DE102006009800A1 - Oral and dental care agent and dental cleaning agent, useful for remineralising the teeth, comprises calcium salts in the form of individual crystallites or particles comprising a multitude of crystallites, and silicic acid precipitant - Google Patents

Abstract

Oral and dental care agent and dental cleaning agent comprises >=0.005 to less than 0.1 wt.% of calcium salts (A) in the form of individual crystallites or particles comprising a multitude of the crystallites, where an individual crystallite exhibits a thickness of 2-50 nm and a length of 10-150 nm and the particles are rod- and/or plate-shaped (preferred), and 2-25 wt.% of silicic acid precipitant(s) with a particle size d50 of lesser than 15 mu m (laser diffraction in accordance with ISO 133-20-1).

Description

The Invention relates to preparations for oral and dental care and cleaning, which have a remineralising effect due to special ingredients, have a high cleaning performance without scratching the tooth surface or to be very abrasive, and moreover, the delusion of Prevent bad breath and reduce bad breath.

Dentifrice are in different forms in the market and serve first Line of cleaning the tooth surface and prevention of Tooth and gum disease. They usually contain a combination of polishes, humectants, surfactants, Binders, flavorings and fluoride-containing and antimicrobial Agents. In addition to toothpowder, because of their increased abrasiveness a subordinate Dentifrices, especially in paste, Creamy and translucent or transparent gel form offered. In Liquid or liquid toothpastes and mouthwashes have also been increasing in recent years gained in importance.

Next cleaning the teeth the consumer expects the generic products also a care the teeth and the oral cavity. In particular, a "clean" feel, i. a smooth and shiny tooth surface as well as a fresh feeling in the mouth essential aspects for the incentive to buy preparations for oral and dental care and cleaning. A successful remedy of the generic type should therefore thoroughly clean the teeth, without damaging the tooth or the tooth surface and at the same time halitosis reduce and / or prevent.

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). But also calcium fluoride is as a component of dentifrices and as a component to Consolidation of enamel and caries prophylaxis described several times Service.

The Availability of these substances 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.

From DE-A-21 34 862, for example, a dentifrice for hypersensitive teeth was known, the ultrafine hydroxyapatite (Ca ₅ [(PO ₄ ) ₃ OH]), the particle size of 6-8 microns (microns) is given because by grinding hardly higher subtleties can be achieved.

In the EP 1 139 995 A1 It is proposed to stabilize suspensions of sparingly soluble in water calcium salts in very finely divided form during precipitation or shortly thereafter, by performing the precipitation in the presence of an agglomeration inhibitor or redispersing the dispersion in the presence of the agglomeration inhibitor. These suspensions can be used in toothpastes, amounts above 0.1% by weight (based on the total composition and calculated as calcium salt) being disclosed.

It The task was to solve the above problems without high amounts of possibly more expensive ingredients in the formulations to have to work in. About that In addition, the object of the present invention was to and to provide dental care and cleaning agents which remineralize the teeth and less sensitive to external influences do.

It it has now been found that nanoparticulate calcium salts also and in particular are effective in small amounts, especially if the funds additionally Silicate (s) included.

• a) ≥ 0,005 bis < 0,1 Gew.-% Calciumsalz(e) in Form von einzelnen Kristalliten oder in Form von Partikeln, umfassend eine Mehrzahl besagter Kristallite, wobei ein einzelner Kristallit eine Dicke im Bereich von 2 bis 50 nm und eine Länge im Bereich von 10 bis 150 nm aufweist;
• b) 2,0 bis 25,0 Gew.-% Fällungskieselsäure(n) mit einer Teilchengröße d50 (Laserbeugung gemäß ISO 133-20-1) < 15 μm,

wobei die Partikel stäbchen- und/oder plättchenförmig, bevorzugt vorwiegend plättchenförmig sind.The present invention is in a first embodiment, an oral and Zahnpflege- and -reinigungsmittel containing - based on its weight -

• a) ≥ 0.005 to <0.1% by weight of calcium salt (s) in the form of individual crystallites or in the form of particles, comprising a plurality of said crystallites, a single crystallite having a thickness in the range 2 to 50 nm and a length in the range of 10 to 150 nm;
• b) 2.0 to 25.0% by weight of precipitated silica (s) having a particle size d50 (laser diffraction according to ISO 133-20-1) <15 μm,

wherein the particles are rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped.

Mouth- and dentifrices as well as mouth and tooth cleaning agents in the sense oral and dental powders, oral and toothpastes, liquid mouthwashes, and toothpastes, mouth and tooth gels. Are preferably suitable Toothpastes and liquid Tooth cleaning agent. You can do this oral and dental care and cleaning products, e.g. in the form of Toothpastes, liquid Toothpastes, toothpowder, mouthwash or optionally also as gum, z. B. as chewing gum, present. Preferably, however, they are more or less flowable or plastic Toothpastes, as used for cleaning the teeth using a toothbrush become.

The Compositions of the invention have a remineralizing effect. About that in addition, it is sparingly soluble Calcium salt and in particular its composites in addition able, from those in the natural Saliva of man in oversaturated Concentrate concentrations of calcium and phosphate ions present. These Nucleation effect leads so for a structure of new tooth material (Neomineralisierung), in particular of the enamel and / or of the dentin, from the body's own Reservoirs. In particular, this achieves a closure of the dentinal tubules.

