Cellulose ethers can be described by the general formula (IV)

R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula (III) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose reacted with the etherifying reagent or how many moles of the etherifying agent were attached on average to an anhydroglucose unit , Hydroxyethylcelluloses are water-soluble from a DS of about 0.6 or an MS of about 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1, 35 (DS) and 1, 5-3 (MS). Hydroxyethyl and propylcelluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propylcelluloses are in cold and hot water as well as in some (hydrous) organic solvents soluble, in contrast, insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Preferred agents according to the invention are characterized in that the suspension comprises hydroxypropylmethylcellulose (HPMC) which has a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) of from 1.0 to 2.0, preferably from 1.4 to 1.9, and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of the cellulose) of from 0.1 to 0.3, preferably from 0.15 to 0.25.

Further polymers which are suitable according to the invention are water-soluble amphopolymers. Amphoteric polymers, ie polymers which contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers which contain quaternary ammonium groups in the molecule. COO ^' - or -SO ₃ ^' groups, and summarized those polymers containing -COOH or SO ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (I ₁ 1, 3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (for example acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and optionally further ionic or nonionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be seen. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium as they are available under the name Merquat ^® 2001 N commercially, are inventively particularly preferred amphopolymers. Other suitable amphoteric polymers are for example those available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate ^ -Hydroxypropylmethacrylat copolymers.

Water-soluble anionic polymers suitable according to the invention are u. a .:

Vinyl acetate / crotonic acid copolymers, such as are commercially available for example under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF). These polymers also have monomer units of the formula (II) above

[-CH (CH ₃ ) -CH (COOH) -] _n (V) Vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is that available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymers.

Acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers sold for example under the name Ultrahold ^® strong (BASF).

Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on polyalkylene glycols are obtained by homogeneous-phase polymerization by reacting the polyalkylene glycols in the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, in The presence of free radical initiator stirs. Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid those with aliphatic alcohols of low molecular weight, ie in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are proven.

Polypropylene glycols (abbreviated PPG) are polymers of propylene glycol which are of general formula VI

H- (O-CH-CH ₂ ) _n -OH (VI)

CH ₃

satisfy, where n can assume values between 1 (propylene glycol) and several thousand. Of particular importance here are di-, tri- and tetra-propylene glycols, i. the

Representatives with n = 2, 3 and 4 in formula VI.

In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used. grafted and crosslinked copolymers from the copolymerization of i) at least one nonionic type monomer, ii) at least one ionic type monomer, iii) polyethylene glycol, and iv) a crosslinker

The polyethylene glycol used has a molecular weight between 200 and more

Million, preferably between 300 and 30,000. The nonionic monomers may be of very different types, and among these, preferred are: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allylaurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.

The non-ionic monomers may equally be of very different types, among which particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the grafting polymers.

Preferred crosslinkers are ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose having 2 to 5 allyl groups per molecule of saccharin.

The grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight of at least one nonionic type monomer, ii) 3 to 80% by weight of at least one ionic type monomer, iii) 2 to 50% by weight, preferably 5% to 30% by weight of polyethylene glycol; and iv) 0.1% to 8% by weight of a crosslinking agent, the percentage of crosslinking agent being formed by the ratio of the total weights of i), ii) and iii) is. copolymers obtained by copolymerization of at least one monomer of each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, ii) unsaturated carboxylic acids, iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C ₈ -i ₈ -alcohols

Short-chain carboxylic acids or alcohols are to be understood as meaning those having 1 to 8 carbon atoms, it being possible for the carbon chains of these compounds to be interrupted, if appropriate, by divalent hetero groups such as -O-, -NH-, -S--.

Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester

These terpolymers contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyl esters of

Formula VII:

R ¹ R ³

R ² -CC (O) -O-CH ₂ - C = CH ₂ (VII) CH ₃ wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight or branched C _1-6 alkyl radical and the sum of

Carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2.

The abovementioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight.

Vinyl acetate and 8 to 20 wt .-%, preferably 10 to 17 wt .-% AlIIyI- or Methallyletsre of the formula VII.

Tetra- and pentapolymers from i) crotonic acid or allyloxyacetic acid ii) vinyl acetate or vinyl propionate iii) branched allyl or methallyl esters iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters

Crotonic acid copolymers with one or more monomers from the group of ethylene,

Vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts

Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic alpha-branched monocarboxylic acid.

Further polymers which are preferably usable in the invention according to the invention are cationic polymers. Among the cationic polymers, the permanent cationic polymers are preferred. According to the invention, "permanently cationic" refers to those polymers which have a cationic group independently of the pH. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as under the trade names Celquat ^® and polymer

^JR® are commercially available. The compounds Celquat ^® H 100, Celquat ^® L 200 and

Polymer ^JR® 400 are preferred quaternized cellulose derivatives.

