BRPI0611912A2 - remineralizing agents for oral and dental hygiene and cleaning - Google Patents

Abstract

REMINERALIZING AGENTS FOR ORAL AND DENTAL HYGIENE AND CLEANING. The present invention relates to mouth and tooth hygiene and cleaning agents which by weight contain <0.002 to <0.1% by weight of calcium salt (salts) in the form of Primary rod-shaped particles with a thickness in the range 2 to 50 nm and a length in the range 10 to 150 nm remineralize the teeth and make them more insensitive to outside influences.

Description

Report of the Invention Patent for "REMINERALIZING AGENTS FOR ORAL AND DENTAL HYGIENE".

The present invention relates to dental and dental cleaning and cleaning preparations which, by virtue of special constituent substances, have a remineralizing effect, have a high cleaning power, entrap the tooth surface or act in a manner that is suitable for use. very abrasive and furthermore prevent the formation of mouth odor and reduce mouth odor.

Dental cleaning compositions are on the market in different forms and primarily serve for cleaning the tooth surface and preventing dental and gum disease. They usually contain a combination of polishing agents, moisture keeping agents, surfactants, adhesives, flavorings and fluoride-containing actives as well as antimicrobials. In addition to toothpaste powders, because of their high abrasiveness they play a secondary role, tooth cleaning compositions are offered, especially in the form of pastes, translucent or transparent egel creams. In recent years, too, fluid or liquid toothpaste and toothpaste antiseptics have gained increasing significance.

In addition to teeth cleaning, the consumer expects from generic products also hygiene of teeth and oral cavity. Thus, especially a "clean" feeling, that is, a shiny smooth dental surface as well as a fresh mouth feel, are the essential aspects for stimulating the purchase of mouth care and cleansing preparations. and teeth. Therefore, an effective generic-type composition should thoroughly clean the teeth without damaging the tooth or tooth surface and simultaneously diminishing and / or preventing oral odor.

Calcium phosphate salts have long been added to the recipes of tooth cleaning compositions and tooth cleaning compositions as both abrasive components and for the promotion of enamel remineralization. This is especially true for hydroxyapatite and fluorapatite, as well as amorphous calcium phosphates and bru-shita (dicalcium phosphate dihydrate). But also calcium fluoride has been repeatedly described as a component of dental cleaning compositions and as a component for enamel fixation and caries prophylaxis.

The availability of these substances for the desired remineralization depends decisively on the particle size of these poorly water-soluble components dispersed in tooth-hygiene compositions. Therefore, it has been proposed to use these poorly soluble calcium salts in the finest distribution.

DE-A-21 34 862 was known, for example, for a hypersensitive teeth-containing hygienic dentin dental hygiene composition (Ca5 [(P04) 30H]), the particle size of which is indicated as 6 - 8 μητι (micrometer), because grinding does not give greater quasi-settings.

In EP 1,139,995 A1 it is proposed to stabilize suspensions of sparingly soluble calcium salts in very fine form during or shortly after precipitation by precipitation in the presence of an agglomeration inhibitor or by redisperging. dispersion in the presence of agglomeration inhibitor. These suspensions may be used in toothpaste creams where application quantities of more than 0.1% by weight (relative to the whole composition and calculated as calcium salt) are published.

The object has been to solve the above mentioned problems without having to incorporate high amounts of constituent substances which may be expensive in the formulations. Furthermore, the object of the present invention was to produce oral and dental hygiene and cleaning compositions which remineralize the teeth and make them less sensitive to external actions.

It has now been found that calcium salt nanoparticles are also effective and especially in small amounts.

The object of the present invention in a first embodiment is a composition for oral and dental hygiene and cleaning, containing - by weight -> 0.005 to <0.1% by weight, desal (salts) of calcium in the form of primary rod-shaped particles having a thickness in the range 2 to 50 nm and a length in the range 10 to 150 nm.

Oral and dental hygiene compositions, as well as oral and dental cleaning compositions in the sense of the invention, are oral buccal powders, oral and dental dentifrices, oral and dental creams as well as oral and dental gels. Preferably, dentifrices and dental cleaning compositions are suitable. To this end, oral buccal compositions and cleaning compositions may be present, for example, in the form of dentifrices, liquid toothpastes, dental powders, oral antiseptics or optionally also as chewable gum, e.g., as gum. chew. Preferably, however, they are present as more or less flowable or plastic toothpastes, such as being used for tooth cleaning as the use of a toothbrush.

Particularly preferably, according to the invention, low water soluble calcium salts are used, which are most preferably selected from phosphates, fluorides and fluorophosphates.

As poorly soluble or poorly soluble salts should be understood those which are soluble in water or the liquid suspension medium at less than 1 g / l (20 ° C). Preferably suitable salts are calcium hydroxyphosphate (Ca5 [OH (P04) 3]) or hydroxyapatite, decalcium fluorophosphate (Ca5 [F (P04) 3]) or fluorapatite, hydroxylapatite with general composition Ca5 (P04) 3 (OH) fluorine. , F) and calcium fluoride (CaF2) or fluorite (Spanish).

Oral and dental hygiene and cleaning compositions contain by weight 0.01 to 0.09 wt%, preferably 0.02 to 0.08 wt%, particularly preferably 0.03 to 0.075 wt%. wt.%, more preferably 0.04 to 0.07 wt.% and especially 0.05 to 0.065 wt.% calcium salt (s) in the form of rod-shaped primary particles of a thickness in the range 2 to 50 nm and with a length in the range 10 to 150 nm. In addition, according to the invention, oral and dental cleaning and cleaning compositions are preferred in which the calcium salt (s) in the form of primary rod-shaped particles having a thickness in the range of 2 to 50 nme and a length in the range from 10 to 150 nm is selected or selected from the hydroxylapatite, fluorapatite and calcium fluoride group.

In addition to the calcium salts mentioned in the particulate form, mouth and tooth cleaning agents according to the invention may contain other calcium salts, which need not necessarily be nanoparticles. Especially proven here is calcium glycerophosphate, which is sold, for example, under the trade name Furdentyl®.

Particularly preferred oral and dental hygiene and cleaning agents according to the invention are therefore characterized by the fact that they additionally contain calcium salt (s) in the form of rod-like primary particles of a thickness in range 2 to 50 nm and a length in the range 10 to 150 nm, other calcium salt (s), preferably calcium glycerophosphate.

Oral and dental hygiene and cleaning agents according to the invention may contain the calcium salts in nanoparticles in different forms. Preferably, the calcium salts are stabilized against deglomeration. In a first preferred embodiment of the present invention, the preparations according to the invention contain the calcium salt (s) in the form of rod-shaped primary particles having a thickness in the range 2 to 50 nm and a length 10 to 150nm in the form of a suspension which, in relation to the weight of the suspension, contains

(a) 0.01 to 15% by weight, preferably 0.1 to 10% by weight and especially 0.5 to 7.5% by weight, of at least one water soluble surfactant and / or at least a water-soluble polymer protective colloid;

(b) 0.01 to 15% by weight, preferably 0.1 to 10% by weight and especially 0.5 to 7.5% by weight, of the calcium salt (s) as primary particulate matter. rods having a thickness in the range 2 to 50 nm and a length in the range 10 to 150 nm.

As a liquid medium in such an embodiment, in which calcium bones may be dispersed, water is appropriate in the first line. But calcium salt particles isolated from an aqueous suspension, for example by filtration or centrifugation, may also be redisperse. In organic solvents, in this case, they provide suspensions of the primary particles in the nanometer range, which are hardly prone to agglomeration. Suitable organic liquid media are, for example, lower alcohols, water soluble and glycols, polyethylene glycols, glycerin or mixtures thereof. water with it.

By primary particles are meant the crystallites, that is, the individual crystals of the mentioned calcium salts. Particle diameter is to be understood here as the diameter of the particles towards their greatest length extension. By thickness here is meant the menordi diameter of the rods, by length, its largest. By the mean particle diameter is a value divided by the total amount of the compound. The determination of particle diameters can be determined by the methods current to the technician, for example by the Transmission Electron Microscopy (TEM) method.

The suspensions used in this preferred embodiment of the present invention contain (by weight of the suspension), 0.01 to 15% by weight, preferably 0.1 to 10% by weight and especially 0.5 to 7.5%. by weight of the calcium salt (s) in the form of primary rod-shaped particles having a thickness in the range 2 to 50 nm and a length in the range 10 to 150 nm. As another constituent substance of the suspension are contained (with respect to the suspension) 0.01 to 15 wt%, preferably 0.1 to 10 wt% and especially 0.5 to 7.5 wt% of at least one water soluble surfactant. and / or at least one water soluble polymer protective colloid.

By the term surfactants are meant active substances which form adsorption layers on boundary surfaces and surfaces or which in volumetric phases may be added to mycelium colloids or lyotropic mesophases. Differentiated surfactants formed from a hydrophobic radical and a negatively hydrophilic top group are distinguished from amphoteric surfactants, which carry both a negative charge, as well as a compensating positive charge, cationic surfactants, which in addition to a hydrophobic radical, They have a positively charged hydrophilic group and nonionic surfactants, which have no charge but rather strong dipole moments and are intensely hydrated in aqueous solution.

