DE102006009797A1 - Method for oral and dental cleaning and / or remineralization - Google Patents

Abstract

The invention relates to a method for cleaning the mouth and teeth, for re-or re-mineralization of the tooth material and / or for reducing the sensitivity to pain of teeth, characterized in that the teeth with an electric toothbrush device, preferably an ultrasonic toothbrush, and a mouth and / or dentifrices comprising poorly water-soluble calcium salts and / or their composite materials, and a kit for use in this method.

Description

The The invention relates to a method for oral and dental cleaning, for Re- or neomineralization of the tooth material and / or for reduction the sensitivity of teeth to teeth, characterized in that the teeth are provided with an electrical, preferably acoustic toothbrush and a mouth and / or Tooth cleaning and / or care products, comprising sparingly water-soluble calcium salts and / or composite materials comprising these sparingly water-soluble Calcium salts, to be treated.

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

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

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

The Bone and tooth substance is a combination of scleroproteins and platelike Hydroxyapatite.

at the restoration of bone material play so-called bone substitute, which the natural Promote biomineralization process, an important role. Such agents are also needed for coating from implants to cohesive To achieve connections between bone and implant, with which also transfer tensile forces can be. Of particular importance here are coatings with a high bioactivity which lead to an effective composite osteogenesis. According to the state of the art, like him B. G. Willmann in Mat.-wiss. u. Werkstofftech. 30 (1999), 317 describes, is usually hydroxyapatite on implants applied. The disadvantage of this approach is in addition to the often insufficient acceleration of the biomineralization process the Chipping the hydroxyapatite layers and their unsatisfactory chemical stability.

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

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

composite materials of the type described are accessible synthetically, such as By B. Flautre et al. in J. Mater. Sci .: Mater. In Medicine 7 (1996), 63. However, in these composites lies the Grain size of the calcium salts above 1000 nm, which is too large to be satisfactory to achieve biological effect as Remineralisierungsmittel.

In contrast, describes Z. Wang et al., J. Mater. Sci. Lett. 14 (1995), 490 a manufacturing method for a Composite of hydroxyapatite and collagen, in which hydroxyapatite with a particle size in the range from 2 to 10 nm in evenly distributed Form is deposited on the collagen matrix. The composite material should be opposite other hydroxyapatite-collagen composites known in the art due to the fineness of the hydroxyapatite a better biological Have effectiveness. As described below, however, met also the R. Z. Wang et al. not described composite material enough the need for composite materials showing the composition and the microstructure natural Imitate bone and tooth material and in fully satisfying Way suitable for remineralization of these natural materials are.

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

The WO 01/01930 discloses composite materials consisting of nanoparticulate sparingly soluble Calcium salts and protein component are built and the one Remineralizing effect on enamel and dentin Have (dentin).

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

Mouth- and / or dentifrice and / or care products used for tooth cleaning of sensitive teeth are suitable, z.T. by having the open dentinal channels with one Close the plug and so on. are capable of hypersensitivity reactions by irritation of the exposed nerves, for example, by heat or cold at the end of the dentinal channels to prevent or reduce. This material is not particularly liable good on the tooth material and therefore can be easily removed.

to thorough Cleaning the teeth, especially for better plaque removal, electric toothbrushes are preferred acoustic toothbrushes (also ultrasonic toothbrushes called), which by a higher frequency of the brush head characterized in comparison to normal brushing with a manual toothbrush are.

These higher Frequency, especially in the ultrasonic range, however, generates mechanical stress on the tooth material, which have a negative impact can.

Especially on the dentin channels grafted material can ultrasonic toothbrushes affect the effect of these toothpastes almost canceled becomes.

It It has now been found that the method is using certain Calcium salts and / or composite materials for overcoming the above Disadvantages of the prior art is suitable. In particular, can with the method according to the invention an effective cleaning of the teeth with simultaneous closure of the dentinal tubules (dentinal tubules) produced be without this closure removed by cleaning again becomes.

The The invention relates to a method for oral and dental cleaning, for Re- or neomineralization of the tooth material and / or for reduction the sensitivity of teeth to teeth, characterized in that the teeth with an electrical Dental cleaning implement, preferably an ultrasonic toothbrush, and an oral and dental care and / or cleaning agent poorly water-soluble Calcium salts and / or their composite materials, including these poorly water-soluble Calcium salts, to be treated. It can be a variety of electrical Toothbrush equipment be used.

Of the tighter closure of the exposed dentinal tubules is reduced or completely inhibits the painful stimulus on stimulation of the tooth with heat, cold, sweetness, acidity, air or tactile stimulation.

The preferably used according to the invention toothbrushes (also acoustic toothbrushes ge Named) are described for example in US Patent Application 2005/0091770 and WO2005 / 000150, the disclosure of which is hereby incorporated by reference in its entirety.

The used according to the invention to brush In particular, have a frequency of the brush head in the range between 30 and 700 Hz.

oscillating electric toothbrushes usually have a frequency of 30 to 100 Hz with a rotation angle from 20 ° to 70 °, preferably 30 ° to 60 °, for example 50 ° up.

The ultrasonic Toothbrushes preferably have a frequency (movement of the brush head) in the range of 100 to 700 Hz, particularly preferably 200 to 500 Hz. Consequently the brushes move up to 42,000 times per minute.

The mouthpiece according to and dentifrices and / or cleansers may be either immediately before cleaning on the brush head the toothbrush be applied, or in one provided in the toothbrush Reservoir are located. In this case, the dental care and / or Cleaning required amount of formulation either directly automatically when turning on the toothbrush or by a separate push of a button on the brush.

One Another object of the present invention is a kit which in the method according to the invention can be used.

This Kit contains an electric toothbrush, preferably an ultrasonic toothbrush, as well as an oral and dental care and / or cleaning composition.

It may also contain instructions for proper use of the toothbrush be.

The used according to the invention Oral and dental care and / or cleaning products include sparingly water-soluble calcium salts and / or composite materials containing the said sparingly water-soluble Include calcium salts.