Polysiloxanes with quaternary groups, such as those commercially available

Products Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone),

Dow ^Corning® 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067

(Manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; di- quaternary Polydime- thylsiloxane, quaternium-80),

Cationic guar derivatives, in particular the contracts under the trade names Cosmedia® ^® Guar and Jaguar ^® products,

Polymers dimethyldiallylammonium salts and their copolymers with esters and amides of

Acrylic acid and methacrylic acid. The under the names Merquat ^® 100

(Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride Acrylamide copolymer) commercially available products are examples of such cationic polymers.

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone quaternized with diethylsulfate

Dimethylaminomethacrylate copolymers. Such compounds are obtainable under the names Gafquat ^® 734 and Gafquat ^® 755 commercially.

Vinylpyrrolidone-methoimidazolinium chloride copolymers, as described under the name

Luviquat ^® are offered. quaternized polyvinyl alcohol and those under the names

Polyquaternium 2,

Polyquaternium 17,

Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the polymer main chain. The polymers mentioned are designated according to the so-called INCI nomenclature, details of which can be found in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, which are expressly incorporated herein by reference becomes.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the commercial product ^Polymer® JR 400, are very particularly preferred cationic polymers.

In preferred oral and dental care and cleaning compositions of this embodiment, the suspension preferably has pH values between 5 and 7, more preferably between 5.5 and 6.9, in particular between 6 and 6.6. Preferred viscosities of the suspension are in the range of 500 to 20,000 mPas, so that preferred oral and dental care and cleaning agents according to the invention are characterized in that the suspension at 2O ⁰ C has a viscosity (after 7 days storage at 2O ⁰ C, measured at 2O ⁰ C and an air pressure of 1 bar, Brookfield RVDV II + viscometer, with helipath at a shear rate of 4 U / min) of 500 to 20,000 mPas, preferably from 750 to 15,000 mPas and in particular from 1000 to 10,000 mPas.

The suspensions which can be used according to the invention can be prepared by precipitation reactions from aqueous solutions of water-soluble calcium salts and aqueous solutions of water-soluble phosphate or fluoride salts. The precipitation is carried out in the presence of water-soluble surfactants or water-soluble polymeric protective colloids. This can be done, for example, in such a way that the surfactants or protective colloids of the aqueous phosphate or fluoride Saline or the solution of the calcium salt are added before the reaction. Alternatively, the aqueous calcium salt solution may be added to an aqueous surfactant or protective colloid solution simultaneously with the phosphate or fluoride salt solution.

A further variant of the method comprises precipitation from a strongly acidic solution of a water-soluble calcium salt and a stoichiometric amount of a water-soluble phosphate salt having a pH below 3 by raising the pH with aqueous alkali or ammonia in the presence of water-soluble surfactants or water-soluble polymeric protective colloids performs.

To prepare suspensions according to the invention in other liquid media, it is expedient to start from aqueous suspensions according to the invention, remove them from the aqueous phase by filtration or centrifugation, optionally dry the nanoparticles and redispers it in organic solvents. In this case, a new addition of surfactants or protective colloids is no longer necessary because the nanoparticles contain the amounts of stabilizers required to inhibit agglomeration adsorbed on the surface. Fineness and stability of such suspensions is therefore comparable to the aqueous suspensions. Another possibility is to mix the aqueous suspension with a higher boiling solvent, e.g. with glycerin, to mix and remove the water by distillation. As an organic liquid medium, especially with regard to the use in dentifrices, especially glycerol and its liquid mixtures with sorbitol and optionally with water is suitable.

As an alternative to the above-mentioned embodiment or in addition thereto, the oral and dental care and cleaning agents according to the invention may also contain the nanoparticulate calcium salts in the form of composite materials.

According to a particular embodiment, the composite materials according to the invention comprise a. sparingly soluble calcium salts in water, wherein the calcium salts are in the form of individual crystallites or in the form of particles comprising a plurality of said crystallites, having an average particle diameter in the range of less than 1000 nm, preferably less than 300 nm, and b. a polymer component, wherein the particles in the composite material are rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped.

Composite materials are composites comprising the components mentioned under a) and b) and microscopically heterogeneous, macroscopic but homogeneous in which the primary particles of the calcium salts are associated with the framework of the polymer component. The proportion of polymer components in the composite materials is from 0.1 to 80% by weight, preferably from 10 to 60% by weight and in particular from 30 to 50 wt .-%, based on the total weight of the composite materials.

According to a particularly preferred embodiment, the polymer component of the composite material contained in the remineralizing product is selected from a protein component, polyelectrolytes and polysaccharides.

A preferred embodiment of the invention is that polyelectrolytes are used as the polymer component.