As anionic surfactants (E1), all the anionic surfactants suitable for use in the human body are provided in the preparations according to the invention. These are characterized by a water solubilising anionic group, such as, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group of about 8 to 30 carbon atoms. The molecule may additionally contain glycol or polyglycolic ether groups, ester, ether and amide groups as well as hydroxyl groups. Examples of suitable surfactants, in each case in the form of sodium, potassium and ammonium salts, as well as mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group,

- linear and branched fatty acids of 8 to 30 carbon atoms (soaps),

- etherercarboxylic acids of the formula R-O- (CH 2 -CH 2 O) x -CH 2 -COOH wherein R is a linear alkyl group of 8 to 30 carbon atoms and χ is 0 or 1 to 16,

- acylsarcosides having 8 to 24 carbon atoms in the acyl group,

- acyltaurides having 8 to 24 carbon atoms in the acyl group,

- acylisethionates having 8 to 24 carbon atoms in the acyl group,

- sulfosuccinic acid mono- and dialkyl esters 8 to 24 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyloxyoxyethyl esters of 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, - linear alkanesulfonates of 8 to 24 carbon atoms ,

- linear alpha olefin sulfonates of 8 to 24 carbon atoms,

- 8 to 30 carbon atoms fatty acid alpha sulfoxylic acid methyl ester,

- alkyl sulphates and alkyl polyglycol ether sulphates of the formula R-O (CH2-CH2O) x -OSO3H, where R is a preferred linear alkyl group having 8 to 30 carbon atoms and χ is O or 1 to 12,

- sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene propylene glycol ethers

- sulfonated unsaturated fatty acids with 8 to 24 carbon atoms and 1 to 6 double bonds

- esters of tartaric acid and citric acid with alcohols, which contain products of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols of 8 to 22 carbon atoms,

- alkyl and / or alkenyl ether phosphates of formula (E1-I), R1 (OCH2CH2) n-O-P (O) (OX) -OR2 (EI-I)

wherein R1 preferably represents an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R2 represents hydrogen, a (CH2CH2O) nR2 or Χ radical, η represents numbers from 1 to 10 and X represents hydrogen, an alkaline or alkaline earth metal or NR3R4R5R6, with R3 to R6 independent of each other, representing hydrogen or a C1 to C4 hydrocarbon radical,

- sulphated fatty acid alkylene glycol esters of the formula (EI-II)

R7CO (AIkO) nSO3M (E1-II),

wherein R7CO- represents a straight or branched aliphatic, unsaturated and / or unsaturated acyl radical of 6 to 22 carbon atoms, Alk represents CH2CH2, COCH3CH2 and / or CH2CHCH3, η represents numbers from 0.5 to 5 and M represents a cation,

- monoglyceride sulfates and monoglyceride ether sulfates of the formula (fórmula1 -III)

<formula> formula see original document page 9 </formula>

wherein R 8 CO represents a straight or branched acyl radical having from 6 to 22 carbon atoms, x, y and ζ in sum represent numbers from 1 to 30, preferably 2 to 10 and X represents an alkaline or alkaline earth metal.

Typical examples of suitable monoglyceride (ether) sulphates are reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and sebacic acid monoglyceride and their products. addition of ethylene oxide sulfur trioxide or chlorosulfonic acid in the form of its sodium salts.

Preferably, monoglyceride sulfates of formula (E1-III), wherein R 8 CO represents a linear acyl radical of 8 to 18 carbon atoms, are used.

- starch ether carboxylic acids,

- condensation products of Ce - C30 alcohols - protein and / or amino acid hydrolyzed fatty acids and derivatives thereof, which are known in the art to albumin fatty acid condensates, such as, for example, Lamepon® types, Gluadina® types, Hosta-pon® KCG types or Amisoft®.

Preferred anionic surfactants are alkyl sulphates, alkyl polyglycolic ether sulphates and etercarboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, mono- and dialkyl sulfosuccinic acid ester of 8 to 18 atoms carbon moieties on the alkyl group and monoalkylpolyoxyethyl ester of sulfosuccinic acids with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxoethyl groups, monoglyceride disulfates, alkenyl alkyl ether phosphates as well as albumin fatty acid condensates. bipolar surfactants (E2) are those surfactant compounds which carry in the molecule at least one quaternary ammonium group and at least one group -COOt "'- or -SO3 (). Particularly suitable bipolar surfactants are called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate N-acyl-aminopropyl-N, N-dimethylammonium acids, for example 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines, cocoacylaminopropyl-dimethylammonium glycinate in each case with 8 to 18 carbon atoms in the alkyl or acyl group as well as decocoacylaminoethyl hydroxyethylcarboxymethyl glycinate. A preferred bipolar surfactant is the fatty acid amide derivative known as the INCI Cocamidopropyl Betaine.

Ampholytic surfactants (E3) are those surfactant compounds which, in addition to a Cs-C24 alkyl or acyl namolecule group, contain at least one free amino group and at least one -COOH or -SO3H group and are capable of formation of Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkylaminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylarcosines, 2-acids. alkylaminopropionic and alkylaminoacetic acids in each case having about 8 to 24 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and aC12 -C18 acylsarcosine.

Non-tonic surfactants (E4) contain as hydrophilic group, for example a polyol group, a polyalkylene glycol ether group or a combination of polyol group and polyglycol ether. These are, for example,

- Additions of 2 to 50 mo of ethylene oxide and / or O to 5 mo of propylene oxide with linear and branched fatty alcohols having 8 to 30 carbon atoms, with 8 to 30 carbon atoms fatty acids and 8 to 30 alkylphenols up to 15 carbon atoms in the alkyl group,

closed end-group additions with a methyl or C 2 -C 6 alkyl radical of 2 to 50 mo of ethylene oxide and / or 0 to 5 mo propylene oxide with linear or branched fatty alcohols of 8 to 30 carbon atoms. carbon with fatty acids of 8 to 30 carbon atoms and alkylphenols of 8 to 15 carbon atoms in the alkyl group such as, for example, the types which may be obtained by trade names Dehydol® LS, Dehydol® LT (Cognis),

- C 12 -C 30 fatty acid mono- and diesters of products of from 1 to 30 mo of ethylene oxide with glycerine,

- Additions of 5 to 60 mo of ethylene oxide with castor oil and solidified castor oil,

- polyolgraphic acid esters, such as, for example, Hydagen® HSP (Cognis) or Sovermol (Cognis) types,

- alkoxylated triglycerides,

- alkoxylated fatty acid alkyl esters of the formula (E4-I) R1CO- (OCH2CHR2) wOR3 (E4-I)

wherein R1CO represents a linear or branched, saturated and / or unsaturated acyl radical of 6 to 22 carbon atoms, R2 represents hydrogen or methyl, R3 represents linear or branched alkyl radicals of 1 to 4 carbon atoms and w represents numbers from 1 to 20,

- amine oxides,

- mixed esters of hydroxy,

- sorbitanograx acid esters and ethylene oxide addition products with sorbitanograx acid esters such as polysorbates,

- saccharic fatty acid esters and ethylene oxide addition products with saccharic fatty acid esters,

- Addition products of ethylene oxide with fatty acid alkanolamides and fatty amines,

- saccharide alkyl and alkenyl glyglycoside type surfactants according to formula (E4-II), R40- [G] p (E4-II), wherein R4 represents an alkyl or alkenyl radical of 4 to 22 atoms carbon, G represents a sugar radical with 5 or 6 carbon atoms and ρ represents numbers from 1 to 10. They can be obtained according to the respective processes of preparative organic chemistry. Alkyl and alkenyloliglycosides may be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. Thus, preferred alkyl and / or alkenyloliglycosides are alkyl and / or alkenyloliglycosides.

The index ρ in the general formula (E4-II) indicates the degree of oligomerization (SD), ie the distribution of mono- and oligoglycosides and represents a number between 1 and 10. While ρ must always be an integer in the molecule indi- can be mainly the values ρ = 1 to 6, the value ρ for a particular alkylglycoside represents an analytically determined arithmetic size, which most often represents a fractional number. Preferably alkyl and / or alkenyloliglycosides having an average oligomerization degree ρ of 1.1 to 3.0 are used. From a technical point of view, those alkyl- and / or alkenyloliglycosides having a degree of oligomerization of less than 1.7 and especially between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R4 may be derived from primary alcohols of 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, caprine alcohol and undecyl alcohol, as well as their technical mixtures, such as are obtained, for example, from the hydrogenation of technical fatty acid methyl esters or over time. hydrogenation of aldehydes from Roelen's synthesis. C 8 -C 10 alkyl length glycol glycosides (DP = 1 to 3), which are obtained as the main product in the distillative separation of technical C 8 -C 18 coco-fatty alcohol, may be preferred and may be contaminated with a fraction of less than than 6% by weight of C12-alcohol as well as technical Cg / n-oxoalkyl-based alkyloliglycosides (SD = 1 to 3). In addition, the alkyl or alkenyl radical R15 may also be derived from primary alcohols of 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauric alcohol, myristic alcohol, cetyl alcohol, palmitoleic alcohol, stearic alcohol, isostearic alcohol, oleic alcohol, elaidic alcohol, petroselin alcohol, arachic alcohol, behenic alcohol, erucic alcohol, brassidyl alcohol, as well as their technical mixtures, which may be obtained as described above. C12 / 14 alcohol based solidified coconut alcohol DP alkylene glycosides are preferred from 1 to 3.

- fatty acid N-alkylhydroxyalkylamide sugar surfactants, a nonionic surfactant of the formula (E4-III)

R5CO-NR6- [Z] (E4-III) wherein R5CO represents an aliphatic acyl radical of 6 to 22 carbon atoms, R6 represents hydrogen, an alkyl or hydroxyalkyl radical of 1 to 4 carbon atoms and [Z] represents a radical linear or branched polyhydroxyalkyl having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups.