These used according to the invention Oral and / or dental cleaning and / or care products form on Dentin and / or Enamel particularly resistant layers, the open dentin close and so are capable of hypersensitivity reactions by irritation of the exposed nerves, for example, by heat or cold at the end of the dentinal channels to prevent. These layers are, unlike others through Dentifrice for sensitive teeth methods used, including by the use of an electric or ultrasonic toothbrush not to destroy.

The Particles of the calcium salts, which consist of individual crystallites according to the invention are built up, can depending on the conditions of the manufacturing process preferred platelet and / or rod-shaped.

According to one particularly preferred embodiment are the particles of calcium salts (also in the composite materials) predominantly platelet-shaped.

mainly platelet-shaped, that at least 50%, preferably at least 70%, is particularly preferred at least 80% of the particles are in the form of platelets.

Especially Preferably, the particles have a substantially plate-like Shape up.

advantageously, are the calcium salts of the invention or composite materials comprising these, with the predominantly platelet-like Calcium particles of the structure of the bone substance in vivo, which also Made of plates, especially similar. This has the special Advantage that they are due to the similarity of the form with the biological apatites (for example bone or dentin apatite) a particularly good ability have to re - and neomineralization, so that the process of Biomineralization can take place even faster and better.

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

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

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

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

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

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

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

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

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

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

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

The platelet-shaped particles are common in such samples also overlapping several times in front. Overlapping Particles are usually in the places of overlap with a higher contrast (stronger blackening) Shown as non-overlapping Particle. The specified lengths, Latitudes and heights will be preferably not overlapping Particles of the sample determined.

The Height (thickness) the platelet-shaped particles can be preferred from such recordings by determining the dimensions the one with its largest surface vertical to the image plane standing particles are obtained. The vertical particles standing to the image plane are characterized by a particularly high contrast and appear rather needle-like. This vertically to the image plane standing platelet-shaped particles can at a tilt of the image plane by the broadening of the dimension and a decrease in intensity The figure identified as standing perpendicular to the image plane become.

to Determination of height it is particularly suitable for the particle, the image plane of the sample several times in different positions to tilt and the dimensions the particle in the setting to determine by the highest contrast and the least dimension of the particles is characterized. The shortest Expansion then corresponds to the height (thickness) of the particles.

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

Prefers the width of these particles is in the range between 10 to 100 nm.

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

The flaky Shape of the particles is formed by the ratio of length to width. Is the ratio between Length and Width significantly larger than 4, are more rod-shaped particles in front.

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

According to a further particular embodiment, the particles have an area of 0.1 × 10 ^-15 m ² to 90 × 10 ^-15 m ² , preferably an area of 1 × 10 ^-15 m ² to 50 × 10 ^-15 m ² , especially preferably 1.5 × 10 ^-15 m ² to 30 × 10 ^-15 m ² , very particularly preferably 2 × 10 ^-15 m ² to 15 × 10 ^-15 m ² .

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

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

As slightly sparingly soluble in water calcium salt should be understood as those salts which are soluble in water at 20 ° C to less than 0.1 wt .-% (1g / l). Such suitable salts include calcium hydroxyphosphate (Ca ₅ [OH (PO _{4) 3])} or hydroxyapatite, Galciumfluorphosphat (Ca ₅ [F (PO _{4) 3)} or fluoroapatite, fluorine-doped hydroxylapatite composition Ca ₅ (PO _{4) 3} ( OH, F) and calcium fluoride (CaF ₂ ) or fluorite or fluorspar and other calcium phosphates such as di-, tri- or tetracalcium phosphate (Ca ₂ P ₂ O ₇ , Ca ₃ (PO ₄ ) ₂ , Ca ₄ P ₂ O ₉ oxyapatite ( Ca ₁₀ (PO ₄ ) ₆ O) or non-stoichiometric hydroxyapatite (Ca _{5 -½ (x + y)} (PO ₄ ) _3-x (HPO ₄ ) _x (OH) _1-y ) Also suitable are carbonate-containing calcium phosphates (eg Ca _{5-½ (x + y + z)} (PO ₄ ) _3-xz (HPO ₄ ) _x (CO ₃ ) _z (OH) _1-y ), calcium hydrogen phosphate (eg CaH (PO ₄ ) 2H ₂ O) and Octacalcium phosphate (eg Ca ₈ H ₂ (PO ₄ ) ₆ .5H ₂ O).

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

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

Thereby For example, the production of composite materials in such make be facilitated in which the calcium salts difficult to disperse to let. The surface modifier becomes to the surface the crystallites and / or particles adsorbs and alters them such that the dispersibility of the calcium salt increases and reduces the agglomeration of the crystallites and / or particles or is essentially prevented.

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

Surface modifiers are understood to mean substances which are present on the surface of the fine particle physically adhere to loose 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.

• – Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe;
• – C_12/18-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin;
• – Glycerinmono- und -diester und Sorbitanmono- und -diester von gesättigten und ungesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen und deren Ethylenoxidanlagerungsprodukte;
• – Alkylmono- und -oligoglycoside mit 8 bis 22 Kohlenstoffatomen im Alkylrest und deren ethoxylierte Analoga;
• – Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• – Polyol- und insbesondere Polyglycerinester, wie z. B. Polyglycerinpolyricinoleat, Polyglycerinpoly-12-hydroxystearat oder Polyglycerindimerat. Ebenfalls geeignet sind Gemische von Verbindungen aus mehreren dieser Substanzklassen;
• – Anlagerungsprodukte von 2 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• – Partialester auf Basis linearer, verzweigter, ungesättigter bzw. gesättigter C_6/22-Fettsäuren, Ricinolsäure sowie 12-Hydroxystearinsäure und Glycerin, Polyglycerin, Pentaerythrit, Dipentaerythrit, Zuckeralkohole (z. B. Sorbit), Alkylglucoside (z. B. Methylglucosid, Butylglucosid, Lauryl-glucosid) sowie Polyglucoside (z. B. Cellulose);
• – Mono-, Di- und Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEG-alkylphosphate und deren Salze;
• – Wollwachsalkohole;
• – Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;
• – Mischester aus Pentaerythrit; Fettsäuren, Citronensäure und Fettalkohol gemäß DE-PS 1165574 und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin oder Polyglycerin sowie
• – Polyalkylenglycole.