Suitable polyelectrolytes for the purposes of the invention are polyacids and polybases, it being possible for the polyelectrolytes to be biopolymers or else synthetic polymers. Thus, the inventive compositions contain, for example, one or more polyelectrolytes selected from

alginic

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 aforementioned substances, in particular amino and / or carboxyl derivatives. In the context of the present invention, preference is given to using polyelectrolytes which carry suitable groups for salt formation with divalent cations. In particular, polymers bearing carboxylate groups are suitable. Polyelectrolytes particularly preferred for the purposes 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. These are to be understood as meaning those polysaccharides which are composed inter alia of glucuronic acid, preferably D-glucuronic acid, and / or iduronic acid, in particular L-iduronic acid. A constituent of the carbohydrate skeleton is formed by glucuronic acid or iduronic acid. The iduronic acid isomeric to glucuronic acid has the other configuration at the C5 carbon atom of the ring. Glucuronic acid and / or iduronic acid-containing polysaccharides are preferably to be understood as meaning those polysaccharides which contain glucuronic acid and / or iduronic acid in a molar ratio of 1:10 to 10: 1, in particular from 1: 5 to 5: 1, particularly preferably 1: 3 to 2: 1, based on the sum of the other monosaccharide building blocks of the polysaccharide. Advantageously, a particularly good interaction with the calcium salt can be achieved by the anionic carboxyl groups of the glucuronic acid and / or iduronic acid-containing polysaccharides, which lead to a particularly stable and at the same time particularly good biomineralizing composite material. Examples of suitable polysaccharides are 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.

An advantage of the composite materials to be used according to the invention is the particular stability in aqueous systems even without the addition of dispersing aids, such as, for example, polyhydric alcohols (such as glycerol or polyethylene glycols).

Here, oral and dental care and cleaning agents according to the invention are preferred which contain the calcium salt (s) in the form of individual crystallites or in the form of rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped particles comprising a plurality of said crystallites 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 the form of composite materials, which - based on the weight of the composite material - a) 0.1 to 80 wt .-% , preferably 10 to 60 wt .-% and in particular 30 to 50 parts by weight

% Protein components selected from proteins, protein hydrolysates and

Protein hydrolyzate derivatives; b) from 0.01 to 80% by weight, preferably from 10 to 75% by weight and in particular from 30 to 65% by weight, of the calcium salt (s) in the form of individual crystallites or in the form of sticks and / or or platelet-shaped, preferably predominantly platelet-shaped particles comprising a plurality of said crystallites, wherein 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 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, i. 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 hydrolyzates, for example those with 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 composite materials according to 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.

The protein component is particularly preferably selected from gelatin, casein and / or its hydrolysates.

According to a very particularly preferred embodiment, the protein component of the composite material contained in the remineralizing product is selected from collagen, gelatin, casein and their hydrolysates, preferably gelatin, particularly preferably gelatin of the type A, B or AB, in particular gelatin of the acid bone type (AB ). In a further embodiment of the invention, the nanoparticulate calcium salt primary particles / crystallites present in the composite materials may be enveloped by one or more surface modifiers.

As a result, for example, the production of composite materials can be facilitated in those cases in which the nanoparticulate calcium salts are difficult to disperse. The surface modifier is adsorbed on the surface of the nanoparticles and changes them so as to increase the dispersibility of the calcium salt and prevent the agglomeration of the nanoparticles.

In addition, the structure of the composite materials and the loading of the polymer component with the nanoparticulate calcium salt can be influenced by a surface modification. In this way, it is possible in the application of the composite materials in remineralization processes to influence the course and the speed of the remineralization process.

Surface modifiers are to be understood as substances which physically adhere to the surface of the finely divided particles but do not react chemically with them. The individual surfaces of the surface modifiers adsorbed on the surface are substantially free of intermolecular bonds with each other. Surface modifiers are to be understood in particular as dispersants. Dispersants are also known to the person skilled in the art, for example, under the terms emulsifiers, protective colloids, wetting agents, detergents, etc.

Such calcium salt particles which have an elongated, in particular rod or needle-like, form can be produced in particular by methods according to the invention in which the precipitation of the composite material is at a pH of between about 9.5 and 14, preferably between 10 and 12, preferably about pH 11 is performed.

Particularly suitable for the preparation of a calcium salt or composite material according to the invention, which contains predominantly platelet-shaped particles, are those processes in which the precipitation of the calcium salt or of the composite material at a pH of between 5 and 9, preferably between 6 and 8, particularly preferably around 7 is carried out.

A solution of a calcium salt with the polymer component is preferably initially introduced to form the preferred composite material according to the invention, and a phosphate solution is slowly added, the pH being between 5 and 9, preferably between 6 and 8, particularly preferably around 7. Particularly preferably, the pH is kept constant during the addition of the phosphate solution by adding appropriate amounts of aqueous base. Depending on the exact composition of the respective composite material, the composite material or materials are used in amounts such that the oral and dental care and cleaning compositions according to the invention contain from 0.005 to <0.1% by weight of calcium salt (e ) in the form of individual crystallites or in the form of rod-shaped and / or platelike, preferably predominantly platelet-shaped particles comprising a plurality of said crystallites, wherein 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. Compositions preferred according to the invention are characterized in that they contain 0.008 to 0.16% by weight, preferably 0.01 to 0.12% by weight and in particular 0.04 to 0.1% by weight of composite material (a).

The oral and dental care and cleaning compositions according to the invention may contain, in addition to the aforementioned essential ingredients, other ingredients of oral cleansers, oral hygiene products, dentifrices and / or dentifrices. The preferred further ingredients are described below.