Particularly according to the invention preferred oral and dental care and cleaning products according to included on her weight - 0.01 to 0.09 wt .-%, preferably 0.02 to 0.08 wt .-%, particularly preferably 0.03 to 0.075 wt .-%, more preferably 0.04 to 0.07 wt .-% and in particular 0.05 to 0.065% by weight of calcium salt (s) in the form of individual crystallites or in the form of predominantly platelet-shaped particles, comprising a plurality of said crystallites, wherein a single Crystallite has a thickness in the range of 2 to 50 nm and a length in the range from 10 to 150 nm, preferably a thickness of 2 to 15 nm and a Length of 10 up to 50 nm; more preferably, a thickness of 3 to 7 nm and a length of 15 to 25 nm.

Further are oral and dental care and cleaning agents in which the or the calcium salt (s) in the form of individual crystallites or in the form of predominantly platelet-shaped particles, comprising a plurality of said crystallites, wherein a single Crystallite has a thickness in the range of 2 to 50 nm and a length in the range from 10 to 150 nm, is selected from the group hydroxyapatite, Fluorapatite and calcium fluoride.

The according to the invention as a further Component contained precipitated silicas are preferably thickening silicates. Especially preferred Leave precipitated silica describe themselves by further physical properties.

So preferably used in the context of the present invention Precipitated silicic acids one more narrower particle size d50. Here are mouthpieces according to the invention. and dentifrices and cleaners which are related on her weight - 2.5 to 15.0, preferably 3.5 to 12.5, particularly preferably 4.5 to 11.0 and in particular 5.0 to 9.5 wt .-% precipitated silica (s) with a particle size d50 (laser diffraction according to ISO 133-20-1) between> 1 and <12 μm, preferably between> 2 and <10 μm and in particular between> 3 and <8 microns included.

Preferably be in the inventive compositions exclusively Precipitated silicas used, which satisfy the above criteria. Oral and Dental Care and cleaners except the particular precipitated silicas no other silicas contained, are preferred according to the invention.

Regardless of whether further precipitated silicas are used or not, the silicas used are preferably characterized by a specific surface area. In this case, oral and dental care and cleaning agents according to the invention have proved to be particularly suitable in which all precipitated silicas contained in the composition have a specific surface area (N ₂ , measured according to ISO 5794-1, Annex D)> 60 m ² / g, preferably> 100 m ² / g, more preferably> 150 m ² / g, particularly preferably> 175 m ² / g and in particular> 185 m ² / g.

Appropriate Information can also be added to the absorption capacity of the invention used Make precipitated silicas. Here, mouthpieces according to the invention have and dental care and cleaning agents have proven to be particularly suitable in which all precipitated silicic acids contained in the middle of a dibutyl phthalate absorption (DBP absorption, measured according to DIN 53601)> 150 g / 100 g, preferably> 200 g / 100 g, especially preferably> 235 g / 100g and in particular> 250 g / 100g.

Appropriate Information can also be given to the density of the invention used Make precipitated silicas. Here, mouthpieces according to the invention have and dental care and cleaning agents have proven to be particularly suitable in which all precipitated silicas contained in the middle of a Tamping density (not sieved, measured according to ISO 787-11) between> 50 and <400 g / l, preferably between> 75 and <350 g / l, especially preferably between> 80 and <120 g / l and in particular between> 85 and <100 g / l.

Next the precipitated silicas mentioned, which are predominantly serve to adjust the rheological properties, the agent according to the invention, in particular the toothpastes or liquid toothpastes preferably one or more polishes, usually contained in an amount of 5 to 50 wt .-%. If silicas or even precipitated silicas as Polishing agents are used, these flow only in calculation the inventive 2.0 up to 25.0% by weight of precipitated silica (s), if their particle size d50 (laser diffraction according to ISO 133-20-1) <15 μm.

When Polishing agents are in principle all known for toothpastes friction body, in particular those that do not contain calcium ions. Preferably suitable polishing agent components are therefore silicas, aluminum hydroxide, Alumina, sodium aluminosilicates, organic polymers or Mixtures of such friction bodies.

calcium-containing Polishing components such as e.g. Chalk, calcium pyrophosphate, dicalcium phosphate dihydrate can but be contained in amounts up to 5 wt .-%.

Of the Total content of polishing agents is preferably in the range of 5-50% by weight of the dentifrice.

Especially preferred are toothpastes and liquid Dentifrices containing silicic acids as a polishing agent. Suitable silicic acids are e.g. silica gels, hydrogels and precipitated silicas. Gel silicas are by reaction of sodium silicate solutions with strong, aqueous mineral acids Formation of a hydrogel, aging to hydrogel, washing and drying produced. Drying takes place under mild conditions on water content of 15 to 35 wt .-%, so are the so-called hydrogels receive. By drying to water contents below 15% by weight There is an irreversible shrinkage of the previously loose structure of the hydrogel to the dense structure of the so-called xerogel.

When another polish component can also be used e.g. Alumina in the form of weakly calcined alumina and alumina in an amount of about 1-5% by weight be included. Such a suitable alumina is under the Trade name "Poliertonerde P10 finest "(Giulini Chemistry) available.