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

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group;
• C _12/18 fatty acid _mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol;
• Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;
• - Alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs;
• - Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• - Polyol and in particular polyglycerol esters, such as. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxy stearate or polyglycerol dimerate. Also suitable are mixtures of compounds of several of these classes of substances;
• - addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• Partial esters based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, Butylglucoside, lauryl glucoside) and polyglucosides (eg, cellulose);
• - Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;
• - wool wax alcohols;
• - polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
• Mixed esters of pentaerythritol; Fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol and
• - Polyalkylene glycols.

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

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

typical examples for anionic emulsifiers are soaps, alkylbenzenesulfonates, alkanesulfonates, Olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfofatty, Alkyl sulfates, alkyl ether sulfates such as fatty alcohol ether sulfates, Glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, sulfate fatty acid amide (ether), Mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfo-succinamates, Sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, taurides, N-acyl amino acids such as acylglutamates and acylaspartates, alkyl oligoglucoside sulfates, Protein fatty acid condensates (especially wheat-based vegetable products), and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, can this a conventional, but preferably a narrow homolog distribution exhibit.

Furthermore, zwitterionic surfactants can be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable Zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammoniumglycinate, for example Kokosalkyldimethylammoniumglycinat, N-acyl-amino-propyl-N, N-dimethylammonium glycinate, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3 carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. Particularly preferred is the fatty acid amide derivative known under the CTFA name co-camidopropyl betaine. Also suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C _8/18 -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12/18 acylsarcosine. In addition to the ampholytic, quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

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

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

Particularly suitable surface-modifying agents are, above all, the nonionic surfactants ⁱⁿ an amount of from 1 to 20% by weight, based on the weight of the calcium salt. The nonionic surfactants of the type of the alkyl C 8 -C 16 (oligo) glucosides and of the ethoxylates of the hardened castor oil have proved to be particularly effective.

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

According to a particular embodiment, composite materials according to the invention are used in the process according to the invention which

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

It is preferred that the particles in the composite rod and / or platelet-shaped, preferably predominantly are platelet-shaped.

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

The used according to the invention Composite materials are therefore structured composite materials in the Contrary to the case of R. Z. Wang et al. described composite Hydroxyapatite and collagen, in which evenly distributed hydroxyapatite nanoparticles available. Another essential difference between the object The present invention and the prior art consists in the size and morphology the inorganic component. The methods described in R. Z. Wang et al. described Hydroxylapatite-collagen composite present hydroxyapatite particles have a size of 2-10 nm. Hydroxylapatite particles in this size range are in the range the amorphous or partially X-ray amorphous Attributable to substances.

Another advantage of composite materials is that they do not tend to aggregate so much that they can be better processed in the production process. In particular, an improved Disper to observe the composability of the composite.

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

A preferred embodiment The invention consists in that as the polymer component polyelectrolytes be used.

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

sowie Derivaten der vorstehend genannten Stoffe, insbesondere Amino- und/der Carboxyl-Derivaten. Bevorzugt werden im Rahmen der vorliegenden Erfindung Polyelektrolyte eingesetzt, die zur Salzbildung mit zweiwertigen Kationen geeignete Gruppen tragen. Insbesondere eignen sich Carboxylat-Gruppen tragende Polymere.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 compositions used according to the invention contain, for example, one or more polyelectrolytes selected from

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

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

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

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

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

One Advantage of the invention used Composite materials is the particular stability in aqueous systems even without Addition of dispersing aids such as polyhydric alcohols (such as Glycerol or polyethylene glycols).

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

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.

Under Protein hydrolysates are degradation products in the context of the present invention of proteins such as collagen, elastin, casein, keratin, Almond, potato, wheat, rice and soy protein to be understood 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. Other suitable enzymes and enzymatic hydrolysis are described, for example, in K. Drauz and H. Waldmann, Enzymes Catalysis in Organic Synthesis, VCH-Verlag, Weinheim 1975. In the Degradation, the proteins are split into smaller subunits, the degradation over the levels of polypeptides over the oligopeptides can go as far as the individual amino acids. To the little ones degraded protein hydrolysates counts for example, those preferred in the context of the present invention Gelatin having molecular weights in the range of 15,000 to 250,000 D. can. Gelatine is a polypeptide primarily produced by hydrolysis of collagen under acid (gelatin type A) or alkaline (gelatin Type B) conditions is obtained. The gel strength of the gelatin is proportional to their molecular weight, d. a more hydrolyzed gelatin gives a lower viscosity solution. The gel strength gelatin is reported in Bloom numbers. In the enzymatic Cleavage of the gelatin, the polymer size is greatly reduced, resulting in leads to 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 NW Steisslinger in Parf.Kosm. 72, (1991) 556 and F. Aurich et al. in Tens.Surf.Det. 29, (1992) 389 appeared. Preferably, protein hydrolysates of collagen, keratin, casein and vegetable proteins are used according to the invention, for example those based on wheat gluten or rice protein, their preparation in the two German patents DE 195 02 167 C1 and DE 195 02 168 C1 (Henkel) is described.

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

Further examples for Protein hydrolysates and protein hydrolyzate derivatives, which are among the 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 used in any of the present invention Composite materials selected by one or more substances the group of proteins, protein hydrolysates and protein hydrolyzate derivatives be formed.

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

According to one Particularly preferred use is the protein component of the composite materials selected from gelatin and casein as well as their hydrolysates.