In the case of the fatty acid N-alkylhydroxyalkylamides these are known substances which are usually obtained by reductive amination of an ammonia reducing sugar, alkylamine or alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or fatty acid chloride. Preferably, the fatty acid N-alkylhydroxyalkylamides are derived from reducing sugars having 5 or 6 carbon atoms, especially glucose. Preferred fatty acid N-alkylhydroxyalkylamides therefore represent fatty acid N-alkylglucamides as represented by formula (E4-IV):

R 7 CO-NR 8 -CH 2 - (CHOH) 4-CH 2 OH (E4-IV).

As N-alkylhydroxyhydroxyalkylamides of fatty acid preferably glucamides of the formula (E4-IV) are used, wherein R8 represents hydrogen or an alkyl group and R7CO represents the acyl radical of capronic acid, caprylic acid, lauric acid. , myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linolic acid, linoleic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or mixtures thereof. Particularly preferred are fatty acid N-alkylglucamides of formula (E4-IV), which are obtained by reductive amination of glycosecom methylamine and subsequent acylation with lauric acid or C12 / 14-cocograx acid or a corresponding derivative. In addition, polyhydroxyalkylamines may also be derived from maltose and palatinose.

As preferred nonionic surfactants, alkylene oxide addition products have been proven with linear unsaturated fatty alcohols and fatty acids in each case with 2 to 30 mo of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations with excellent properties are also obtained when they contain ethoxylated glycerin acid acid esters as nonionic surfactants.

These compounds are characterized by the following parameters. The alkyl radical R contains 6 to 22 carbon atoms and may be tantolinear as well as branched. Preferred linear and aliphatic methyl-branched radicals at position 2. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. By using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms prevail in the alkyl chain.

In addition, sugar surfactants are particularly preferred nonionic surfactants. These may be contained in the agents used according to the invention, preferably in amounts of 0.1 - 20% by weight, relative to the entire agent. Amounts of 0.5-15 wt.% Are preferred and particularly particularly 0.5 - 7.5 wt.% Are preferred.

In the case of compounds with alkyl groups used as the surfactant, these may in each case be uniform substances. However, it is generally preferable in the case of preparation of such substances from native vegetable or animal raw materials to obtain mixtures of materials with different lengths of the dependent alkyl chain of the respective raw material.

For surfactants, which represent ethylene oxide and / or propylene oxide death products with fatty alcohols or derivatives thereof, products with a "normal" homologous distribution as well as those with a narrow homologous distribution can be used. . By "normal" distribution of homologues is meant, in this case, mixtures of homologues, which are obtained by the narration of fatty alcohol and alkylene oxide using alkaline metals, alkali metal hydroxides or alkaline alkaline metal alcoholates as co-catalysts. . Narrow homologous distributions are obtained, in contrast, when using as catalysts, for example, hydrotalcites, alkaline earth metal salts of alkaline earth metal oxides, hydroxides or alcoholates. The use of products with close distribution of homologs may be preferred.

In accordance with the invention, quaternary ammonium compound, esterquate and amidoamine type surfactants are useful. Preferred quaternary ammonium compounds are ammonium halogenides, especially chlorides and bromides such as alkyltrimethylammonium chloride, dialkyl dimethyl ammonium chloride and trialkyl methyl ammonium chloride, for example cetyltrimethyl ammonium chloride, steatryltrimethyl ammonium chloride, distearyl dimethyl chloride, lauryl dimethyl ammonium, lauryl dimethyl benzyl ammonium chloride and tricethyl methyl ammonium chloride, as well as the imidazole compounds known as INCI

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, preferably QAVs with behenyl radicals are applicable, especially those substances known by the name behentrimonium chloride or bromide (do-cosanyltrimethylammonium chloride or bromide). Other preferred QAVs have at least two behenyl radicals, with particularly preferred QAVs having two behenyl radicals in an imidazolium backbone. These substances are commercially sold, for example under the names Genamin® KDMP (CIariant) and Crodazosoft® DBQ (Crodauza).

In the case of esterquats these are known substances which contain at least both an ester function and at least one quaternary ammonium group as a structural element. Preferred esterquats are quaternary fatty acid ester salts with triethanolamine, quaternary fatty acid ester salts with diethanolalkylamines, and quaternary fatty acid ester salts with 1,2-dihydroxypropylalkylamines. These products are sold, for example, by the trademarks Ste. pantex®, Dehyquart® and Armocare®. Armocare® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart® F-75, Dehyquart®C-4046, Dehyquart® L80 and Dehyquart® AU-35 are examples. You have esterquats.

Alkylamidoamines are usually prepared by fatty acid amidation and sections of natural or synthetic fatty acids. A particularly suitable compound of this group of substances according to the invention represents commercially available stearamidopropyl dimethylamine under the designation Tegoamid® 18.

Protective colloids are water soluble polymers which are understood to be high molecular weight compounds which are adsorbed onto the nanoparticles and modify them in such a way that they are prevented from coagulating and agglomerating. Suitable polymer protective colloids are, for example, natural water-soluble polymers such as, for example, gelatin, casein, albumin, starch, vegetable gums and water-soluble derivatives. Natural water-insoluble polymeric substances, such as cellulose ether ( methylcellulose, hydroxyethylcellulose, carboxymethylcellulose), hydroxyethyl starch or hydroxypropyl guar.

Water-soluble synthetic polymers which are suitable as protective coloids are, for example, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, polyasparagic acid and the like.

In preferred compositions of this embodiment according to the invention, the suspension comprises one or more materials (optionally acetalized) of the polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, gelatin materials. , cellulose and their derivatives, especially MC, HEC, HPC, HPMC and / or CMCe / or copolymers, as well as mixtures thereof.

Within the scope of the present invention, polyvinyl alcohols are particularly preferred as water soluble polymers. "Polyvinyl alcohols" (abbreviated PVAL, possibly also PVOH), in this case, is the designation for polymers of general structure

<formula> formula see original document page 17 </formula>

which in small fractions (around 2%) also contain structural units of the type

<formula> formula see original document page 17 </formula>

Commercially available polyvinyl alcohols, which are offered as yellowish-white powders or granules with polymerization degrees in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have hydrolysis degrees of 98-99 or 87. -89 mole% therefore still have a residual content of acetyl groups. Polyvinyl alcohols on the manufacturer's side are characterized by recording the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification index or the viscosity of the solution.

Preferred agents of this embodiment within the scope of the present invention are characterized in that the suspension comprises polyvinyl alcohols and / or PVAL copolymers, whose degree of hydrolysis amounts to 70 to 100 mol%, preferably 80 to 90 mol%, Particularly preferred is 81 to 89 mol% and especially 82 to 88 mol%.

Preferably, polyvinyl alcohols of a certain molecular weight range are used, agents of such embodiment according to the invention being preferred, wherein the suspension comprises polyvinyl alcohols and / or PVAL copolymers, whose molecular weight is against in the range of 3,500 to 100,000 gmol "1, preferably from 10,000 to 90,000 gmol" 1, particularly preferably from 12,000 to 80,000 gmol "1 and especially from 13,000 to 70,000 gmol" 1.

The degree of polymerization of such preferred polyvinyl alcohols is from about 200 to about 2100, preferably from about 220 to about 1890, particularly preferably from about 240 to about 1680 and especially from about 260 to about 1500.

The polyvinyl alcohols described above are widely available commercially, for example by the trademark Mowiol® (Clari-ant). Particularly suitable polyvinyl alcohols within the scope of the present invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88, as well as Mowiol® 8-88.

Other particularly suitable polyvinyl alcohols as a protective colloid for the suspension are deduced from the following table:

<table> table see original document page 18 </column> </row> <table>

Other suitable polyvinyl alcohols as a protective colloid for suspension are ELVANOL® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (DuPont trademark) , ALCOTEX® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemi-cal 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 ( registered trademark of Nippon Gohsei KK). Also suitable are ERKOL daWacker types.

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

<formula> formula see original document page 19 </formula>

which are produced by radical polymerization of 1-vinylpyrrolidone according to solution or suspension polymerization processes using radical formers (peroxides, azo compounds) as initiators. Ion polymerization of the monomer provides only mixed molar mass products. Commercially available polyvinylpyrrolidones have molar masses in the range of about 2500-750000 g / mol, which are characterized by recording the K-values depending on the K-value having glass transition temperatures of 130 - 175 ° C.

Vinylpyrrolidone copolymers with other monomers, especially vinylpyrrolidone / vinyl ester copolymers, such as are sold, for example, by the Luviskol® (BASF) trademark are also suitable. Luviskol® VA 64 and Luviskol® VA 73, in each case devinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

Vinyl ester polymers are polymers accessible from vinyl esters with the grouping of formula (II)

<formula> formula see original document page 19 </formula>

as the basic composition element characteristic of macromolecules.

Of these, vinyl acetate (R = CH3) polymers with polyvinyl acetate have the greatest technical significance as the most important space representatives.

Polymerization of vinyl esters is radically carried out by different processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization). Vinyl acetate-vinylpyrrolidone copolymers contain monomer units of the formulas (I) and (II).

Other suitable water-soluble polymers are polyethylene glycols (polyethylene oxides), which are abbreviated as PEG.PEG are ethylene glycol polymers which satisfy the general formula (III).

H- (O-CH 2 -CH 2) n-OH (III),

where η can assume values between 5 and> 100,000.