When Polishing agents are also suitable for all known for toothpastes friction body as z. B. sodium aluminum silicates such. As zeolite A, organic polymers such as As polymethacrylate or mixtures of these and the above called friction body.

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

The mouthpiece according to and dentifrices and cleaners may additionally contain carboxymethylcellulose contain; this is in terms of rheological properties the means desired, In addition, an effect enhancement the calcium salt (s) in the form of individual crystallites or in the form of particles comprising a plurality of said crystallites, wherein a single crystallite has a thickness in the range of 2 to 50 nm and a length in the range of 10 to 150 nm, found when the compositions of the invention Carboxymethylcellulose included.

The carboxymethyl cellulose (CMC for short) is generally the sodium salt of the glycolic acid ether of cellulose. CMC can be described by the following formula in which the radicals R are selected from H, CH ₂ -COONa:

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

preferred mouthpiece according to the invention and dental care and cleaning products are characterized that they - related on her weight - 0.25 to 2.0 wt .-%, preferably 0.5 to 1.75 wt .-% and in particular Containing 0.75 to 1.5 wt .-% carboxymethycellulose (CMC).

Especially preferred is the use of CMC grades with certain rheological Properties. Here are mouth and Zahnpflege- and inventive cleaning agents containing a Na-CMC are particularly preferred, their 2% by weight solution in water a viscosity (after 7 days of storage at 20 ° C, measured at 20 ° C and an air pressure of 1 bar, Brookfield Viscometer RVDV II +, with helipath at a shear rate of 4 rpm) of 200 up to 1000 mPas, preferably from 300 to 800 mPas and in particular from 350 to 700 mPas.

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

Particularly according to the invention preferred oral and dental care and cleaning agents are characterized that in addition to the calcium salt (s) in the form of individual crystallites or in the form of predominantly platelet-shaped particles, comprising a plurality of said crystallites, wherein a single Crystallite has a thickness in the range of 2 to 50 nm and a length in the range from 10 to 150 nm, further calcium salt (s), preferably Calcium glycerophosphate, included.

• a) 0,01 bis 15 Gew.-%, vorzugsweise 0,1 bis 10 Gew.-% und insbesondere 0,5 bis 7,5 Gew.-% mindestens eines wasserlöslichen Tensids und/oder mindestens eines wasserlöslichen polymeren Schutzkolloids;
• b) 0,01 bis 15 Gew.-%, vorzugsweise 0,1 bis 10 Gew.-% und insbesondere 0,5 bis 7,5 Gew.-% des bzw. der Calciumsalze(s) in Form von einzelnen Kristalliten oder in Form von vorwiegend plättchenförmigen Partikeln, umfassend eine Mehrzahl besagter Kristallite, wobei ein einzelner Kristallit eine Dicke im Bereich von 2 bis 50 nm und eine Länge im Bereich von 10 bis 150 nm aufweist,

enthält.The oral and dental care and cleaning agents according to the invention may contain the nanoparticulate calcium salts in different forms. Preferably, the calcium salts are stabilized against agglomeration. In a first preferred embodiment of the present invention, the oral and dental care compositions of the invention contain the calcium salt (s) in the form of single crystallites or predominantly platelet-shaped particles comprising a plurality of said crystallites, wherein a single crystallite has a thickness in the Range of 2 to 50 nm and a length in the range of 10 to 150 nm, in the form of a suspension, which - based on the weight of the suspension -

• a) 0.01 to 15 wt .-%, preferably 0.1 to 10 wt .-% and in particular 0.5 to 7.5 wt .-% of at least one water-soluble surfactant and / or at least one water-soluble polymeric protective colloid;
• b) 0.01 to 15 wt .-%, preferably 0.1 to 10 wt .-% and in particular 0.5 to 7.5 wt .-% of the or the calcium salts (s) in the form of individual crystallites or in A form of predominantly platelet-shaped particles comprising a plurality of said crystallites, wherein a single crystallite has a thickness in the range of 2 to 50 nm and a length in the range of 10 to 150 nm,

contains.

In this embodiment is as liquid Medium in which the calcium salts may be dispersed is primarily suitable for water. Those derived from an aqueous suspension, e.g. by However, filtration or centrifugation of isolated calcium salt particles can be done be redispersed and deliver in organic solvents also suspensions of the primary particles in the nanometer range, which hardly tend to agglomerate. Suitable organic liquid media are e.g. water-soluble, lower alcohols and glycols, polyethylene glycols, glycerol or their mixtures with each other or with water.

Primary particles are understood as meaning the crystallites, ie the individual crystals of the stated calcium salts. The particle diameter is to be understood here as the diameter of the particles in the direction of their greatest length expansion. Thickness here is to be understood as the smallest diameter of the rods, under length her biggest. The mean particle diameter is to be understood as a value which is averaged over the total amount of the composite. The determination of the particle diameter can be determined by methods familiar to the person skilled in the art, in particular by the evaluation of the broadening of the reflections observed during X-ray diffraction. Preferably, 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.

Surprisingly has succeeded in including calcium salts or composite materials these provide a predominantly platelike structure of the hard water-soluble Have calcium salt.