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

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

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

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

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

Surprisingly has now been found that the composite materials, the gelatin of Type AB, "acid contain bone, have a particularly strong neomineralization.

composite materials those made of a slightly water-soluble Calcium salt can be obtained with gelatin of type AB (acid-bone) can, are therefore particularly suitable for use with bones and teeth (cf. Examples). The inventively used Composite materials are therefore compared to the composites mentioned preferred for the use in particular for the rapid closure of dentinal tubules, the Remineralization of the tooth material, for use in teeth and Bones for prevention and / or therapy of damage, the on external influences, in particular of body-related, chemical, physical and / or microbiological nature, e.g. in erosion, primary lesions and Initial caries and caries prophylaxis, to improve resistance against mechanical stress and generally for improvement cleaning properties of teeth and dental health generally suitable.

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

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

at the manufacturing process, the assembly of the individual components in principle in all possible Sequences take place. The alkalizing agent is preferably ammonia used.

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

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

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

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

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

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

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

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

Prefers is used to form the inventively preferred Composite material thereby a solution a calcium salt with the polymer component and presented a phosphate solution slowly added, with the pH between 5 and 9, preferably between 6 and 8, more preferably around 7 lies. Especially preferred Way is the pH with the addition of the phosphate solution kept constant by adding appropriate amounts of aqueous base.

For the preparation of dispersions of surface-modified calcium salts, other methods can be used, such as those in the German application DE 19858662.0 described.

The used according to the invention Calcium salts or composite materials, including these, and in particular such composite materials with a protein component selected from Collagen, casein or gelatin, especially those of hydroxyapatite, Fluorapatite and calcium fluoride, are suitable as mineralizing Component for the preparation of compositions for cleaning and / or Care of the teeth.

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

Advantageously, the process according to the invention results from the use according to the invention of Calcium salts or composite materials, including these, and in particular such composite materials with a protein component selected from collagen, casein or gelatin, which acts as neo- or remineralizing components, for the strengthening of the enamel.

One Another advantage of the method according to the invention using the calcium salts or composite materials comprising these, and in particular of such composite materials with a protein component selected from Collagen, casein or gelatin, it is that biomineralization for the Treatment of dental or bone defects is induced or promoted.

Farther does that inventive method using calcium salts or composite materials, comprising these, and in particular such composite materials with a protein component selected from collagen, casein or gelatin, or corresponding compositions for smoothing the surface of teeth.

The inventive method protects and / or is used for the therapeutic and / or preventive treatment of teeth or in case of damage, the on external influences, in particular of body-related, chemical, physical and / or microbiological nature, especially for prevention and repair of erosions on bones and teeth, in particular tooth enamel, Care of the enamel, as well as to protect the teeth from attack by acids, in particular by bacterial activity or by the action of acids from food, to protect against demineralization of the teeth, to Seal of fissures for protection and / or repair of primary lesions and / or Initial caries in the enamel and for smoothing the tooth surface, for Caries prevention, to improve cleanability, the mechanical resistance of the teeth as well as dental health in general.

The inventive method can when using calcium salts, and preferably the composite materials, comprising these, and in particular such composite materials a protein component selected made of collagen, casein or gelatin, used against attacks by acids.

Under the term acids Here are both the intrinsic acids and the extrinsic Acids too understand. The injury by intrinsic acids concerns in particular medically related diseases that with a contact of stomach acid associated with the oral region, especially in belching, regurgitation, Heartburn or vomiting, also in connection with pathological Eating disorder, like bulimia in particular.

Especially suitable is the use in case of attack by extrinsic acids, in particular due to bacterial activity or the action of acids Food.

Farther could be observed that in addition to prevention, before erosion of teeth (Dentin and enamel) and bones, especially enamel, a repair erosion on tooth and bone, especially the enamel the composite materials according to the invention takes place.

The calcium salts according to the invention, and preferably the composite materials comprising these, and in particular such composite materials with a protein component selected from Collagen, casein or gelatin are therefore also therapeutic the repair of damage, especially erosions, bones and teeth, especially enamel, apply.

Prefers are the calcium salts according to the invention, and preferably the composite materials comprising these, and in particular such composite materials with a protein component selected from collagen, Casein or gelatine, for the protection and / or repair of Primary lesions and / or Initial caries in the enamel and to seal fissures used. According to the invention can by use according to the invention Fissures (i.e., those on the occlusal surface the jaws and molars located columnar Recoveries) and thus their caries susceptibility be reduced.

Farther does that inventive method using the calcium salts, or preferably the composite materials, including these, in particular those with a protein component selected from collagen, casein or gelatin, to a better mechanical Resistance. In particular, the extent of micro-scratches, craters or reduced mechanical abrasion.

The inventive method using the calcium salts or the composite materials also leads to a better resistance to mechanical stress of the teeth, in addition to chewing as well can be caused in particular by vigorous brushing teeth. Damage or erosion of softened enamel can thus be avoided.

by virtue of the said positive effects of the method according to the invention It is used to improve the cleanability of the teeth and of dental health in general.

The Compositions for cleaning and care of the teeth can, for example, in Form of pastes, liquid Creams, gels or mouthwashes available. Even in liquid Preparations, the composite materials according to the invention distribute themselves easily, remain stably dispersed and do not tend to sediment.

Of the Content of the sparingly water-soluble Calcium salts and / or composite materials, including these, preferably the composite materials, in particular those with a Protein component selected from collagen, casein or gelatin, in the mouth and dentifrices 0.0001 to 10 wt .-%, preferably 0.01 to 2 wt .-%, based on the Total weight of the agent.

The mouthpiece according to and dentifrices furthermore from 0.1 to 9% by weight, in particular from 2 to 8% by weight, at least a cleaning agent included.

cleaning supplies belong to the essential ingredients of a toothpaste and are ever according to their intended function alone or in combination with other cleaning objects or polishes. They serve for the mechanical removal of the uncalcified dental plaque and should ideally shine the tooth surface (Polishing effect) with minimal scrubbing effect (abrasion effect) and damage of enamel and dentin. The abrasion behavior the polishing agent and cleaning body is mainly due to their hardness, grain size distribution and surface structure certainly. When selecting suitable cleaning bodies are therefore in particular those are preferably selected with a high cleaning performance over a minimum abrasion effect feature.

nowadays be as a cleaning body mainly used substances that have small particle sizes, largely free of sharp corners and edges are and their hardness and mechanical properties the tooth or the tooth substance is not stressed too much.