The oral and dental care and cleaning agents according to the invention, in particular the toothpastes, z. B. also contain antimicrobial substances as preservatives or as antiplaque agents. Such substances may, for. B. be selected from p-Hydroxybenzoesäuremethyl-, ethyl or propyl, sodium sorbate, sodium benzoate, bromochlorophene, triclosan, phenyl salicylates, biguanides z. As chlorhexidine, thymol, etc ..

Oral and dental care and cleaning agents which are preferred according to the invention are characterized in that they additionally have antiplaque active substances, preferably methyl, ethyl or propyl p-hydroxybenzoate, sodium sorbate, sodium benzoate, bromochlorophene, triclosan, phenylsalicylic acid esters, biguanides, for example. As chlorhexidine, thymol, preferably in amounts of 0.1 to 5 wt.%, Preferably from 0.25 to 2.5 wt.% And in particular from 0.5 to 1, 5 wt.%, Each based on the total Means, included.

Another preferred group of ingredients that may be included in the compositions of the invention are the anti-caries agents. These may be selected, for example, from organic or inorganic fluorides, for. Example of sodium fluoride, potassium fluoride, sodium monofluorophosphate and sodium fluorosilicate. Also zinc fluoride, stannous fluoride are preferred. An amount of 0.01-0.2% by weight of fluorine should preferably be present in the form of the compounds mentioned.

Oral and dental care and cleaning compositions according to the invention, which additionally anti-caries agents, preferably fluorine compound (s), in particular sodium fluoride, potassium fluoride, sodium monofluorophosphate, zinc fluoride, stannous fluoride and sodium fluorosilicate, preferably in Amounts of from 0.01 to 5% by weight, preferably from 0.1 to 2.5% by weight and in particular from 0.2 to 1.1% by weight, in each case based on the total agent, are preferred according to the invention.

The oral and dental care and cleaning agents, in particular the toothpastes, for example, may also contain substances that are effective against tartar. Such substances may be, for example, chelating agents such. As ethylenediaminetetraacetic acid and its sodium salts, pyrophosphate salts such as the water-soluble dialkali or Tetraalkalimetallpyrophosphat- salts, z. B. Na ₄ P ₂ O ₇ , K ₄ P ₂ O ₇ , Na ₂ K ₂ P ₂ O ₇ , Na ₂ H ₂ P ₂ O ₇ and K ₂ H ₂ P ₂ O ₇ or polyphosphate salts, the z. B. from water-soluble Alkalimethalltripolyphosphaten as sodium tripolyphosphate and potassium tripolyphosphate can be selected.

Oral and dental care and cleaning agents which are preferred according to the invention are characterized in that they additionally contain phosphate (s), preferably alkali metal phosphate (s) and in particular sodium tripolyphosphate, preferably in amounts of from 1 to 10% by weight, more preferably from 2 to 8% by weight .-% and in particular from 3 to 7 wt .-%, each based on the total agent included.

The compositions according to the invention, in particular toothpastes or liquid toothpastes, preferably contain one or more polishing agents, usually in an amount of from 5 to 50% by weight.

As a polishing agent are in principle all known for toothpastes friction body, in particular those that do not contain calcium ions. Preferably suitable polishing agent components are therefore silicic acids, aluminum hydroxide, aluminum oxide, sodium aluminum silicates, organic polymers or mixtures of such friction bodies.

Calcium containing polishing components such as e.g. However, chalk, calcium pyrophosphate, dicalcium phosphate dihydrate can be present in amounts of up to 5% by weight.

The total content of polishing agents is preferably in the range of 5 to 50% by weight of the dentifrice.

Particular preference is given to toothpastes and liquid dentifrices which contain silicic acids as a polishing agent. Suitable silicic acids are, for example, gel silicas, hydrogel silicic acids and precipitated silicas. Gel silicas are prepared by reacting sodium silicate solutions with strong, aqueous mineral acids to form a hydrosol, aging to the hydrogel, washing and drying. If the drying is carried out under mild conditions to a water content of 15 to 35 wt .-%, the so-called hydrogel silicic acids are obtained. Drying to water contents below 15% by weight results in an irreversible shrinkage of the previously loose structure of the hydrogel to the dense structure of the so-called xerogel. 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 in which aggregation to the sol and gel can not occur. Preferably, a precipitated silica having a BET surface area of 15 - 110 m2 / g, a particle size of 0.5 - 20 microns, wherein at least 80 wt .-% of the primary particles should be less than 5 microns, and a viscosity in 30% Glycerol-water (1: 1) dispersion of 30-60 Pa. s (2O ⁰ C) in an amount of 10 - 20 wt .-% of the toothpaste. Preferred precipitated silicas of this type also have rounded corners and edges and are available under the trade name Sident12 DS (DEGUSSA).

Other precipitated silicas of this type are Sident 8 (DEGUSSA) and Sorbosil AC 39 (Crosfield Chemicals). These silicas are characterized by a lower thickening effect and a slightly higher average particle size of 8-14 microns with a specific surface area of 40 - 75 m2 / 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 - 100 Pa.s.