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 platelet and / or rod-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 composite value to understand average value. He is lying according to the invention 1000 nm, preferably below 300 nm.

According to one another preferred embodiment The invention relates to the calcium salts used according to the invention and / or the composite materials comprising these with a middle one Particle diameter of the particles in the range of below 1000 nm, preferably below 300 nm.

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 typically imaged at the points of overlap with greater blackening as non-overlapping Particle. The specified lengths, Widths and heights are preferably not overlapping per se Particles of the sample determined (measured).

The height of 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 (high density) and appear more like a rod. These platelet-shaped particles which are perpendicular to the image plane can be referred to as indeed be identified standing perpendicular to the image plane, when at a tilting of the image plane a broadening of the dimension (at least in a spatial direction) and show a decrease in the density of the image.

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

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

Prefers the width of these particles is in the range between 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 0.5 × 10 ^-15 m ² to 50 × 10 ^-15 m ² , particularly preferably 1.0 × 10 ^-15 m ² to 30 × 10 ^-15 m ² , very particularly preferably 1.5 × 10 ^-15 m ² to 15 × 10 ^-15 m ^2, for example 2 × 10 ^-15 m ² , As area of the particles, the area of the plane, spanned by the length and the vertical width, is determined according to the usual geometric calculation methods.

The in this preferred embodiment Contain the suspensions used in the present invention (based on the weight of the suspension) 0.01 to 15 wt .-%, preferably 0.1 to 10 wt .-% and in particular 0.5 to 7.5 wt .-% of or Calcium salts (s) in the form of predominantly platelet-shaped primary particles having a thickness in the Range of 2 to 50 nm and a length in the range of 10 to 150 nm. As another ingredient of the suspension (based on the Suspension) 0.01 to 15 wt .-%, preferably 0.1 to 10 wt .-% and in particular 0.5 to 7.5 wt .-% of at least one water-soluble Surfactant and / or at least one water-soluble polymeric protective colloid contain.

Under The term surfactants are surface-active substances, the on surfaces and interfaces Form adsorption or in volume phases to micellar colloids or lyotropic mesophases, understood. One differentiates Anionic surfactant consisting of one hydrophobic residue and one negative charged hydrophilic head group, amphoteric surfactants containing both carry a negative as well as a compensating positive charge, cationic surfactants which, in addition to a hydrophobic radical, are positively charged have hydrophilic group, and nonionic surfactants, which no Charges but strong dipole moments and strong in aqueous solution are hydrated.

• – lineare und verzweigte Fettsäuren mit 8 bis 30 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_X-CH₂-COOH, in der R eine lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Acyltauride mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 24 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 24 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 8 bis 24 C-Atomen,
• – lineare Alpha-Olefinsulfonate mit 8 bis 24 C-Atomen,
• – Alpha-Sulfofettsäuremethylester von Fettsäuren mit 8 bis 30 C-Atomen,
• – Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-OSO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 12 ist,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether
• – Sulfonate ungesättigter Fettsäuren mit 8 bis 24 C-Atomen und 1 bis 6 Doppelbindungen
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2-15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen,
• – Alkyl- und/oder Alkenyletherphosphate der Formel (E1-I), R¹(OCH₂CH₂)_n-O-P(O)(OX)-OR² (E1-I)in der R¹ bevorzugt für einen aliphatischen Kohlenwasserstoffrest mit 8 bis 30 Kohlenstoffatomen, R² für Wasserstoff, einen Rest (CH₂CH₂O)_nR² oder X, n für Zahlen von 1 bis 10 und X für Wasserstoff, ein Alkali- oder Erdalkalimetall oder NR³R⁴R⁵R⁶, mit R³ bis R⁶ unabhängig voneinander stehend für Wasserstoff oder einen C₁ bis C₄-Kohlenwasserstoffrest, steht,
• – sulfatierte Fettsäurealkylenglykolester der Formel (E1-II) R⁷CO(AlkO)_nSO₃M (E1-II) in der R⁷CO- für einen linearen oder verzweigten, aliphatischen, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 C-Atomen, Alk für CH₂CH₂, CHCH₃CH₂ und/oder CH₂CHCH₃, n für Zahlen von 0,5 bis 5 und M für ein Kation steht,
• – Monoglyceridsulfate und Monoglyceridethersulfate der Formel (E1-III)
  
  in der R⁸CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x, y und z in Summe für 0 oder für Zahlen von 1 bis 30, vorzugsweise 2 bis 10, und X für ein Alkali- oder Erdalkalimetall steht. Typische Beispiele für im Sinne der Erfindung geeignete Monoglycerid(ether)sulfate sind die Umsetzungsprodukte von Laurinsäuremonoglycerid, Kokosfettsäuremonoglycerid, Palmitinsäuremonoglycerid, Stearinsäuremonoglycerid, Ölsäuremonoglycerid und Talgfettsäuremonoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze. Vorzugsweise werden Monoglyceridsulfate der Formel (E1-III) eingesetzt, in der R⁸CO für einen linearen Acylrest mit 8 bis 18 Kohlenstoffatomen steht,,
• – Amidethercarbonsäuren,
• – Kondensationsprodukte aus C₈-C₃₀-Fettalkoholen mit Proteinhydrolysaten und/oder Aminosäuren und deren Derivaten, welche dem Fachmann als Eiweissfettsäurekondensate bekannt sind, wie beispielsweise die Lamepon^®-Typen, Gluadin^®-Typen, Hostapon^® KCG oder die Amisoft^®-Typen.