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

Products with molar masses <about 25,000 g / mol are liquid at room temperature and are referred to as the polyethylene glycols themselves, abbreviated PEG. Such short-chain PEGs may be especially added to other water soluble polymers, for example polyvinyl alcohols or cellulose ethers as plasticizers. Solid room temperature polyethylene glycols, usable according to the invention, are referred to as polyethylene oxides, abbreviated PEOX. High molecular weight depolyethylene oxides have an extremely low concentration of reactive hydroxy end groups and therefore show no more than weak glycol properties.

Furthermore, according to the invention, gelatin is also suitable as a water soluble coating material, which is preferably used in conjunction with other polymers. Gelatin is a polypeptide (molar mass: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and animal bones under acidic or alkaline conditions. The amino acid composition of gelatin largely corresponds to that of collagen, from which it is derived and varies according to its origin. The use of gelatin as a water-soluble coating material is extremely widespread, especially in pharmacy, in the form of hard or soft gelatin capsules. Gelatin in the form of films is little used due to its high price compared to the polymers mentioned above.

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

cellulose ethers, such as hydroxypropylcellulose, hydroxyethylcellulose and methylhydroxypropylcellulose, such as are sold, for example, under the trademark Culminai® and Benecel® (AQUALON).

Cellulose ethers may be described by the general formula (IV)

<formula> formula see original document page 21 </formula>

wherein R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula (III) represents -CH 2 CH 2 CH 2 -OH or -CH 2 CH 2 -OH. Cellulose ethers are technically produced by etherification of soda-cellulose (eg, ethylene oxide). Cellulose ethers are characterized by the mean DS disubstitution degree or the MS molar substitution degree, which indicate how many hydroxy groups of a cellulose anhydroglucose unit reacted with the etherification reagent or how many moles of the etherification reagent were added on average to one unit of anhydroglucose. Hydroxyethylcelluloses are water soluble from a DS of about 0.6 or an MS of about 1. Commercially available hydroxyethyl- or hydroxypropylcelluloses have degrees of substitution in the range of 0.85-1.35 (DS) or 1,5-3 (MS). Hydroxyethyl and propylcelluloses are marketed as yellowish, odorless and tasteless powders in very different degrees of polymerization. Hydroxyethyl and propylcelluloses are soluble in cold and hot water, as well as in some aqueous organic solvents, in most organic (anhydrous) solvents, by contrast, are insoluble; their aqueous solutions are relatively insensitive to changes in pH value or addition of electrolytes.

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

Other suitable polymers according to the invention are water soluble amphopolymers. By the concept of amphoteric polymers are meant amphoteric sepolymers, ie polymers, which contain both free amino groups and free -COOH or SO3 groups in the molecule and are capable of forming internal salts, bipolar polymers, which contain quaternary ammonium groups in the molecule. and -COO "or -SO3" groups and bring together those polymers, which contain the -COOH or SO3H groups and quaternary ammonium groups. An example of an amphopolymer usable according to the invention is acrylic resin for sale under the name Amphomer®, which represents a tert.-butylaminoethyl methacrylate copolymer, N- (1,1,3,3-tetramethylbutyl) acrylamide as well as two or more acrylic acid group monomers, methacrylic acid and their simple esters. Equally preferred amphopolymers are unsaturated carboxylic acids (eg acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyl trimethyl ammonium chloride) and optionally other ionic monomers or Non-ionic, as, for example, can be deduced from the publication of German Report 3929 973 and the prior art cited therein. Acrylic acid, methacrylate, and methacrylamidopropyltrimmonium chloride terpolymers, such as are commercially available under the designation Merquai® 2001 N1 are particularly preferred ampopolymers according to the invention. Other suitable amphoteric polymers are, for example, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers for sale under the names Amphomer® and Amphomer® LV-71 (DELFT NATI-ONAL).

Suitable water soluble anionic polymers according to the invention are, among others:

- vinyl acetate / crotonic acid copolymers, as sold for example by Resyn® (NATIONAL STARCH), Luviset® (BASF) and Gafset® (GAF) designations. These polymers, in addition to the demonomer units of the above mentioned formula (II), also have monomer units of the general formula (V):

[-CH (CH3) -CH (COOH) -] n (V)

- Vinylpyrrolidone / vinyl acrylate copolymers obtainable, for example, by the trademark Luviflex® (BASF). A preferred polymer is vinylpyrrolidone / acrylate terpolymer for sale under the designation Luviflex® VBM-35 (BASF).

Terpolymers of acrylic acid / ethyl acrylate / N-tert.butylacrylamide, which is sold, for example, under the designation Ultra-hold® strong (BASF).

Grafting polymers of vinyl esters, esters of Î ± -crylic acid or methacrylic acid alone or in the mixture copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene glycols and / or polyalkylene glycols. Such grafted vinyl ester polymers of acrylic acid or methacrylic acid alone or in admixture with other polyalkylene glycol copolymerizable compounds are obtained by heat polymerization in a homogeneous phase by the mixing of polyalkylene glycols in the vinyl ester monomers, acrylic acid esters or methacrylic acid, in the presence of radical formers.

Suitable vinyl esters have been proven, for example, vinyl acetate, vinyl propionate, vinyl butyrate, benzoate devinyl and as acrylic acid or methacrylic acid esters, which may be obtained with low molecular weight aliphatic alcohols. especially ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol.

Polypropylene glycols (abbreviated PPG) are propylene glycol polymers which satisfy the general formula V1

<formula> formula see original document page 24 </formula>

where η can assume values between 1 (propylene glycol) and several thousand. Here are technically significant especially di-, tri- and tetrapropylene glycol, ie the representatives with η = 2, 3 and 4 in formula VI.

In particular, polyethylene glycol grafted devinyl acetate copolymers and polyethylene glycol grafted vinyl acetate and crotonic acid polymers may be used.

- Grafted and crosslinked copolymers from the copolymerization of

(i) at least one nonionic monomer;

(ii) at least one ionic monomer;

iii) polyethylene glycol and

iv) a crosslinker.

The polyethylene glycol used has a molecular weight of between 200 and several million, preferably between 300 and 30,000.

Nonionic monomers may be of a very different type and the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl acetate allyl, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.

Likewise, nonionic monomers may be of very different types, among which crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are particularly preferably contained in graft polymers.

As crosslinkers, preferably ethylene glycol dimethacrylate, diallylphthalate, ortho-, meta- and para-divinylbenzene, tetraalyloxyethane and polyalylacchares having 2 to 5 allyl groups per saccharin molecule are used.

The grafted and crosslinked copolymers described above are preferably formed from:

(i) 5 to 85% by weight of at least one nonionic monomer;

(ii) 3 to 80% by weight of at least one type ionic monomer;

iii) 2 to 50% by weight, preferably 5 to 30% by weight, depolyethylene glycol and

iv) 0.1 to 8% by weight of a crosslinker, the percentage of the crosslinker being formed by the proportion of the total weights of i), ii) and iii).

- by copolymerizing at least one monomer of each copolymer obtained from the following three groups:

(i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of unsaturated short-chain saturated alcohols and carboxylic acids;

(ii) unsaturated carboxylic acids;

iii) esters of long chain carboxylic acids and unsaturated alcohols and / or esters of carboxylic acids of group ii) with Ce-ie-unsaturated or straight chain or branched alcohols.

By carboxylic acids or short chain alcohols are meant in this case those having 1 to 8 carbon atoms, and the carbon chains of such compounds may be optionally interrupted by two-bonded hetero groups such as -O-, -NH- , -S-.

- Terpolymers of crotonic acid, vinyl acetate and a esterallyl or metalyl ester.

These terpolymers contain monomer units of the general formulas (II) and (IV) (see above), as well as monomer units of one or more allyl or metallylic esters of formula VII: <formula> formula see original document page 26 </ formula>

wherein R 3 represents -H or -CH 3 R 2 represents -CH 3 or -CH (CH 3) 2 and R 1 represents -CH 3 or a saturated straight chain or C 1-6 saturated alkyl radical and the sum of the carbon atoms in the radicals R 1 and R 2 preferably 7, 6, 5, 4, 3 or 2. The terpolymer mentioned above preferably results from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83 wt.% Vinyl acetate and 8 to 20 wt.%, Preferably 10 to 17 wt.%, Allyl or metallyl ester of formula VII.

- Tetra- and pentapolymers of

(i) crotonic acid or allyloxyacetic acid

ii) vinyl acetate or vinyl propionate

iii) branched allyl or metallylic esters

iv) vinyl ethers, vinyl esters or straight chain allyl or metalyl esters.

- Crotonic acid copolymers with one or more ethylene group monomers, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts

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

Other polymers according to the invention, preferably applicable to the suspension, are cationic polymers. Among cationic polymers, in this case, permanent cationic polymers are preferred. According to the invention, "cationically permanent" are those polymers which, regardless of the pH value, have a cationic group. These are usually polymers, which contain a quaternary nitrogen atom, for example, in the form of an ammonium group. Preferred cationic polymers are, for example, quaternized cellulose derivatives such as are sold under the names Celquat® and Polymer JR®. Celquat® H 10O1 Celquat® L 200 and Polymer JR® 400 are preferred quaternized cellulose derivatives.

- Quaternary group polysiloxanes, such as, for example, commercially available Q2-7224 products (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino modified silicone, which is also Amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker), as well as Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; di-quaternary polydimethylsiloxanes, Quaternium-80 ),

- cationic guar derivatives, such as especially products sold under the trade names Cosmedia® Guar and Jaguar®,

- Polymer dimethyldiallylammonium salts and their copolymers, esters and amides of acrylic acid and methacrylic acid. Products for sale under the trade names Merquat® 100 (po-li (dimethyldiallylammonium chloride)) and Merquat® 550 (dimethyldiallylammonium acrylamide chloride copolymer) are examples of such cationic polymers.