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. -% of a silica with a particle size of 1 - 3 microns. To such toothpastes, it is therefore preferable to add finely divided, so-called thickened silicas having a BET surface area of 150-250 m 2 / g, in addition to the precipitated silicas mentioned, for example. the commercial products Sipernat 22 LS or Sipernat 320 DS.

As a further polishing agent component, e.g. Aluminum oxide in the form of slightly calcined clay containing - and -Aluminiumoxid in an amount of about 1-5% by weight. Such a suitable alumina is available under the trade designation "Polianton earth P10 finest" (Giulini Chemie).

As a polishing agent are all further known for toothpastes friction body such. B. sodium aluminum silicates such. As zeolite A, organic polymers such. As polymethacrylate or mixtures of these and the aforementioned friction body.

In summary, oral and dental care and cleaning compositions according to the invention are preferred which additionally comprise cleaning bodies, preferably silicic acids, aluminum hydroxide, aluminum oxide, calcium pyrophosphate, chalk, dicalcium phosphate dihydrate (CaHPO ₄ -2H ₂ O) ₁ sodium aluminum silicates, in particular zeolite A, organic polymers, in particular Polymethacrylates or mixtures of these Reibkörper.vorzugsweise in amounts of 1 to 30 wt.%, preferably from 2.5 to 25% by weight and in particular from 5 to 20% by weight, in each case based on the total agent.

As a carrier for the toothpastes, which allows the setting of a suitable consistency for the dosage from tubes, dispensing containers or flexible bottles, for example, a combination of humectants, binders and water is suitable.

Humectants are, for example, the sorbitol or glycerol or 1,2-propylene glycol contained in the compositions according to the invention. In addition to these substances, of which at least one is present in amounts of at least 10% by weight in the compositions of the invention, suitable humectants are preferably alcohols having at least 2 OH groups, preferably mannitol, xylitol, polyethylene glycol, polypropylene glycol and mixtures thereof.

Among these compounds, those having 2 to 12 OH groups, and especially those having 2, 3, 4, 5, 6 or 10 OH groups are preferred.

Polyhydroxy compounds having 2 OH groups are, for example, glycol (CH ₂ (OH) CH ₂ OH) and other 1, 2-diols such as H- (CH ₂ J _n -CH (OH) CH ₂ OH where n = 2, 3, 4 , 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20. Also 1,3-diols such as H- (CH ₂ ) _n -CH ( OH) CH ₂ CH ₂ OH with n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 The (n, n + 1) or (n, n + 2) -diols with non-terminal OH groups can also be used.

Important representatives of polyhydroxy compounds having 2 OH groups are also the polyethylene and polypropylene glycols.

As preferred further humectants z. B. xylitol, propylene glycols, polyethylene glycols, especially those having average molecular weights of 200-800 are used.

The additional humectant (s) may be employed in the compositions of the invention in varying amounts. While amounts of a few% (for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10% by weight, in each case based on the total agent) may be present depending on the other optional ingredients, they also exist Formulations that have significantly higher humectant levels. The total dampening solution content (including the sorbitol, glycerol and 1,2-propylene glycols contained in the agents according to the invention) is for example 50, 55, 60, 65, 70, 75% by weight, in each case based on the total agent. Usual and preferred are agents according to the invention which contain (including the sorbitol, glycerol and 1,2-propylene glycols contained in the agents according to the invention) between 10 and 75% by weight of humectant. Contents between 15 and 70, preferably between 20 and 60 wt.%, In each case based on the total agent, may be preferred. As a consistency regulator (or binder) serve z. As natural and / or synthetic water-soluble polymers such as alginates, Carragheenate, tragacanth, starch and starch ethers, cellulose ethers such. Carboxymethylcellulose (Na-SaIz), hydroxyethylcellulose, methylhydroxypropylcellulose, guar, acacia, agar, xanthan gum, succinoglycan gum, locust bean gum, pectins, water-soluble carboxyvinyl polymers (e.g., Carbopol® types), polyvinyl alcohol, polyvinylpyrrolidone, Polyethylene glycols, in particular those having molecular weights of 1 500-1 000 000.

Other substances that are suitable for viscosity control, z. B. phyllosilicates such. As montmorillonite clays, colloidal thickened silicas such. B. airgel silicas, fumed silicas or feinstvermahlene precipitated silicas. It is also possible to use viscosity-stabilizing additives from the group of cationic, zwitterionic or ampholytic nitrogenous surfactants, hydroxypropyl-substituted hydrocolloids or polyethylene glycol / polypropylene glycol copolymers having an average molecular weight of 1000 to 5000 or a combination of the compounds mentioned in the toothpastes.

The oral and dental care products, especially the toothpastes, may also contain the insensitivity of the teeth-enhancing substances, such as potassium salts such. As potassium nitrate, potassium citrate, potassium chloride, potassium bicarbonate and potassium oxalate. In accordance with the invention, preferred oral and dental care and cleaning agents 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 entire remedy, included.