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

• - linear and branched fatty acids with 8 to 30 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _X -CH ₂ -COOH, in which R is a linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 8 to 24 C atoms in the acyl group,
• Acyltaurides having 8 to 24 carbon atoms in the acyl group,
• Acyl isethionates having 8 to 24 C atoms in the acyl group,
• Sulfosuccinic acid mono- and dialkyl esters having 8 to 24 C atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• - linear alkanesulfonates having 8 to 24 carbon atoms,
• - linear alpha-olefin sulfonates having 8 to 24 carbon atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 C atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -OSO ₃ H, in which R is a preferably linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 12,
• - Sulfated Hydroxyalkylpolyethylen- and / or Hydroxyalkylenpropylenglykolether
• - Sulfonates of unsaturated fatty acids having 8 to 24 carbon atoms and 1 to 6 double bonds
• Esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms,
• Alkyl and / or alkenyl ether phosphates of the formula (E1-I), R ¹ (OCH ₂ CH ₂ ) _n -OP (O) (OX) -OR ² (E1-I) in the R ^{1 is} preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R ^{2 is} hydrogen, a radical (CH ₂ CH ₂ O) _n R ² or X, n is from 1 to 10 and X is hydrogen, an alkali metal radical or alkaline earth metal or NR ³ R ⁴ R ⁵ R ⁶ , where R ³ to R ⁶ independently of one another represent hydrogen or a C ₁ to C ₄ -hydrocarbon radical,
• Sulfated fatty acid alkylene glycol esters of the formula (E1-II) R ⁷ CO (AlkO) _n SO ₃ M (E1-II) in the R ⁷ CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, Alk for CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , n for numbers from 0.5 to 5 and M is a cation,
• Monoglyceride sulfates and monoglyceride ether sulfates of the formula (E1-III)
  
  in which R ⁸ CO is a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z are in total 0 or numbers of 1 to 30, preferably 2 to 10, and X is an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. It is preferred to use monoglyceride sulfates of the formula (E1-III) in which R ⁸ CO is a linear acyl radical having 8 to 18 carbon atoms,
• - amide ether carboxylic acids,
• - condensation products of C ₈ -C ₃₀ fatty alcohols with protein hydrolysates and / or amino acids and their derivatives, which are known to the skilled person as protein fatty acid condensates, such as Lamepon ^® grades, Gluadin ^® grades, Hostapon ^® KCG or Amisoft ^® grades ,

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

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

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

• – Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – mit einem Methyl- oder C₂-C₆-Alkylrest endgruppenverschlossene Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe, wie beispielsweise die unter den Verkaufsbezeichnungen Dehydol^® LS, Dehydol^® LT (Cognis) erhältlichen Typen,
• – C₁₂-C₃₀-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• – Polyolfettsäureester, wie beispielsweise das Handelsprodukt Hydagen^® HSP (Cognis) oder Sovermol-Typen (Cognis),
• – alkoxilierte Triglyceride,
• – alkoxilierte Fettsäurealkylester der Formel (E4-I) R¹CO-(OCH₂CHR²)_wOR³ (E4-I)in der R¹CO für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder Methyl, R³ für lineare oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen und w für Zahlen von 1 bis 20 steht,
• – Aminoxide,
• – Hydroxymischether,
• – Sorbitanfettsäureester und Anlagerungeprodukte von Ethylenoxid an Sorbitanfettsäureester wie beispielsweise die Polysorbate,
• – Zuckerfettsäureester und Anlagerungsprodukte von Ethylenoxid an Zuckerfettsäureester,
• – Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide und Fettamine,
• – Zuckertenside vom Typ der Alkyl- und Alkenyloligoglykoside gemäß Formel (E4-II), R⁴O-[G]_p (E4-II)in der R⁴ für einen Alkyl- oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden. Die Alkyl- und Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise von Glucose, ableiten. Die bevorzugten Alkyl- und/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Die Indexzahl p in der allgemeinen Formel (E4-II) gibt den Oligomerisierungsgrad (DP), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p im einzelnen Molekül stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt. Der Alkyl- bzw. Alkenylrest R⁴ kann sich von primären Alkoholen mit 4 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Bevorzugt sind Alkyloligoglucoside der Kettenlänge C₈-C₁₀ (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C₈-C₁₈-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C₁₂-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C_9/11-Oxoalkohole (DP = 1 bis 3). Der Alkyl- bzw. Alkenylrest R¹⁵ kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C_12/14-Kokosalkohol mit einem DP von 1 bis 3.
• – Zuckertenside vom Typ der Fettsäure-N-alkylpolyhydroxyalkylamide, ein nichtionisches Tensid der Formel (E4-III), R⁵CO-NR⁶-[Z] (E4-III)in der R⁵CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R⁶ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Fettsäure-N-alkylpolyhydroxyalkylamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden. Vorzugsweise leiten sich die Fettsäure-N-alkylpolyhydroxyalkylamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab. Die bevorzugten Fettsäure-N-alkylpolyhydroxyalkylamide stellen daher Fettsäure-N-alkylglucamide dar, wie sie durch die Formel (E4-IV) wiedergegeben werden: R⁷CO-NR⁸-CH₂-(CHOH)₄-CH₂OH (E4-IV)Vorzugsweise werden als Fettsäure-N-alkylpolyhydroxyalkylamide Glucamide der Formel (E4-IV) eingesetzt, in der R⁸ für Wasserstoff oder eine Alkylgruppe steht und R⁷CO für den Acylrest der Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Arachinsäure, Gadoleinsäure, Behensäure oder Erucasäure bzw. derer technischer Mischungen steht. Besonders bevorzugt sind Fettsäure-N-alkylglucamide der Formel (E4-IV), die durch reduktive Aminierung von Glucose mit Methylamin und anschließende Acylierung mit Laurinsäure oder C12/14-Kokosfettsäure bzw. einem entsprechenden Derivat erhalten werden. Weiterhin können sich die Polyhydroxyalkylamide auch von Maltose und Palatinose ableiten.