Vinylpyrrolidone copolymers with quaternized dialkylaminoacrylate and methacrylate derivatives, such as, for example, quaternized vinylpyrrolidone dimethylaminomethacrylate copolymers with diethyl sulfate. Such compounds are commercially available under the names Gafquat®734 and Gafquat® 755.

Vinylpyrrolidone-methoimidazoline chloride copolymers as offered under the name Luviquat®.

quaternized polyvinyl alcohol also as the polymers known by the designations

- Poliquaternium 2,

- Poliquaternium 17,

- Poliquaternium 18 and

- Poliquaternium 27

with quaternary nitrogen atoms in the polymer backbone. In this case, the mentioned polymers are designated by the so-called INCI nomenclature, where detailed information can be found in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5th Edition, The Cosmic, Toiletry and Fragrance Association, Washington, 1997, which is made by reference here.

Preferred cationic polymers according to the invention are quaternized cellulose derivatives as well as dimethyldiallylammonopolymers salts and their copolymers. Cationic cellulose derivatives, especially the commercial product Polymer® JR 400, are very particularly preferred cationic polymers.

In the oral and dental hygiene and cleaning agents of this embodiment, the suspension preferably has depH values between 5 and 7, particularly preferably between 5.5 and 6.9, especially between 6 and 6.6. Preferred viscosities of the suspension are in the range of 500 to 20,000 mPas, so that preferred mouth and tooth cleaning agents according to the invention are characterized by the fact that the suspension at 20 ° C has a viscosity (measured with Brookfield DV III viscometer, spindle 4, 4 revolutions / minute) from 500 to 20,000 mPas, preferably from 750 to 15,000 mPas and especially from 1000 to 10,000 mPas.

The suspensions usable according to the invention may be prepared by precipitation reaction from aqueous solutions of water-soluble calcium salts and aqueous solutions of water-soluble phosphate or fluoride salts. In this case, precipitation is effected in the presence of water-soluble surfactants or water-soluble polymer protective colloids. This may be effected, for example, in such a way that surfactants or colloids protecting the phosphate or fluorine saline or calcium salt solution are added prior to the reaction. Alternatively, the aqueous calcium saline solution may be added simultaneously with the phosphate or fluoride saline in a surfactant or protective colloid aqueous solution.

Another process variant is to precipitate from a strongly acidic solution of a water-soluble calcium salt and a stoichiometric amount of a water-soluble phosphate salt with a pH value below 3 by increasing the pH. the pH value with alkali or ammonia in the presence of water soluble surfactants or water soluble polymer protective colloids.

For the preparation of the suspensions according to the invention in other liquid media conveniently, aqueous suspensions according to the invention are conveniently departed from the aqueous phase by filtration or centrifugation, if necessary, dried. nanoparticles and redisperse them into organic solvents. In this case, a further addition of surfactants or protective colloids is no longer necessary as the nanoparticles contain the amounts of stabilizers required to inhibit adsorbed surface agglomeration. Therefore, the fine dispersibility and stability of these suspensions is comparable to aqueous suspensions. Another possibility is to mix the aqueous suspension with a high boiling solvent, for example, with glycerine and distilively remove the water. As an organic liquid medium, it is especially suitable for use in tooth-cleaning agents, especially glycerin and its liquid mixtures with sorbitol and eventually with water.

Alternatively to the above-mentioned embodiment or in addition thereto, the mouth and teeth cleansing agents may contain the nanoparticulate calcium salts also in the form of composite materials. Here, mouth and tooth cleaning agents are preferred, which contain the calcium salt (s) in the form of primary rod-shaped particles having a thickness in the range 2 to 50 nm and a length in the range. 10 to 150 nm in the form of composite materials, which - in relation to the weight of the composite material - contain

c) 0.05 to 15% by weight, preferably 0.5 to 10% by weight and especially 1 to 7.5% by weight, of protein-selected protein components, protein hydrolysates and hydrolysate derivatives. protein;

d) 0.01 to 15 wt.%, preferably 0.1 to 10 wt.% and especially 0.5 to 7.5 wt.%, of the calcium salt (s) in the form of primary particles in the form of of rods having a thickness of 2 to 50 nm and a length of 10 to 150 nm.

By composite materials are meant composite materials which comprise the components mentioned in a) and b) and represent microscopically heterogeneous aggregates, but macroscopically have a homogeneous appearance and in which the primary particles of decalcium salts are present associated with the protein component structure. Fraction of protein components in composite materials amounts to 0.05 to 15 wt.%, Preferably 0.5 to 10 wt.%, And especially 1.0 to 7.5 wt. composite materials.

As proteins within the scope of the present invention, fundamentally all proteins are considered regardless of their origin or production. Examples of animal proteins are que rat, elastin, collagen, fibroin, albumin, casein, whey protein, placenta protein. According to the invention, these are preferred collagen, keratin, casein, whey protein, proteins of plant origin, such as, for example, wheat protein and wheat germ protein, rice protein, soy protein, Oat protein, pea protein, debatata protein, almond protein and yeast protein may also be preferred according to the invention.

By protein hydrolysates within the scope of the present invention are meant protein degradation products such as, for example, collagen, elastin, casein, keratin, almond protein, potato, wheat, rice and soy which are obtained by acid, alkaline and / or enzymatic hydrolysis of the proteins themselves or their breakdown products, such as, for example, gelatin. For enzymatic degradation all hydrolytically effective enzymes such as, for example, alkaline proteins are suitable. Other suitable enzymes as well as enzymatic hydrolysis processes are described, for example, in K. Drauz and H. Waldmann, Enzyme Catalysis in Organic Synthesis, VCH-VerIag1 Weinheim 1975. In their association, proteins are broken down into small subunits, whereby that degradation can be through the polypeptide stages through the oligopeptides to the individual amino acids. Poorly degraded protein hydrolysates include, for example, the preferred gelatin within the scope of the present invention, which may have molar masses in the range of 15,000 to 250,000 D. Gelatin is a polypeptide, which is obtained primarily by collagen hydrolysis under acidic conditions ( A) or alkaline (type gel gelatin) gelatin. The strength of the gelatin gel is proportional to its molecular weight, that is, a more strongly hydrolyzed gelatin provides a less viscous solution. The strength of gelatin gel indicated in Bloom numbers. In enzymatic dissociation of gelatin, the polymer size decreases sharply, which leads to very low Bloom numbers.

Further, within the scope of the present invention, protein hydrolysates are preferred as the usual cosmetic protein hydrolysates with an average molecular weight in the range of 600 to 4000, particularly preferably from 2000 to 3500. Summaries for the preparation and use of protein hydrolysates are published, for example, by G. Schuster and A. Domsch in Seifen Ole Fette Wachse 108, (1982) 177 or Cosm. To-il. 99, (1984) 63, by H. W. Steisslinger in Parf. Kosm. 72, (1991) 556 and F.Aurich and colleagues in Tens.Surf.Det. 29, (1992) 389. Preferably, collagen protein hydrolysates, keratin, casein as well as plant proteins are used according to the invention, for example those based on wheat gluten or wheat protein. rice, the preparation of which is described in two German patent documents DE 19502167 C1 and DE 19502168C1 (Henkel).

By protein hydrolyzate derivatives within the scope of the present invention are meant chemically and / or chemoenzymatically modified protein hydrolysates, such as, for example, the compounds known by the INCI names. Sodium Cocoyl Hydrolyzed Wheat Protein, Laurdimonium Hydroxypropyl CocoylHydrolyzed Collagen, Potassium Undecylenoyl Hydrolyzed Collagen and Laur-dimonium Hydroxypropyl Hydrolyzed Collagen. Preferably according to the invention, derivatives of collagen, keratin and casein protein hydrolysates as well as vegetable protein hydrolysates such as, for example, Sodium Cocoyl Hydrolyzed Wheat Protein or Laur-dimonium Hydroxypropyl Hydrolyzed Wheat Protein are used.

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

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

Protein components are preferred all structure-forming proteins, protein hydrolysates and protein hydrolysates derivatives, among which are those protein components, which, based on their chemical constitution, form certain three-dimensional spatial structures which are common to the protein chemist by the terms secondary, tertiary or also quaternary structure.

Particularly preferred is the selected protein component of gelatin, casein and / or hydrolysates thereof.

In another embodiment of the invention, the nanoparticulate calcium salt primary particles present in the composite materials may be coated with one or more surface modifying agents.

Thus, for example, the preparation of composite materials can be facilitated in those cases where the nanoparticle calcium salts are poorly dispersed. The surface modifying agent is adsorbed on the surface of the nanoparticles and is modified in such a way that the dispersibility of the calcium salt increases and prevents the agglomeration of the nanoparticles.

In addition, the structure of the composite materials as well as the protein component burden with the nanoparticulate calcium salt may be influenced by a surface modification. Thus, by applying composite materials in remineralization processes, it is possible to influence the course and speed of the remineralization process.

By surface modifying agents are meant substances which adhere physically to the surface of finely divided particles, but do not chemically react with them. The individual molecules of surface modifying agents adsorbed on the surface are essentially free of intermolecular bonds with one another. By surface modifying agents are meant especially dispersing agents. Dispersing agents are known in the art, for example also by the terms emulsifiers, protective colloids, humectants, detergents and the like.