The compositions according to the invention, in particular the toothpastes, can also additionally further wound-healing and anti-inflammatory substances, for. B. agents for gingivitis included. Such substances may, for. B. be selected from allantoin, azulen, chamomile extracts, tocopherol, panthenol, bisabolol, sage extracts. Suitable non-cationic, bactericidal components are, for example, phenols, resorcinols, bisphenols, salicylanilides and their halogenated derivatives, halogenated carbanilides and p-hydroxybenzoic acid esters. Particularly preferred antimicrobial components are halogenated diphenyl ethers, for example 2,4-dichloro-2'-hydroxydiphenyl ether, 4,4'-dichloro-2'-hydroxydiphenyl ether, 2,4,4'-tribromo-2'-hydroxydiphenyl ether and 2,4, 4 ^{1-trichloro-2'-hydroxydiphenyl} ether (triclosan). They are preferably used in amounts of from 0.01 to 1% by weight in the dentifrices according to the invention. Triclosan is particularly preferably used in an amount of 0.01-0.3% by weight.

D-panthenol D - (+) - 2,4-dihydroxy-N- (3-hydroxypropyl) -3,3-dimethyl-butyramide exhibits a biological activity corresponding to pantothenic acid. The pantothenic acid (R - (+) - N - (2,4- Dihydroxy-3,3-dimethylbutyryl-β-alanine) is a precursor in the biosynthesis of coenzyme A and is counted to the vitamin B complex (B3). These substances are known to promote wound healing and have a beneficial effect on the skin. They have therefore also been occasionally described in toothpastes. The dentifrices according to the invention preferably contain 0.05-5% by weight of panthenol or a salt of pantothenic acid.

Retinol (3,7-dimethyl-9- (2,6,6-trimethyl-1-cyclohexenyl) -2,4,6,8-nonatetraen-1-ol is the international common name for vitamin Al. In place of the retinol may also one its derivatives having similar biological activity, for example an ester or the retinoic acid (tretinoin), one of its salts or its esters, preferably a retinol ester, in particular a fatty acid ester of a fatty acid having 12-22 carbon atoms When using a retinol ester, eg retinol palmitate with an activity of 1, 7 ^· 10 ⁶ IU per g, an amount of 0.001 to 0.1% by weight is preferred If other retinol derivatives are used It is recommended to use at a concentration of 10 ³ to 10 ⁶ IU (international units) per 100 g.

Preferred dentifrices according to the present invention preferably contain, in addition to polishing agents, fluorine compounds, humectants and binders

0.01 - 1 wt .-% of a halogenated diphenyl ether

0.05 - 5 wt .-% panthenol or a salt of pantothenic acid and

0.01-0.1% by weight of a retinol ester, preferably retinol palmitate.

The agents according to the invention, in particular the toothpastes, may also contain substances for increasing the mineralizing potential, for example calcium-containing substances such as, for example, Calcium chloride, calcium acetate and dicalcium phosphate dihydrate. The concentration of the calcium-containing substance depends on the solubility of the substance and the interaction with other substances contained in the oral and dental care products.

In addition to the compulsory components mentioned, the dentifrices according to the invention may contain further adjuvants and additives known per se. An additive which has been known for a long time as a toothpaste component is particularly effective in the dentifrices according to the invention: calcium glycerophosphate, the calcium salt of glycerol-1-phosphoric acid or glycerol-2-phosphoric acid or the glycerol-1-phosphoric acid enantiomer Glycerol-3-phosphoric acid - or a mixture of these acids. The compound has a remineralizing effect in dentifrices as it provides both calcium and phosphate ions. In the dentifrices according to the invention calcium glycerophosphate is preferably used in amounts of 0.01 to 1 wt .-%. Overall, the dentifrices according to the invention may contain customary auxiliaries and additives in amounts of up to 10% by weight. The dentifrices according to the invention can be improved, for example, by adding aromatic oils and sweeteners in their organoleptic properties.

As aroma oils, all the natural and synthetic flavors customary for oral and dental care products can be used. Natural flavors can be contained both in the form of the natural essential oils isolated from drugs and the individual components isolated therefrom.

Suitable flavors are e.g. Peppermint oil, spearmint oil, eucalyptus oil, aniseed oil, fennel oil, caraway oil, menthyl acetate, cinnamic aldehyde, anethole, vanillin, thymol and mixtures of these components.

Suitable sweeteners are e.g. Saccharin sodium, sodium cyclamate, sucrose, lactose, meltose, fructose.

Further customary auxiliaries and additives for toothpastes are

Surfactants, preferably anionic, zwitterionic, amphoteric, nonionic surfactants or a combination of several different surfactants, solvents and solubilizers, e.g. lower monohydric or polyhydric alcohols or ethers, e.g. Ethanol, 1,2-propylene glycol, diethylene glycol or butyldiol glycol pigments, e.g. Titanium dioxide dyes

Buffer substances, e.g. primary, secondary or tertiary alkali phosphates or citric acid / Na citrate other wound healing or anti-inflammatory substances, e.g. Allantoin, urea, azulene, chamomile agents, acetylsalicylic acid derivatives or rhodanide, other vitamins, e.g. Ascorbic acid, biotin, tocopherol or rutin mineral salts such as e.g. Manganese, zinc or magnesium salts.