Usually be as a cleaning body or polishes water-insoluble inorganic substances used. Particularly advantageous is the use very finely divided polish with a mean particle size of 1-200 microns, preferably 1-50 μm and more preferably 1-10 μm.

in principle can the polishing agent according to the invention selected be made of silicas, Aluminum hydroxide, alumina, silicates, organic polymers or mixtures thereof. Furthermore, however, so-called metaphosphates, Alkaline earth metal carbonates or bicarbonates and calcium-containing polishing components in the inventive compositions be included.

It may be preferred according to the invention be silicas as a polishing agent in toothpastes or liquid dentifrices use. Among the silica polishing agents, a distinction is generally made between gel silicic acids, hydrogel silicic acids and Precipitated silicas. precipitation and gel silicas are particular to the invention preferred because they can be varied widely in their preparation and Particularly well with fluoride drugs are compatible. They are own also very good for the production of gel or liquid toothpastes.

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

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

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

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

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

When Alumina polishing agent is preferably a weakly calcined Alumina containing α- and γ-alumina in an amount of about 0.01 to 5 wt .-%, preferably 0.1 to 2 wt .-%, based on the total weight of the agent.

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

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

In contrast to α-Al ₂ O _3, the γ-Al ₂ O ₃ can be stained red with an aqueous ammoniacal solution of Alizarin S (1,2-dihydroxy-9,10-anthraquinone-4-sulfonic acid). One can choose the degree of dyeability as a measure of the degree of calcination or for the proportion of δ-Al ₂ O ₃ in a calcined alumina:
Approximately 1 g Al ₂ O ₃ , 10 ml of a solution of 2 g / l Alzarin S in water and 3 drops of an aqueous, 10 wt .-% solution of NH 3 are placed in a test tube and boiled briefly. The Al ₂ O ₃ is then filtered off, washed, dried and evaluated under the microscope or evaluated colorimetrically.

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

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

A preferred suitable quality "polishing clay P10 Fine "has a Agglomerate size below 20 μm, one average primary crystal size of 0.5-1.5 microns and a bulk weight from 500-600 g / l.

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

Examples for water-insoluble metaphosphates according to the invention are mainly sodium metaphosphate, calcium phosphate such as Tricalcium phosphate, calcium hydrogen phosphate, calcium hydrogen phosphate dihydrate and calcium pyrophosphate.

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

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

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

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

According to the invention preferred Remineralization components are magnesium salts.

suitable embodiments of the oral and dentifrices are solid, liquid or semi-liquid toothpastes and dental gels.

The mouthpiece according to and dentifrices according to another preferred embodiment additional Toothpaste ingredients such as surfactants, humectants, binders, Flavors and active ingredients against tooth and gum diseases.

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

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

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

anionic surfactants

Suitable surfactants with good foaming action are anionic surfactants which also have some enzyme have inhibitory effect on the bacterial metabolism of plaque.

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

Preference is given to the use of at least one anionic surfactant, in particular a sodium lauryl alkyl sulfate having 12-18 C atoms in the alkyl group. Such a surfactant is sodium lauryl sulfate which is commercially available for example under the name Texapon.RTM ^® K12 G commercially.

zwitterionic and ampholytic surfactants

It may be preferred according to the invention be zwitterionic and / or ampholytic surfactants, preferably in Combination with anionic surfactants, use. As zwitterionic Surfactants become such surface active Compounds referred to in the molecule at least one quaternary ammonium group and carry at least one carboxylate and one sulfonate group.

Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammoniumglycinate, for example the Trimethylammoniumglycinat, Kokosalkyldimethylammoniumglycinat, N-acylamino-propyl-N, N-dimethyl-ammoniumglycinate, for example Kokosacylaminopropyldimethyl-ammoniumglycinat, and 2-alkyl 3-carboxymethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethylglycinate. Particularly preferred is the known under the CTFA name Cocamidopropyl Betaine fatty acid amide derivative. Such products are available, for example under the name Tego betaine ^® BL 215 and ZF 50 and Genagen ^® CAB commercially.

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

nonionic surfactants

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

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

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group;
• - C ₁₂ -C ₁₈ fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol;
• Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;
• - Alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogues;
• - Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• Polyol and in particular polyglycerol esters, such as, for example, polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate.

• – Anlagerungsprodukte von 2 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• – Partialester auf Basis linearer, verzweigter, ungesättigter bzw. gesättigter C₆-C₂₂-Fettsäuren, Ricinolsäure sowie 12-Hydroxystearinsäure und Glycerin, Polyglycerin, Pentaerythrit, Dipentaerythrit, Zuckeralkohole (z.B. Sorbit), Sucrose, Alkylglucoside (z.B. Methylglucosid, Butylglucosid, Laurylglucosid) sowie Polyglucoside (z.B. Cellulose);
• – Mono-, Di- und Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEGalkylphosphate und deren Salze;
• – Wollwachsalkohole;
• – Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;
• – Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol gemäß DE-PS 1165574 und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin oder Polyglycerin sowie
• – Polyalkylenglycole.

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

• - addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• - Partial ester based on linear, branched, unsaturated or saturated C ₆ -C ₂₂ fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (eg sorbitol), sucrose, alkylglucosides (eg methylglucoside, butylglucoside, laurylglucoside) as well as polyglucosides (eg cellulose);
• - Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEGalkylphosphate and their salts;
• - wool wax alcohols;
• - polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
• - Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol and
• - Polyalkylene glycols.

The addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products and are preferred according to the invention. These are homolog mixtures whose mean degree of alkoxylation corresponds to the ratio of the molar amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C ₁₂ -C ₁₈ fatty acid mono- and diesters of addition products of ethylene oxide with glycerol are known from DE-PS 2024051 as refatting agents for cosmetic preparations.