Mouth and tooth cleaning agents according to the invention may contain in addition to the above-mentioned essential constituents other constituents of mouth-cleaning agents, mouth-cleaning agents, teeth cleaning agents and / or tooth hygiene agents. Other preferred constitutive substances are described below.

Mouth and tooth cleaning agents according to the invention may contain especially also antimicrobial substances as preservatives or as anti-plate active substances. Such substances may be selected from, for example, methyl ester, p-hydroxybenzoic acid ethyl or propyl, sodium sorbate, disodium benzoate, bromochlorophene, triclosane, phenyl salicylic acid ester, biguanides, for example chlorhexidine, thymol and others. Preferred teeth and teeth cleaning and cleaning agents according to the invention are characterized by the fact that they further contain antiplaque active substances, preferably methyl, ethyl or propyl ester of p-hydroxybenzoic acid, sodium sorbate, sodium benzoate, bromochlorophene, triclosane, phenyl salicylic acid ester, biguanides, for example chlorhexidine, thymol, preferably in amounts of 0.1 to 5 wt%, preferably 0.25 to 2.5 wt% and especially 0.5 to 1, 5% by weight, in each case for each agent.

Another preferred group of constituent substances, which may be contained in the agents according to the invention, are anti-cavity substances. These may be selected, for example, from fluororganic or inorganic, for example from sodium fluoride, potassium fluoride, sodium monofluorophosphate and sodium fluororsilicate. Zinc fluoride, tin (11) fluoride are also preferred. Preferably, an amount of 0.01 - 0.2% by weight of fluorine should be contained in the form of the mentioned compounds.

Mouth and teeth cleaning agents according to the invention, which additionally contain anti-decay active substances, preferably fluorine (s), especially sodium fluoride, potassium fluoride, sodium monofluorophosphate, zinc fluoride, fluoride tin and sodium fluorosilicate, preferably in amounts from 0.01 to 5% by weight, preferably from 0.1 to 2.5% by weight and especially from 0.2 to 1.1% by weight, in each case in to the total agent are preferred according to the invention.

Mouth and tooth hygiene and cleaning agents, especially dentifrices, may contain, for example, substances which are effective against tartar. Such substances may be, for example, chelate formers, such as, for example, ethylenediaminetetraacetic acid and its sodium salts, pyrophosphate salts, such as the water-soluble tetraalkaline metal pyrophosphate dialkali metal salts, for example, Na4PaO7, K4P2O7, Na2K2P2O7, Na2H2P2O7 and K2H2P2O7 or polyphosphate salts, which may be selected from, for example, water soluble alkaline metal tripolyphosphates, such as sodium tripolyphosphate and polyphosphate tripolyphosphate.

Preferred mouth and tooth cleaning agents according to the invention are characterized in that they additionally contain phosphate (s), preferably alkaline metal phosphate (s) and especially sodium tripolyphosphate, preferably in amounts. from 1 to 10% by weight, particularly preferably from 2 to 8% by weight and especially from 3 to 7% by weight, in each case with respect to the total agent.

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

Polishing agents are primarily suitable for all known friction bodies for toothpastes, especially those which 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, for example, chalk, calcium pyrophosphate, dicalcium phosphate dihydrate, may be contained in amounts of up to 5% by weight.

The total content of polishing agents is preferably in the range of 5 - 50% by weight of the tooth cleaning agent.

Particularly preferred are toothpastes and liquid tooth cleaners which contain silicic acids as a polishing agent.

Suitable silicic acids are, for example, gel silicic acids, hydrogel acidic silicic acids and precipitation silicic acids. Freezing silicic acids are produced by the reaction of strong aqueous sodium hydroxide solutions with sodium hydroxide, aging to form the hydrogel, washing and drying. If drying is carried out under protective conditions at a water content of 15 to 35% by weight, so-called hydrogel silicic acids are obtained. By drying to water contents of less than 15% by weight, the previously released structure of the hydrogel is irreversibly shrunk to a dense structure of the so-called xerogel.

A second preferably suitable group of silicic acid thinning agents is precipitation silicic acids. These are obtained by precipitation of silicic acid from dilute alkali metal silicate solutions by the addition of strong acids under conditions where aggregation to the sun and gel cannot take place. Preferably a precipitation silicic acid having a BET surface of 15-110 m 2 / g, with a particle size of 0.5 - 20 pm, with at least 80 wt.% Of the primary particles should be below 5 wt. 30-60 Pa.s (20 ° C) 30% glycerine-water dispersion viscosity (1: 1) in a 10-20% by weight amount of the dentifrice. Preferably suitable precipitation silicic acids of this type are: They also have vertices and rounded corners and are sold under the tradename Sidentl 2 DS (DEGUSSA).

Other precipitation silicic acids of this type are Sident 8 (DEGUSSA) and Sorbosil AC 39 (Crosfield Chemicals). These silicic acids stand out for a lower thickening effect and a higher average particle size of 8 - 14 pm with a specific surface area of 40-75 m2 / g (according to BET) and are particularly good for liquid toothpastes. These must have a viscosity (25 ° C, shear rate D = 10 s -1) of 10 - 100 Pa.s.

Toothpastes, which have a markedly higher viscosity of more than 100 Pa.s (25 ° C, D = 10 s -1), in contrast, require a sufficiently high fraction of silicic acids with a particle size of less of 5 pm, preferably at least 3% by weight, of a silicic acid having a particle size of 1 - 3 pm. Therefore, in addition to the precipitation silicic acids mentioned above, the so-called even more finely divided thickening silicic acids with a BET surface area of 150 - 250 m2 / g are added to these dentifrices, for example Sipernat 22 commercial products. LS or Si-pernat 320 DS.

As another component of the polishing agent it may also be contained, for example, aluminum oxide in the form of lightly calcined alumina having an aluminum oxide content in an amount of about 1 - 5% by weight. Such an appropriate aluminum oxide is sold under the tradename "Poliertonerde P10 feinst" (Giulini Chemie).

Further, all known friction bodies for dentifrices such as, for example, sodium aluminum silicate, such as, for example, zeolite A, organic polymers such as, for example, polymethacrylate or mixtures thereof and those mentioned above.

In summary, mouthwash and tooth cleaning agents according to the invention are preferred, which additionally contain cleaning bodies, preferably silicic acids, aluminum hydroxide, aluminum oxide, calcium pyrophosphate, chalk, dihydrate, dicalcium phosphate (CaHP04, 2H20), sodium aluminum aluminum silicates, especially zeolite A, organic polymers, especially polymethacrylates or mixtures thereof, preferably in amounts of 1 to 30% by weight, preferably from 2.5 to 25% by weight and especially from 5 to 20% by weight, in each case in relation to the total agent.

As an excipient for dentifrices, which enables the adjustment of a suitable consistency for the dosing of flexible tubes, dispensing reservoirs or vials, a combination of moisture maintenance agents, adhesives and water is provided.

Moisture holding agents are, for example, sorbitol or glycerin or 1,2-propylene glycol contained in the compositions according to the invention. In addition to these substances, of which at least one is contained in amounts of at least 10% by weight, in the agents according to the invention, they are provided as moisture keeping agents, preferably alcohols with at least 2 OH groups. preferably mannitol, xylitol, polyethylene glycol, polypropylene glycol and mixtures thereof.

Among these compounds, those with 2 to 12 OH groups and especially those with 2, 3, 4, 5, 6 or 10 OH groups are preferred. Polyhydroxy compounds with 2 OH groups are, for example, glycol (CH 2 (OH ) CH 2 OH) and other 1,2-diols, such as H- (CH 2) n -CH (OH) CH 2 OH with η = 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 , 14, 15, 16, 17, 18, 19, 20. 1,3 diols, such as H- (CH 2) n -CH (OH) CH 2 CH 2 OH with η = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 are also usable according to the invention. (N, n + 1) - or (n, n + 2) diols with non-terminal OH groups may also be used.

Important representatives of 2-OH polyhydroxy compounds are also polyethylene glycols and polypropylene glycols.

As other preferred moisture holding agents, for example, xylitol, propylene glycols, polyethylene glycols, especially those with average molecular weights of 200-800, may be used.

The additional moisture keeping agent (s) may be used in the agents according to the invention in varying amounts. Whilst depending on the optional residual constituent substances may be contained amounts of less% (e.g. 1, 2, 3, 4,5, 6, 7, 8, 9, 10 wt%, in each case with respect to the agent total), there are also formulations which have significantly higher moisture holding agent contents. The total content of the moisture keeping agent (including sorbitol, glycerine and 1,2-propylene glycol contained in the agents according to the invention) is, for example, 50, 55, 60, 65, 70.75 wt.%. case in relation to the total agent. Agents according to the invention are usual and preferred, which (including sorbitol, glycerine and 1,2-propylene glycol contained in the agents according to the invention) contain from 10 to 75% by weight of agents. Maintaining moisture content. Levels between 15 and 70, preferably between 20 and 60% by weight, in proportion to the total agent, may be preferred.

As a consistency regulator (or adhesive), for example, natural and / or synthetic water-soluble polymers such as alginates, carrageenates, traganth, starch and starch ether, cellulose ether, such as carboxymethylcellulose (salt), are used. Na), hydroxyethylcellulose, methylhydroxypropylcellulose, guar, acacia gum, agar, xanthan gum, gum succinoglycan, locust bean flour, pectin, hydrosoluble carboxyvinyl polymers (e.g. Carbopol® types), polyvinyl alcohol, polyvinylpyrridone, polyethylene glycols, especially those with molecular weights of 1,500-1,000,000.