Another important group of ingredients that may be included in the compositions of the invention are the so-called bioactive glasses.

In the context of the present application, the term "bioactive glasses" encompasses glasses which are biologically active and / or biologically active The biological effectiveness of a glass can be demonstrated in its antimicrobial properties, for example, biologically active glass differs from conventional lime-sodium silicate For example, biologically active glass refers to a glass that forms a firm bond with body tissue to form a hydroxyl apatite layer. "Bioactive glass" is also understood to mean a glass that contains antimicrobial and / or inorganic glass shows anti-inflammatory effect. The glass powders show a biocidal or biostatic effect against bacteria, fungi and viruses; are in contact with humans skin-friendly, toxicologically safe and especially suitable for consumption. Oral and dental care and cleaning agents which are particularly preferred 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 compositions of this embodiment contain 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 when melting 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 fractions are to be adjusted by the ceramization, must be present in the glass in correspondingly high concentrations. K ₂ O acts as a flux when melting the glass. In addition, potassium is released in aqueous systems. If high potassium concentrations are present in the glass, potassium-containing phases such as calcium silicates are also eliminated. The P ₂ O content of silicate glasses, glass ceramics or composites can be used to adjust the chemical resistance of the glass and thus the release of ions in aqueous media. For Phospaht 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 ceramization 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 ₁ 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 O 0 to 35 wt .-%, preferably 5 to 30 wt .-%,

K ₂ O 0 to 35 wt .-%, preferably 0 to 20 wt .-%,

P ₂ O ₅ 0 to 10 wt .-%, preferably 2 to 10 wt .-%,

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

CaO 0 to 35% by weight, preferably 5 to 30% by weight, Al ₂ O ₃ 0 to 25 wt .-%, preferably 0 to 5 wt .-%,

B ₂ O ₃ 0 to 25 wt .-%, preferably 0 to 5 wt .-%,

TiO ₂ 0 to 10 wt .-%, preferably O, 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 compositions according to the invention of this embodiment are outstandingly suitable for tooth cleaning and care. They gently cleanse the teeth and have the additional benefit of smoothing the tooth surface. For scratch value determinations (treatment of teeth under standardized conditions with different compositions and comparison of the surfaces versus treatment of a standard polishing agent), the compositions according to the invention have distinct advantages:

It has been found that during and after the application of the compositions according to the invention, in particular in the form of a toothpaste, a particularly smooth, good mouthfeel and perceived as particularly clean by test persons results.

Claims

claims:

An oral and dental care and cleaning composition containing ≥ 0.005% by weight of calcium salt (s) in the form of individual crystallites or in the form of particles, comprising a plurality of said crystallites, wherein 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, characterized in that the particles are rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped and that the agent has a viscosity (after 7 days storage at 20 ° C, measured at 20 ° C and an air pressure of 1 bar, Brookfield RVDV II + viscometer, with helipath at a shear rate of 4 rpm) of 450,000 to 1,000,000 mPas, preferably from 500,000 to 700,000 mPas and in particular from 550,000 to 650,000 mPas ,

2. Oral and dental care and cleaning agent according to claim 1, characterized in that the platelet-shaped particles have a length of 10 to 150 nm and a width of 5 to 150 nm, preferably a length of 30 to 100 nm and a width of 10 to 100 nm.

3. Oral and dental care and cleaning agent according to one of the preceding claims, characterized in that the particles have a ratio of length to width of 1 to 4, preferably from 1 to 3, more preferably between 1 and 2.

4. Oral and dental care and cleaning agent according to one of the preceding claims, characterized in that the particles have an area of 0.1 * 10 ^'15 m ² to 90 ^* 10 ^"15 m ² , preferably an area of 0.5 ^* 10 ^'15 m ² to 50 ^* 10 ^"15 m ² , more preferably 1, 0 ^* 10 ^{' 15} m ² to 30 ^* 10 ^{" 15} m ² , very particularly preferably 1, 5 * 10 ^"15 m ² to 15 * 10 ^'15 m ² have.

5. Oral and dental care and cleaning agent according to one of the preceding claims, characterized in that it - based on its weight - 0.01 to 0.5 wt .-%, preferably 0.02 to 0.4 wt. %, more preferably 0.03 to 0.25 wt .-%, more preferably 0.04 to 0.2 wt .-% and in particular 0.05 to 0.15 wt .-% calcium salt (s) in the form of individual Crystallites or in the form of rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped particles comprising a plurality of said crystallites.

6. Oral and dental care and cleaning composition according to one of the preceding claims, characterized in that a single crystallite has a thickness of 2 to 15 nm and a length of 10 to 50 nm; particularly preferably has a thickness of 3 to 11 nm and a length of 15 to 25 nm.

7. oral and dental care and cleaning agent according to any one of the preceding claims, characterized in that the or the calcium salt (s) in the form of individual crystallites or in the form of rod-shaped and / or platy-shaped, preferably predominantly platelet-shaped particles comprising a plurality of said crystallites, wherein 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 is selected or are from the group hydroxyapatite, fluorapatite and calcium fluoride.