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

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

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

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

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

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

The agents according to the invention additionally contain at least one in a preferred embodiment Binding or thickening agent. These have a consistency-regulating effect and continue to prevent the separation of the liquid and solid components.

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

Natural and / or synthetic water-soluble polymers such as alginates, carrageenans, agar agar, guar gum, gum arabic, succinoglycan gum, guar gum, locust bean gum, tragacanth, karaya gum, xanthan, pectins, cellulose and their ionic and nonionic derivatives such as carboxymethylcellulose, hydroxyethylcellulose or methylhydroxypropylcellulose, hydrophobically modified celluloses, starch and starch ethers.

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

In a further preferred embodiment contains the mouthpiece of the invention and dentifrices additional Active ingredients against tooth and gum diseases. Among such According to the invention, active substances are anti-caries active substances, Antimicrobial agents, tartar inhibitors, flavorings or to understand any combination of these substances.

Anti-caries agents

Fluorine compounds, preferably from the group of fluorides or monofluorophosphates in an amount of 0.1-0.5% by weight of fluorine, are especially suitable for controlling and preventing caries. Suitable fluorine compounds are, for. For example, sodium fluoride, potassium fluoride, stannous fluoride, disodium monofluorophosphate (Na ₂ PO ₃ F), dipotassium monofluorophosphate or the fluoride of an organic amino compound.

Anti-plaque agents

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

antimicrobial drugs

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

Under the antimicrobial components are particularly suitable which inhibit the growth of plaque bacteria. For example halogenated diphenyl ethers, such as 2,4-dichloro-2'-hydroxydiphenyl ether, 4,4'-dichloro-2'-hydroxydiphenyl ether, 2,4,4'-tribromo-2'-hydroxydiphenyl ether, 2,4,4'-trichloro-2'-hydroxydiphenyl ether (Triclosan) are suitable as antimicrobial agents. In addition to bromochlorophene, Bisbiguanides such as chlorhexidine and alexidine, phenylsalicylic acid esters and 5-amino-1,3-bis (2-ethylhexyl) hexahydro-5-methylpyrimidine (hexetidine) Zinc and copper ions also act antimicrobial, with synergistic Effects especially in combination with hexetidine and triclosan occur. Also quaternary Ammonium compounds, such as. Cetylpyridinium chloride, benzalkonium chloride, Domiphen bromide and dequalinium chloride can be used. As antimicrobial octapinol, octenidine and sanguinarine have also been effective.

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

Tartar inhibitors

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

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

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

drugs against hypersensitive teeth

Preferably contain the agents of the invention continue active against hypersensitive teeth, they are selected from potassium and strontium salts such as potassium chloride, potassium sulfate, Potassium bicarbonate, potassium citrate, potassium acetate, potassium nitrate, strontium chloride, Strontium nitrate, strontium citrate, strontium acetate and strontium lactate and eugenol.

The Eugenol can with aromatic oils be mixed in the oral and dental care products. Prefers it is in the form of clove bud oil contained in the compositions.

Preferably contain the oral and dentifrices contain at least 0.5% by weight of potassium or strontium ions in the form of a dissolved one Salt and at least 0.01% by weight of eugenol in pure form or in Form of clove bud oil.

flavorings

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

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

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

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

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

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

All these optional dentifrice ingredients are all in one Amount of about 2 to 10 wt .-%, based on the total weight, in the agents according to the invention contain. To be used according to the invention Preparations, preferably oral and dental care products, in particular the toothpastes, too the insensitivity of the teeth contain increasing substances, such as potassium salts z. As potassium nitrate, potassium citrate, potassium chloride, potassium bicarbonate and potassium oxalate. Preferred oral and dental care and cleaning products are characterized that they increase 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 .-%, especially preferably from 1.0 to 15% by weight, 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.

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

Particularly according to the invention preferred oral and dental care and cleaning agents are characterized in that they are 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.

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

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

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

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

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

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

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

Furthermore, the base glass according to the above composition to achieve further effects such as color or UV filtering ions such as Fe, Co, Cr, V, Ce, Cu, Mn, Ni, Bi, Sn, Ag, Au, J individually or in total to be added to 10 wt .-%. A further glass composition may be as follows: SiO ₂ : 35-80 wt.%, Na ₂ O: O-35 wt.%, P ₂ O ₅ : O-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:

As already mentioned above, the bioactive glass is preferably used in particulate form. Here are Particularly preferred oral and Zahnpflege- invention and detergent characterized in that the antimicrobial Glass particle sizes <10 microns, preferably from 0.5 to 4 μm, more preferably from 1 to 2 μm, having. a preferred embodiment are toothpastes containing silicic acid, polishes, humectants, Binders and flavors that are .00001 to 10, especially .01 to 4% by weight; prefers 0.01 to 2% by weight of composite materials according to the invention with nanoparticulate calcium salts from the group hydroxyapatite, fluorapatite and calcium fluoride.

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

According to a further preferred embodiment, the compositions according to the invention contain, in addition to the calcium salt according to the invention and / or the composite materials comprising these, additionally at least one fluoride salt. Surprisingly, it has been found that the addition of fluoride leads to a synergistic enhancement of the nucleating effect of the composite materials according to the invention. Particularly preferred is the addition of sodium and / or potassium fluoride. With the simultaneous addition of active compounds according to the invention and small amounts of fluoride, ^{an approximately} five-fold synergistic amplification is evident.

According to the invention, preference is given to amounts of from 0.01 to 1.2% by weight, in particular from 0.1 to 0.90% by weight of fluoride salt, depending on the fluoride salt used (for example sodium fluoride). ^This corresponds to an amount of fluoride ions used of 0.05 to 0.15 wt .-%, in particular from 0.08 to 0.12 wt .-%.