Other substances which lend themselves to viscosity control are, for example, layer silicates such as, for example, montmorillonite alumina, colloidal thickening silicic acids, such as, for example, silicic acids. airgel, pyrogenic silicic acids or spray precipitated silicic acids. In dentifrices, viscosity stabilizing additives may also be used from the group of cationic, bipolar or ampholytic nitrogen surfactants, hydroxypropyl-substituted hydrocolloids or polyethylene glycol / polypropylene glycol copolymers having an average molar weight of 1000 to 5000 or a combination of the mentioned compounds.

Surfactants are also contained in the dentifrices to aid in the cleaning effect and eventually also for the development of toothbrush foam as well as for stabilizing the dispersion of the polishing body in the excipient in an amount of 0.1-5% by weight. Weight.

Suitable surfactants are, for example, linear sodium alkyl sulfates with 12-18 carbon atoms in the alkyl group. These substances additionally have an enzyme inhibiting effect on bacterial fungi metabolism. Other suitable surfactants are alkali metal salts, preferably sodium salts of alkyl polyglycol ether ether sulfate with 12-16 carbon atoms in the linear alkyl group and 2-6 linear glycolic ether groups in the molecule, of alkan (C1 -C8) -sulfonate of (C12 -C18) monoalkylsulfosuccinic acid esters, sulfated fatty acid monoglycerides, sulfatized fatty acid alkanolamides, sulphoacetic acid alkyl esters, acylsarcosines, acylisurionate acyltauridase in each case with 8 Carbon atoms in the acyl group. Also suitable are bipolar, ampholytic and non-tonic surfactants, for example, fatty acid mono- and diglyceride oxetylates, fatty acid sorbitan esters and alkyl (oligo) glycosides.

Mouth and tooth hygiene agents, especially toothpastes, may also contain substances that increase tooth insensitivity, for example potassium salts, such as, for example, potassium nitrate, potassium citrate, potassium, potassium bicarbonate and potassium oxalate. Mouth hygiene and cleansing agents are characterized by the fact that they contain the substances that increase tooth insensitivity, preferably potassium salts, particularly preferred diode, 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 1.0 to 15 wt.%, more preferably 2, 5 to 10 wt% and especially 4.0 to 8.0 wt%, in each case with respect to the total agent.

The agents according to the invention, especially dentifrices, may additionally also contain other anti-inflammatory curative substances, for example active substances against dagengive inflammation. Such substances may be selected, for example, from allantoin, azulene, chamomile extracts, tocopherol, panthenol, bisabolol, dalvia extracts.

As a non-cationic bactericidal component, for example, phenols, resorcinols, bisphenols, salicylanilides and their halogenated derivatives, halogenated carbanylides and esters of p-hydroxybenzoic acid are particularly preferred. Halogenated diphenyl ethers, for example, are particularly preferred. 2,4-dichloro-2'-hydroxydiphenyl ether, 4,4'-dichloro-2'-hydroxydiphenyl ether, 2,4,4'-tribromo-2'-hydroxydiphenyl ether and 2,4,4'-trichloro-2 ether 'hydroxydiphenyl (triclosane). They are preferably used in amounts of 0.01-1% by weight in the cleansing agents according to the invention. Triclosane is particularly preferably used in an amount of 0.01 - 0.3 wt.%.

D-panthenol D - (+) - 2,4-dihydroxy-N- (3-hydroxypropyl) -3,3-dimethylbutyramide shows a biological activity corresponding to pantothenic acid. Pantothenic acid (R - (+) - N - (2,4-dihydroxy-3,3-dimethylbutiri (-p-alanine) is a pre-stage in coenzyme A biosynthesis and is included in the vitamin B (B3) complex These substances are known to promote healing and have a favorable effect on the skin, so they have also possibly been described in dentifrices.The teeth whitening agents 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 an international name for vitamin A1. One of its derivatives with similar biological effect may also be used, for example an ester or retinoic acid (tretinoin), one of its salts or esters, preferably a retinol ester, especially a fatty acid ester of a 12-22 carbon atoms fatty acid Retinol palmitate is particularly particularly suitable When using a retinol ester, for example retinol palmitate with an activity of 1.7.106 IU per 0.001 to 0.1% by weight is preferred.When using other retinol derivatives, an application amount of 103 to 106 Ul (international units) per 100 g.

Preferred dentifrices according to the present invention contain, in addition to polishing agents, fluorine compounds, moisture keeping agents and adhesives, 0.01 - 1% by weight of a halogenated diphenyl ether. 5% by weight of panthenol or a salt of pantothenic acid and 0.01 - 0.1% by weight of a retinol ester, preferably palmitate deretinol.

Agents according to the invention, especially dentifrices, may also contain substances to increase mineralizing potential, for example calcium-containing substances, such as, for example, calcium chloride, calcium acetate and phosphate dihydrate. dicalcium. Concentration of the calcium-containing substance depends on the solubility of the substance and the interaction with other substances contained in the mouth and teeth hygiene agents.

In addition to the mandatory components mentioned, the teeth cleansing agents according to the invention may contain other adjuvants and additives known per se. In this case, an additive, which has long been known as a dentifrice component, is particularly effective in the tooth-cleaning agents according to the invention: calcium glycerophosphate, the calcium salt of glycerin-1-acid. phosphoric acid or glycerin-2-phosphoric acid or glycerin-3-phosphoric acid enantiomer to glycerin-1-phosphoric acid - or a mixture of such acids. The compound has a remineralizing effect on tooth hygiene agents as it provides both calcium and phosphate ions. In the cleaning agents according to the invention, calcium glycerophosphate is preferably used in amounts of 0.01-1% by weight. In total, tooth cleaning agents according to the invention may contain customary co-adjuvants and additives in amounts of up to 10% by weight.

Teeth hygiene agents according to the invention may be improved in their organoleptic characteristics, for example by the addition of aromatic essences and sweeteners.

As aromatic essences all the usual natural and synthetic scents for tooth-cleaning agents can be used. Natural scents can be contained in the form of both the isolated ethereal natural essences of drugs and their individual isolated components.

Suitable aromas are, for example, peppermint essence, peppermint essence, eucalyptus essence, anise essence, fennel essence, fennel essence, menthol acetate, cinnamic aldehyde, anethole, vanillin, as well as mixtures of these components.

Suitable sweeteners are, for example, sodium saccharin, sodium cyclamate, sucrose, lactose, maltose, fructose.

Other common adjuvants and additives for toothpastes are surfactants, preferably bipolar, amphoteric, nonionic surfactants, or a combination of several different surfactants,

- solvents and dissolution promoters, for example lower monovalent or polyvalent alcohols or ethers, for example ethanol, 1,2-propylene glycol, diethylene glycol or butyldiglycol

- pigments such as, for example, titanium dioxide

- dyes

- buffering substances, eg primary, secondary or tertiary alkaline metal phosphates or citric acid / sodium citrate

- other curative or anti-inflammatory substances, for example allantoin, urea, azulene, chamomile active substances, acetylsalicylic acid or rhodanide derivatives

- other vitamins, such as, for example, ascorbic acid, bio-tine, tocopherol or rutin

mineral salts, such as, for example, manganese, zinc or magnesium salts.

Another important group of constituent substances, which may be contained in the agents according to the invention, are called bioactive glasses.

The term "bioactive glasses" encompasses within the scope of this application glasses which are biologically effective and / or biologically active. The biological efficacy of a glass can be shown, for example, in its antimicrobial characteristics, biologically active glass differs from conventional lime-sodium silicate glasses in that it binds living tissue. In this case, biologically active glass designates, for example, a glass, which performs a solid bond with body tissues, forming its layer of hydroxyapatite. By bioactive glass is also meant a glass, which shows antimicrobial and / or anti-inflammatory effect. The empo glasses compared to bacteria, fungi as well as viruses, show a biological effect or a biostatistic; In contact with man, they are tolerable to skin, toxicologically harmless and especially also suitable for consumption.

Particularly preferred mouth and tooth treatment and cleaning agents according to the invention are characterized in that they contain 0.2 to 20 wt.%, Preferably 0.4 to 14 wt.%, Particularly preferably. 0.5 to 3% by weight and especially 0.6 to 2% by weight of at least one bioactive glass.

Mouth and tooth hygiene and cleaning agents according to the invention, in this embodiment, contain bioactive glass or glass powder or glass powder ceramics or composite materials which comprise such bioactive glass. Glass powders within the scope of this patent application also include glass granules and beads.

Based on the requirements for the toxicological insensitivity of glass as well as its suitability for consumption, glass powder must be particularly pure. The load through the heavy metals is preferably low.

Thus, the maximum concentration in the range of cosmetic formulations preferably for Pb is <20 ppm, Cd <5 ppm, As <5 ppm, Sb <10 ppm, Hg <1 ppm, Ni <10 ppm.

The non-ceramized starting glass, which is obtained directly from the preferred compositions according to the invention or is optionally used for the manufacture of a glass ceramic usable according to the invention, contains SiO2 as a network former, preferably between 35-80 ° C. % by weight. At lower concentrations, the spontaneous tendency to crystallization greatly increases and chemical resistance greatly decreases. At higher SiO2 values, the crystallization stability may decrease and the processing temperature is markedly increased, so that the heat molding characteristics worsen. Na2O is used as a fuse for glass fusion. At concentrations below 5%, the melting behavior is negatively influenced. Sodium is a component of the phases that form in ceramization and, since fractions of high crystalline phases must be adjusted through ceramization, it must be contained in the glass at correspondingly high concentrations. K2O acts as a flux in the melting of glass. In addition, potassium is distributed in aqueous systems. If high concentrations of new potassium are present, the potassium-containing phases, such as calcium silicates, are also separated. Through the P2O5 content, the chemical resistance of the glass and hence the ion distribution can be adjusted in aqueous media in glass, glass ceramics or silicate composites. In phosphate glasses, P2O5 is the network builder. The P2 O5 content is preferably from 0 to 80% by weight. To improve melting capacity, the glass may contain up to 25% by weight of B2O3. Al 2 O 3 is used to adjust the chemical resistance of the glass.