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

• - Addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• - with a methyl or C ₂ -C ₆ alkyl radical end-capped addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 C atoms and onto alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as those available under the trade names Dehydol ^® LS, LT Dehydol ^® types (Cognis),
• C ₁₂ -C ₃₀ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,
• Adducts of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,
• - polyol, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol types (Cognis),
• - alkoxylated triglycerides,
• Alkoxylated fatty acid alkyl esters of the formula (E4-I) R ¹ CO- (OCH ₂ CHR ² ) _w OR ³ (E4-I) in which R ¹ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ² is hydrogen or methyl, R ³ is linear or branched alkyl radicals having 1 to 4 carbon atoms, and w is a number from 1 to 20 stands,
• - amine oxides,
• - hydroxymix ether,
• Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,
• Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters,
• Adducts of ethylene oxide with fatty acid alkanolamides and fatty amines,
• Sugar surfactants of the alkyl and alkenyl oligoglycoside type of formula (E4-II), R ⁴ O- [G] _p (E4-II) in which R ^{4 is} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. The alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (E4-II) indicates the degree of oligomerization (DP), ie the distribution of mono- and While p in the single molecule must always be an integer, and in particular can assume the values p = 1 to 6, the value p for a given alkyloligoglycoside is an arithmetically determined arithmetic value, .alpha usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R ⁴ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl oligoglucosides of the chain length C ₈ -C ₁₀ (DP = 1 to 3) which are obtained as a feedstock in the distillative separation of technical C ₈ -C ₁₈ coconut fatty alcohol and in a proportion of less than 6% by weight C ₁₂ - Alcohol may be contaminated as well as alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹⁵ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C _12/14 coconut alcohol having a DP of 1 to 3.
• Sugar surfactants of the fatty acid N-alkyl polyhydroxyalkylamide type, a nonionic surfactant of the formula (E4-III), R ⁵ CO-NR ⁶ - [Z] (E4-III) R ^{5 is} CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{6 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands. The fatty acid N-alkyl polyhydroxyalkylamides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (E4-IV): R ⁷ CO-NR ⁸ -CH ₂ - (CHOH) ₄ -CH ₂ OH (E4-IV) The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (E4-IV) in which R ^{8 is} hydrogen or an alkyl group and R ^{7 is} CO for the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Particular preference is given to fatty acid N-alkylglucamides of the formula (E4-IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C 12/14 coconut fatty acid or a corresponding derivative. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

When preferred nonionic surfactants are the alkylene oxide addition products to saturated linear Fatty alcohols and fatty acids with in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations with excellent properties will also be obtained when they are fatty acid esters as nonionic surfactants of ethoxylated glycerol.

These Connections are identified by the following parameters. The alkyl radical R contains 6 to 22 carbon atoms and can be both linear and branched be. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such Alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-Lauryl, 1-myristyl. When using so-called "oxo-alcohols" as starting materials predominate Compounds with an odd number of carbon atoms in the alkyl chain.

Farther Very particularly preferred nonionic surfactants are the sugar surfactants. these can in the invention used Agents preferably in amounts of 0.1-20 wt .-%, based on the total Means be included. Amounts of 0.5-15% by weight are preferred and most preferred are amounts of 0.5-7.5 wt.%.

at it may be the compounds with alkyl groups used as surfactant each are uniform substances. It is, however, in usually preferred in the preparation of these substances by native to go out with vegetable or animal raw materials, so that one Substance mixtures with different, from the respective raw material dependent alkyl chain lengths receives.

at the surfactants, the adducts of ethylene and / or propylene oxide represent fatty alcohols or derivatives of these addition products, can both products with a "normal" homolog distribution as well as those with a narrow homolog distribution become. Under "normal" homolog distribution are understood to mean mixtures of homologs which are used in the Reaction of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. Narrowed homolog distributions are obtained when, for example Hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with narrow homolog distribution may be preferred.

Usable according to the invention are cationic surfactants of the quaternary ammonium type, the Esterquats and amidoamines. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as Alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, Lauryldimethylbenzylammoniumchlorid and tricetylmethylammonium chloride, as well as those under the INCI names Quaternium 27 and Quaternium-83 known imidazolium compounds. The long alkyl chains The above-mentioned surfactants preferably have 10 to 18 carbon atoms on.