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

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

Examples

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

1.1 Production of a Apatite Protein Composite

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

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

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

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

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

2.1 Composite material Hydroxylapatite and Gelatin AB First, the solutions A were separated and B produced.

Solution A:

25.4g Calcium nitrate tetrahydrate and 8.50 g diammonium hydrogen phosphate were each dissolved in 100% deionized water. Both solutions were under training a white precipitate combined. After addition of 10 ml of 37 wt .-% HCl was obtained a clear solution.

Solution B:

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

These Dispersion was prepared at room temperature to 100 ml of a similar example to Example 1.1 10 wt .-% aqueous solution of gelatin type AB (manufacturer: DGF Stoess) added, then on Heated to 80 ° C and stirred at this temperature for 5 minutes. Then they left the Mass under formation of the composite material at room temperature solidify.

3. Tooth creams with calcium salt composite materials

The following commercial products were used: Plantacare® ^® 1200: C ₁₂ -C ₁₆ alkyl glycoside about 50 wt .-% in water Manufacturer: Cognis President ^® 8: Synth. amorphous. Silica, BET 60 m ² / g Tamped density: 350 g / l Manufacturer: DEGUSSA Sident ^® 22 S: Hydrogel silicic acid, BET 140 m ² / g Tamping density: 100 g / l Manufacturer: DEGUSSA Polywachs ^® 1550: Polyethylene glycol, MW: 1550 Softening point 45-50 ° C Manufacturer: RWE / DEA Texapon.RTM ^® K 1296: Sodium lauryl sulfate powder Manufacturer: Cognis Cekol ^® 500 T: Sodium carboxymethylcellulose Viscosity (2% in water, Brookfield LVF 20 ° C): 350-700 mPa s Supplier: Noviant Tagat ^® S: Polyoxyethylene (20) -glycerylmonostearat Manufacturer: Tego Cosmetics (Goldschmidt)

Example 4:

a) Preparation of the mild SBF

Dissolving 1.1025 g of CaCl ₂ · 2H ₂ O with stirring in 200 ml water (solution 1). 0.6129 g of KH ₂ PO _{4 were dissolved} with stirring in 300 ml of water (solution 2). 48.4570 g of KCl were dissolved with stirring in 300 ml of water (solution 3). 23.8293 g of HEPES were dissolved with stirring in 300 ml of water (solution 4). 2500 ml of water were placed in a 5 l volumetric flask. While stirring, the individual solutions were added slowly in the order of 1, 2, 3, 4, while the respective beaker was rinsed 3 times with water into the solution. The pH was adjusted to pH = 7.00 with sodium hydroxide solution. It was then filled to 5,000 l with water.

b) Cleaning attempts

Out the roots of cattle incisors Slices were cut out in the way that the dentinal tubules nearly perpendicular to the disk surface stood (size about 6 × 6 mm). The discs were polished smoothly before use and for removal of polishing residues 5 min treated in tap water in an ultrasonic bath. Subsequently were the dentine slabs by means of ESEM (device "The Quanta FEG 200" from FEI Company, execution in low vac mode in 1 mbar steam atmosphere and at 15 kV HV, 4000 times Enlargement) examined. For the subsequent attempt at cleaning was only such slices taken where almost all tubules were completely open.

For the treatment the dentin slices was first a homogeneous slurry from about 1.0 g toothpaste (example of the invention: toothpaste after Recipe example 4.3, cf. Table), with the 3.00-fold amount demineralized water. As a comparative example was according to the same procedure a commercially available Toothpaste for sensitive teeth used which contains 17% hydroxyapatite.

For each examined Dentin disc was a separate Slurry attached. The slurries were each for a maximum of 2 days, then used new slurries were produced.

Two Dentin slabs became random select. The staffs were for 10 min in the respective associated Slurrys stored (= "dipping") and then without rinse in 20 ml of mild SBF at 37 ° C stored. Every working day was for each dentin slice performed a morning and evening dive. After Diving in the morning, the Dentinslabs for 6-8 h (= during the day) in the mild SBF stored after dipping in the evening for 16-18 h (= over Night). Following storage in the mild SBF, the Dentinslabs taken from the SBF and rinsed with mild SBF.

In each case before the first dive of the day the Dentinslabs were cleaned with an ultrasonic toothbrush (Philips Sonicare elite e5500, brush dipped in glycerine / water 1: 1) for 1 min and again with mild SBF rinsed off.

Subsequently were the slabs are dipped as described above and freshened in 20 ml each mild SBF stored as described. 2 working days per 10 min. carried out. Leave on the weekend the slabs in the mild SBF. A total of 10 days, i. a total of 20 dives performed.

To In the last dive the slabs were rinsed with mild SBF and how described with the US toothbrush cleaned. The slabs were again rinsed vigorously with mild SBF and finally by ESEM examined. The results are shown in the figures entitled "After the Treatment ".

Subsequently were the dentin slabs again under tap water for 4 min with the ultrasonic toothbrush brushed and re-examined by ESEM. The results are below the name "After second US brush ".

c) result of the comparative cleaning tests

The toothpaste according to the invention leads as well when using a powerful ultrasonic toothbrush for Formation of a very thick layer on the dentin surface, the also longer Brushing with this ultrasonic toothbrush survives while the comparative experiments with the conventional Sensitive toothpaste only to form a very thin layer leads, which closes the dentinal tubules.

Further shows mechanical stress with the ultrasonic toothbrush doing a noticeable destruction this layer.

following are representative ESEM images of the dentinal labs after the individual treatment steps shown. All pictures are magnified 4000 times.

Legend to the pictures:

1 Before the treatment: The open dentinal tubules are clearly visible.

2 After the treatment with the toothpaste according to the invention: A dense layer was found, which lies above the tubules and obscures the contours of the tubules.

3 After the treatment with the toothpaste according to the invention and the second brushing with the ultrasonic toothbrush: the layer is unchanged. Furthermore, no tubules can be seen.