8. oral and dental care and cleaning agent according to any one of the preceding claims, characterized in that it - based on its weight - 0.25 to 2.0 wt .-%, preferably 0.5 to 1, 75 wt. % and in particular 0.75 to 1, 5 wt .-% carboxymethycellulose (CMC).

9. Oral and dental care and cleaning agent according to claim 8, characterized in that the agent contains a Na-CMC whose 2 wt .-% - solution in water, a viscosity (after 7 days storage at 2O ⁰ C, measured at 20 ⁰ C and an air pressure of 1 bar, Brookfield viscometer RVDV II +, with a helipath at a shear rate of 4 U / min) of 200 to 1000 mPas, preferably from 300 to 800 mPas and in particular from 350 to 700 mPas.

10. oral and dental care and cleaning agent according to any one of the preceding claims, characterized in that in addition to the or the calcium salt (s) in the form of individual crystallites or in the form of rod and / or platelike, preferably predominantly platy Particles comprising a plurality of said crystallites, wherein 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, further calcium salt (s), preferably calcium glycerophosphate.

11. Oral and dental care and cleaning agent according to one of the preceding claims, characterized in that it or the calcium salt (s) in the form of individual crystallites or in the form of rod and / or platelike, preferably predominantly platelet-shaped particles, comprising a plurality of said crystallites, wherein 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 the form of a suspension, which - based on the weight of the suspension - a) 0, From 01 to 15 wt .-%, preferably 0.1 to 10 wt .-% and in particular 0.5 to 7.5 wt .-% of at least one water-soluble surfactant and / or at least one water-soluble polymeric protective colloid; b) 0.01 to 15 wt .-%, preferably 0.1 to 10 wt .-% and in particular 0.5 to 7.5 wt .-% of the or the calcium salts (s) in the form of individual crystallites or in A form of rod-shaped and / or platelike, preferably predominantly platelike, particles comprising a plurality of said crystallites, wherein 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.

12. Oral and dental care and cleaning agent according to claim 11, characterized in that the suspension at 2O ⁰ C has a viscosity (after 7 days storage at 20 ⁰ C, measured at 2O ⁰ C and an air pressure of 1 bar, Brookfield Viscosimeter RVDV II +, with helipath at a shear rate of 4 U / min) of 500 to 20,000 mPas, preferably from 750 to 15,000 mPas and in particular from 1000 to 10,000 mPas having.

13. Oral and dental care and cleaning composition according to one of the preceding claims, characterized in that it contains a composite material comprising a.in calcium sparingly water-soluble salts, wherein the calcium salts in the form of individual crystallites or in the form of particles, comprising a plurality said crystallites having an average particle diameter in the range of less than 1000 nm, preferably less than 300 nm, and b. a polymer component, wherein the particles in the composite material rod and / or platelet-shaped, preferably predominantly platelet-shaped.

14. Oral and dental care and cleaning agent according to claim 13, characterized in that the polymer component of the composite material contained is selected from a protein component, polyelectrolytes and polysaccharides.

15. Oral and dental care and cleaning agent according to claim 14, characterized in that said protein component is selected from collagen, gelatin, casein and their hydrolysates, preferably gelatin, more preferably gelatin type A, B or AB, in particular gelatin from Type Acid bone.

16. oral and dental care and cleaning agent according to any one of claims 13 to 15, characterized in that it or the calcium salt (s) in the form of individual crystallites or in the form of rod and / or platelet-shaped, preferably predominantly platelet-shaped Particles comprising a plurality of said crystallites, wherein 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 the form of composite materials containing, based on the weight of the composite material, 0.1 to 80 wt .-%, preferably 10 to 60 wt .-% and in particular 30 to 50 wt .-% protein components selected from proteins, protein hydrolysates and protein hydrolyzate derivatives; b) from 0.01 to 80% by weight, preferably from 10 to 75% by weight and in particular from 30 to 65% by weight, of the calcium salt (s) in the form of individual crystallites or in the form of sticks and / or or platelet-shaped, preferably predominantly platelet-shaped particles comprising a plurality of said crystallites, wherein 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 contains.

17. Oral and dental care and cleaning agent according to one of the preceding claims, characterized in that it is 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 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. %, in each case based on the total mean.

18. oral and dental care and cleaning agent according to any one of the preceding claims, characterized in that it additionally antiplaque agents, preferably p-hydroxybenzoic acid methyl, ethyl or propyl ester, sodium sorbate, sodium benzoate, bromochlorophene, triclosan, phenyl salicylic acid ester, Biguanids z. As chlorhexidine, thymol, preferably in amounts of 0.1 to 5 wt.%, Preferably from 0.25 to 2.5 wt.% And in particular from 0.5 to 1, 5 wt.%, Each based on the total Means containing.

19. oral and dental care and cleaning agent according to any one of the preceding claims, characterized in that it is 0.2 to 20 wt .-%, preferably 0.4 to 14 wt .-%, particularly preferably 0.5 to 3 wt .-% and in particular 0.6 to 2 wt .-% of at least one bioactive glass contains.