To reinforce the antimicrobial characteristics, especially the antibacterial characteristics of glass ceramics, antimicrobial ions such as, for example, Ag, Au, I, Ce, Cu, Zn may be contained at concentrations of less than 5% by weight.

Color-imparting ions, such as, for example, Nm, Cu, Fe, Cr, Co, V, may be contained individually or in combination, preferably in a total concentration of less than 1% by weight.

Usually glass or glass ceramics are used in the form of dust. The ceramization can be carried out either with a glass block or glass strips or with glass dust. After ceramization, the glass ceramic blocks or strips have to be ground to form dust. If the powder has been ceramized, it must eventually be ground again to remove clumps that formed during the ceramization stage. Grinding can be done both dry, as well as in aqueous or non-aqueous grinding media. Usually the particle sizes are smaller than 500 μιτι. Particle sizes <100 μιτι or <20 μιτι have been found to be convenient. Particle sizes <10μιτι as well as smaller than 5μιτι as well as smaller than 2μιτι are particularly suitable, see below.

Bioactive glasses or glass powders or glass ceramic powders or composite compositions contained in the preferred compositions according to the invention comprise glasses, preferably comprising the following components: SiO 2: 35-80 wt%; Na2O: 0-35 wt%, P2O5: 0-80 wt%, MgO: 0-5 wt%, Ag2O: 0-0.5 wt%, Agi: 0-0.5 wt%, NaI: 0-5 wt%, TiO2: 0-5 wt%, K2O: 0-35 wt%, ZnO: 0-10 wt%, Al2O3: 0-25 wt% and B2O3: 0-25 wt% Weight.

In addition, ions such as Fe, Co, Cr, V, Ce, Cu, Nm, Ni, Bi, Sn, Ag1 Au, I alone or in sum up to 10% by weight may be added to the basic glass. according to the above composition for other effects such as, for example, UV staining or filtration. Another glass composition may be as follows: SiO 2 35-80% by weight, Na 2 O: 0-35 wt%, P2O5: 0-80 wt%, MgO: 0-5 wt%, Ag2O: 0-0.5 wt%, Agi: 0-0.5 wt%, NaI: 0-5% by weight TiO2: Ο-5 wt%, K2O: 0-35 wt%, ZnO: 0-10 wt%, Al2O3: 0-25 wt%, B2O3: 0-25 wt%, SnO: 0-5 wt%, CeO 2: 0-3 wt% and Au: 0.001-0.1 wt%.

Particularly preferred mouth and tooth cleaning agents according to the invention are characterized by the fact that bioactive glass - in relation to its weight - has the following composition:

SiO2 25 to 60 wt%, preferably 40 to 60 wt%, Na2O 0 to 35 wt%, preferably 5 to 30 wt%, K2O 0 to 35 wt%, preferably 0 to 20 wt%, P2O50 up to 10 wt%, preferably 2 to 10 wt%, MgO 0 to 10 wt%, preferably 0 to 5 wt%, CaO 0 to 35 wt%, preferably 5 to 30 wt%, Al2 O3 0 to 25 wt%, preferably 0 to 5 wt%, B2O3 0 to 25 wt%, preferably 0 to 5 wt%, TiO2 0 to 10 wt%, preferably 0.1 to 5 wt%.

As mentioned above, bioactive glass is preferably used in particle form. Particularly preferred mouth and tooth cleaning agents according to the invention are characterized by the fact that antimicrobial glass has particle sizes <10 μιτι, preferably 0.5 to 4 μιη, Particularly preferred is from 1 to 2 μπι.

The compositions according to the invention, thus decoding, are particularly suited for cleaning and hygiene. They clean the teeth carefully and in this case have the additional utility of polishing the tooth surface. In the case of risk value determinations (treatment of teeth with standard conditions with different compositions and comparison of surfaces with respect to treatment of a standard polishing agent), the compositions according to the invention have clear advantages: they scratch the tooth surface significantly less than corresponding compositions, which do not contain or contain less than 10% by weight, of sorbitol and / or glycerin and / or 1,2-propylene glycol. In addition, it has been found in comparison to compositions, which do not contain or contain less than 0.25 wt.% Bioactive, compared to compositions, which do not contain or contain less than 10 wt.%, Of sorbitol and and / or glycerin and / or 1,2-propylene glycol and in comparison with compositions containing both no and less than 0.25% by weight of bioactive glass and no or less than 10% by weight of sorbitol and / or glycerin and / or 1,2-propylene glycol, a marked reduction in the presence of buccal odor. Similarly, the volunteers found in unison that the compositions according to the invention, in relation to the comparative compositions, more effectively prevent the formation of a new buccal odor or that the intensity of the newly formed buccal odor after the course of a period. The time defined in the compositions according to the invention relative to the comparative compositions decreases markedly.

Claims (10)

1. Hygiene and cleaning agent for the mouth and teeth, containing by weight>> 0,005 to <0,1% by weight of calcium salt (salts) in the form of primary rod-shaped particles with a thickness in the range 2 to 50 nm and a length in the range 10 to 150 nm. Mouth and tooth hygiene and cleaning agent according to claim 1, characterized in that - in relation to its weight it contains 0.01 to 0.09% by weight, preferably 0.02 to 0.08% by weight. particularly preferably 0.03 to 0.075% by weight, more preferably 0.04 to 0.07% by weight and especially 0.05 to-0.065% by weight of calcium salt (salts) in the rod-shaped primary particle form having a thickness in the range 2 to 50 nm and a length in the range 10 to 150 nm. Mouth and tooth hygiene and cleaning agent according to one of claims 1 or 2, characterized in that the or ossal (salts) of calcium in the form of primary rod-shaped particles having 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 selected from the hydroxylapatite, fluorapatite and calcium fluoride group. Mouth and tooth hygiene and cleaning agent according to one of Claims 1 to 3, characterized in that it additionally contains calcium salt or salts (salts) in the form of rod-shaped primary particles having a thickness of 2 µm. up to 50 nm and a length in the range 10 to 150 nm, other calcium salt (s), preferably calcium glycerophosphate. Mouth and tooth cleaning agent according to one of Claims 1 to 4, characterized in that it contains the calcium salt (s) in the form of primary rod-shaped particles with a thickness 2 to 50 nm and a length in the range 10 to 150 nm in the form of a suspension, which - with respect to the weight of the suspension, contains) 0.01 to 15% by weight, preferably 0.1 to 10%. by weight and especially 0.5 to 7.5% by weight, of at least one water-soluble surfactant and / or at least one water-soluble polymer protective colloid, (b) 0.01 to 15% by weight preferably 0.1 to 10 wt.% and especially 0.5 to 7.5 wt.% of the calcium salt (s) as primary rod-shaped particles of thickness 2 to 50 nm and a length in the range 10 to 150 nm. Mouth and tooth hygiene and cleaning agent according to claim 5, characterized in that the suspension at 20 ° has a viscosity (measured with the Brookfield DV III viscometer, spindle 4, 4 revolutions / min) of 500 to 20,000 mPas, preferably from 750 to -15,000 mPas and especially from 1000 to 10,000 mPas. Mouth and tooth hygiene and cleaning agent according to one of Claims 1 to 4, characterized in that it contains the calcium salt (s) in the form of rod-shaped primary particles having a thickness of 2 µm. up to 50 nm and a length in the range 10 to 150 nm in the form of composite materials, which - by weight of the composite material - contain) 0,05 to 15% by weight, preferably 0,5 to 10% by weight and especially 1 to 7.5% by weight of protein-selected protein components, protein hydrolysates and protein hydrolyzate derivatives b) 0.01 to 15% by weight, preferably 0.1 to 10% by weight. and especially 0.5 to 7.5% by weight of the primary salt (s) of the rod-shaped particle calculus having a thickness in the range 2 to 50 nm and a length in the range from 10 to 150 nm. Mouth and tooth hygiene and cleaning agent according to one of Claims 1 to 7, characterized in that it contains substances that increase the insensitivity of the teeth, 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% by weight, particularly preferably from 1.0 to 15% by weight. Preferably, from 2.5 to 10 wt% and especially from 4.0 to 8.0 wt%, in each case relative to the total agent. Mouth and tooth cleaning agent according to one of Claims 1 to 8, characterized in that it additionally contains antiplaque active substances, preferably methyl, ethyl or propyl ester of p-hydroxybenzoic acid, sodium sorbate, disodium benzoate, bromochlorophene, triclosane, phenyl salicylic acid ester, biguanides, for example chlorhexidine, thymol, preferably in amounts from 0.1 to 5% by weight, preferably from 0.25 to 2.5% by weight and especially 0.5 to 1.5% by weight, in each case for the entire agent. Mouth and tooth hygiene and cleaning agent according to one of Claims 1 to 9, characterized in that it contains 0.2 to 20% by weight, preferably 0.4 to 14% by weight, particularly preferably. 0.5 to 3% by weight and especially 0.6 to 2% by weight of at least one bioactive glass.