4 Comparative experiment before treatment: The dentinal tubules are largely open.

5 Comparative experiment after treatment: The dentinal tubules are largely closed. The contours of the tubules are still very clearly visible, which makes it clear that only a very thin protective layer has formed. A lower contrast of the tubules compared to the treatment indicates that a thin layer has formed over the tubule opening. On a few tubules, the strong black color indicates that the tubules are still partially open (arrow).

Abb. 2: Nach der Behandlung mit der erfindungsgemäßen Zahncreme:

Abb. 3: Nach Behandlung mit der erfindungsgemäßen Zahncreme und nach dem zweitem Bürsten mit der Ultraschallzahnbürste:

Abb. 4: Vergleichsversuch vor der Behandlung:

Abb. 5: Vergleichsversuch nach der Behandlung:

Abb. 6: Vergleichsversuch nach der Behandlung und dem zweitem US-Bürsten:

6 : Comparative experiment after the treatment and the second brushing with the ultrasonic toothbrush:
By re-brushing with the ultrasonic toothbrush a variety of tubules have reopened on the dentin disc in the comparative experiment. Fig. 1: Before the treatment:

Fig. 2: After the treatment with the toothpaste according to the invention:

Fig. 3: After treatment with the toothpaste according to the invention and after the second brushing with the ultrasonic toothbrush:

Fig. 4: Comparative experiment before treatment:

Fig. 5: Comparative experiment after treatment:

Fig. 6: Comparative experiment after the treatment and the second US brushing:

Claims (22)

A method for oral and dental cleaning, for re-or neomineralization of the tooth material and / or for reducing the sensitivity of teeth, characterized in that the teeth with an electric Zahnputzgerät, preferably an ultrasonic toothbrush, and an oral and / or dental care product comprising poorly water-soluble calcium salts and / or their composite materials. Method according to claim 1, characterized in that the oral and dental hygiene or detergents included calcium salts in the form of individual Crystallites or in the form of particles comprising a plurality said crystallites, having a mean particle diameter in the Range of less than 1000 nm, preferably less than 300 nm. Method according to claim 2, characterized in that that said particles are rod-shaped and / or platelet-shaped, preferably are predominantly platelet-shaped. Method according to one of the preceding claims, characterized in that a single crystallite of the calcium salts and / or of the composite materials comprising this, a thickness in the range from 2 to 50 nm and one length in the range of 10 to 150 nm, preferably a thickness of 2 to 15 nm and a length of 10 to 50 nm; particularly preferably a thickness of 3 to 11 nm and a length from 15 to 25 nm. Method according to one of the preceding claims, characterized characterized in that the mean particle diameter of the particles calcium salts and / or composite materials comprising these, in the range of less than 1000 nm, preferably less than 300 nm. Method according to one of the preceding claims, characterized characterized, the platelet-shaped particles a length from 10 to 150 nm and a width of 5 to 150 nm. Method according to one of the preceding claims, characterized characterized in that the particles have a length to width ratio between 1 and 4, preferably from 1 to 3, more preferably between 1 and 2, have. Method according to one of the preceding claims, characterized in that the particles have an area of 0.1 × 10 ^-15 m ² to 90 × 10 ^-15 m ² , preferably an area of 0.5 × 10 ^-15 m ² to 50 × 10 ^-15 m ² , particularly preferably 1.0 × 10 ^-15 m ² to 30 × 10 ^-15 m ² , very particularly preferably 1.5 × 10 ^-15 m ² to 15 × 10 ^-15 m ² . Method according to one of the preceding claims, characterized characterized in that the crystallites or particles of the present Calcium salts are coated by one or more surface modifiers. Method according to one of the preceding claims, characterized characterized in that the calcium salts is selected from phosphates, fluorides and fluorophosphates optionally containing additional hydroxyl and / or carbonate groups can contain in particular from the group hydroxylapatite and fluorapatite. Method according to one of the preceding claims, characterized characterized in that the composite materials a) sparingly soluble calcium salts in water, wherein the calcium salts in the form of individual crystallites or in the form of particles comprising a plurality of said crystallites a mean particle diameter in the range of less than 1000 nm, preferably below 300 nm, and b) a polymer component include. Method according to claim 11, characterized in that that the particles in the composite material rod and / or platelet-shaped, preferred predominantly platelet-shaped. Method according to claim 11 or 12, characterized that said polymer component of the composite material is selected from a protein component, polyelectrolytes and polysaccharides. Method according to claim 13, characterized in that that said polyelectrolytes of the composite material are selected from the group formed by polyaspartic acids, alginic acids, pectins, deoxyribonucleic acids, ribonucleic acids, polyacrylic and polymethacrylic acids. Method according to claim 13, characterized in that that said polysaccharides are selected from glucuronic acid and / or Iduronic acid-containing polysaccharides, preferably from glycosaminoglycans, in particular selected from Chondroitin sulfates, heparin and hyaluronic acid, and xanthan gum. Method according to claim 13, characterized in that that said protein component of the composite material is selected from proteins, protein hydrolysates and protein hydrolyzate derivatives. Method according to claim 16, characterized in that that said protein component of the composite material is selected from collagen, gelatin, keratin, casein, wheat protein, rice protein, Soy protein, almond protein and their hydrolyzates and hydrolyzate derivatives. Method according to claim 17, characterized in that that said protein component is selected from collagen, gelatin, Casein and its hydrolysates, preferably gelatin, more preferably Gelatin of the type A, B or AB, in particular gelatin of the acid type bone. Method according to one of claims 11 to 18, characterized that the proportion of protein components in the composite material between 0.1 and 80 wt .-%, preferably between 10 and 60, in particular between 30 and 50 wt .-% based on the total weight of the composite material is. Method according to one of the preceding claims, characterized characterized in that the oral and dental care and cleaning agents additionally Fluoride contained therein. Method according to one of the preceding claims, characterized characterized in that it is in the oral and dental care and cleaning products about toothpastes or tooth gels. Kit for use in any of the above methods, comprising an electric toothbrush, preferably an ultrasonic toothbrush, and an oral and / or dental care formulation.