According to the invention, preference is given to using QAV with behenyl radicals, in particular the substances known as behentrimonium chloride or bromide (docosanyltrimethylammonium chloride or bromide). Other preferred QAV's have at least two behenyl residues, with QAV being particularly preferred, which are two behenyl residues on an imidazolinium backbone. Commercially available, these substances, for example, under the names Genamin ^® KDMP (Clariant) and Crodazosoft ^® DBQ (Crodauza) are.

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

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

When water-soluble polymeric protective colloids are understood to be high molecular weight compounds, to the surface are adsorbed to the nanoparticles and modify them so that they are prevented from coagulation and agglomeration. suitable polymeric protective colloids are e.g. natural water-soluble polymers such as. Gelatin, casein, albumin, starch, vegetable gums and water-soluble derivatives of water-insoluble polymeric natural products such as e.g. Cellulose ethers (methylcellulose, Hydroxyethylcellulose, carboxymethylcellulose), hydroxyethyl starch or Hydroxypropyl guar.

synthetic water-soluble Polymers useful as protective colloids are e.g. Polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, polyaspartic and other.

In preferred compositions of this embodiment of the invention, the Sus pension one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and derivatives thereof, in particular MC, HEC, HPC, HPMC and / or CMC, and / or copolymers and mixtures thereof.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten.In the context of the present invention, polyvinyl alcohols are particularly preferred as water-soluble polymers. "Polyvinyl alcohols" (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure

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

contain.

Commercially available polyvinyl alcohols, the as white-yellowish Powders or granules with degrees of polymerization in the range of approx. 100 to 2500 (molecular weights of about 4000 to 100,000 g / mol) offered have hydrolysis degrees of 98-99 and 87-89 mol%, respectively So still a residual content of acetyl groups. To be characterized the polyvinyl alcohols from the manufacturers by specifying the Degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

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

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

Of the Degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680 and especially between about 260 to about 1500th

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

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

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

die durch radikalische Polymerisation von 1-Vinylpyrrolidon nach Verfahren der Lösungs- oder Suspensionspolymerisation unter Einsatz von Radikalbildnern (Peroxide, Azo-Verbindungen) als Initiatoren hergestellt werden. Die ionische Polymerisation des Monomeren liefert nur Produkte mit niedrigen Molmassen. Handelsübliche Polyvinylpyrrolidone haben Molmassen im Bereich von ca. 2500-750000 g/mol, die über die Angabe der K-Werte charakterisiert werden und – K-Wertabhängig – Glasübergangstemperaturen von 130-175° besitzen.A further preferred group of water-soluble polymers which can serve according to the invention as a protective colloid for the suspension are the polyvinylpyrrolidones. These are marketed under the name Luviskol ^® (BASF). Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula (I)

which are prepared by free-radical polymerization of 1-vinylpyrrolidone by the method of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer provides only low molecular weight products. Commercially available polyvinylpyrrolidones have molar masses in the range of about 2500-750000 g / mol, which are characterized by the specification of the K values and - depending on K value - have glass transition temperatures of 130-175 °.

Also suitable are copolymers of vinylpyrrolidone with other monomers, in particular vinylpyrrolidone / Vinylester copolymers, such as for example, under the trade name Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred non-ionic polymers.

als charakteristischem Grundbaustein der Makromoleküle. Von diesen haben die Vinylacetat-Polymere (R = CH₃) mit Polyvinylacetaten als mit Abstand wichtigsten Vertretern die größte technische Bedeutung.The vinyl ester polymers are vinyl ester-accessible polymers having the moiety of the formula (II)

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

The Polymerization of the vinyl ester takes place radically according to different Process (solution polymerization, Suspension polymerization, emulsion polymerization, bulk polymerization.). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (I) and (II)

Further suitable water-soluble polymers are the polyethylene glycols (polyethylene oxides), which are referred to as PEG for short. PEG are polymers of ethylene glycol which are of the general formula (III) H- (O-CH ₂ -CH ₂ ) _n OH (III) satisfy, where n can take values between 5 and> 100,000.

PEGs are technically prepared by anionic ring-opening polymerization of ethylene oxide (oxirane) usually in the presence of small amounts of water. They have depending on the reaction Molar masses in the range of about 200-5 000 000 g / mol, corresponding degrees of polymerization from about 5 to> 100 000th

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

Further as water-soluble Nüllmaterial According to the invention, gelatin is also suitable, these preferably being used together with other polymers becomes. Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), the primarily by hydrolysis of the skin and bones of animals Collagen is obtained under acidic or alkaline conditions. The amino acid composition The gelatin largely corresponds to that of the collagen from which they are made was obtained and varies depending on its provenance. The use of gelatin as the water-soluble coating material is in particular in pharmacy in the form of hard or soft gelatin capsules extremely far common. In the form of slides, gelatin is because of their compared to the above-mentioned polymers of high price only small Use.

• – Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal^® und Benecel^® (AQUALON) vertrieben werden. Celluloseether lassen sich durch die allgemeine Formel (IV) beschreiben,
  
  in R für H oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in Formel (III) für -CH₂CH₂CH₂-OH oder -CH₂CH₂-OH. Celluloseether werden technisch durch Veretherung von Alkalicellulose (z.B. mit Ethylenoxid) hergestellt. Celluloseether werden charakterisiert über den durchschnittlichen Substitutionsgrad DS bzw. den molaren Substitutionsgrad MS, die angeben, wie viele Hydroxy-Gruppen einer Anhydroglucose-Einheit der Cellulose mit dem Veretherungsreagens reagiert haben bzw. wie viel mol des Veretherungsreagens im Durchschnitt an eine Anhydroglucose-Einheit angelagert wurden. Hydroxyethylcellulosen sind ab einem DS von ca. 0,6 bzw. einem MS von ca. 1 wasserlöslich. Handelsübliche Hydroxyethyl- bzw. Hydroxypropylcellulosen haben Substitutionsgrade im Bereich von 0,85-1,35 (DS) bzw. 1,5-3 (MS). Hydroxyethyl- und -propylcellulosen werden als gelblich-weiße, geruch- und geschmacklose Pulver in stark unterschiedlichen Polymerisationsgraden vermarktet. Hydroxyethyl- und -propylcellulosen sind in kaltem und heißem Wasser sowie in einigen (wasserhaltigen) organischen Lösungsmitteln löslich, in den meisten (wasserfreien) organischen Lösungsmitteln dagegen unlöslich; ihre wäßrigen Lösungen sind relativ unempfindlich gegenüber Änderungen des pH-Werts oder Elektrolyt-Zusatz.

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

• - cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methylhydroxypropyl cellulose, as for example under the trademark Culminal® ^® and Benecel ^® (AQUALON). Cellulose ethers can be described by the general formula (IV)
  
  R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula (III) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose reacted with the etherifying reagent or how many moles of the etherifying agent were attached on average to an anhydroglucose unit , Hydroxyethylcelluloses are water-soluble from a DS of about 0.6 or an MS of about 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS), respectively. Hydroxyethyl and propylcelluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propylcelluloses are soluble in cold and hot water as well as in some (hydrous) organic solvents but insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

preferred inventive agent are characterized in that the suspension hydroxypropylmethylcellulose (HPMC), one degree of substitution (average number of methoxy groups per anhydroglucose unit of cellulose) of 1.0 to 2.0, preferably from 1.4 to 1.9, and a molar substitution (average Number of hydroxypropoxyl groups per anhydroglucose unit of the Cellulose) of from 0.1 to 0.3, preferably from 0.15 to 0.25.

Further polymers which are suitable according to the invention are water-soluble amphopolymers. Amphoteric polymers, ie polymers which contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers which contain quaternary ammonium groups in the molecule. COO ^- - or -SO ₃ ^- groups, and summarized those polymers containing -COOH or SO ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is the acrylic resin commercially available as Amphomer ^® is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (for example acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and optionally further ionic or nonionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be seen. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropy Ltrimonium chloride, as they are commercially available under the name Merquat ^® 2001 N, according to the invention are particularly preferred ampho polymers. Other suitable amphoteric polymers are for example sold under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) available octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

• – Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen Resyn^® (NATIONAL STARCH), Luviset^® (BASF) und Gafset^® (GAF) im Handel sind. Diese Polymere weisen neben Monomereinheiten der vorstehend genannten Formel (II) auch Monomereinheiten der allgemeinen Formel (V) auf: [-CH(CH₃)-CH(COOH)-]_n (V)
• – Vinylpyrrolidon/Vinylacrylat-Copolymere, erhältlich beispielsweise unter dem Warenzeichen Luviflex^® (BASF). Ein bevorzugtes Polymer ist das unter der Bezeichnung Luviflex^® VBM-35 (BASF) erhältliche Vinylpyrrolidon/Acrylat-Terpolymere.
• – Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere, die beispielsweise unter der Bezeichnung Ultrahold^® strong (BASF) vertrieben werden.
• – Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen Solche gepfropften Polymere von Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch mit anderen copolymerisierbaren Verbindungen auf Polyalkylenglycolen werden durch Polymerisation in der Hitze in homogener Phase dadurch erhalten, dass man die Polyalkylenglycole in die Monomeren der Vinylester, Ester von Acrylsäure oder Methacrylsäure, in Gegenwart von Radikalbildner einrührt. Als geeignete Vinylester haben sich beispielsweise Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylbenzoat und als Ester von Acrylsäure oder Methacrylsäure diejenigen, die mit aliphatischen Alkoholen mit niedrigem Molekulargewicht, also insbesondere Ethanol, Propanol, Isopropanol, 1-Butanol, 2-Butanol, 2-Methy-1-Propanol, 2-Methyl-2-Propanol, 1-Pentanol, 2-Pentanol, 3-Pentanol, 2,2-Dimethyl-1-Propanol, 3-Methyl-1-butanol; 3-Methyl-2-butanol, 2-Methyl-2-butanol, 2-Methyl-1-Butanol, 1-Hexanol, erhältlich sind, bewährt. Polypropylenglycole (Kurzzeichen PPG) sind Polymere des Propylenglycols, die der allgemeinen Formel VI
  
  genügen, wobei n Werte zwischen 1 (Propylenglycol) und mehreren tausend annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d.h. die Vertreter mit n = 2, 3 und 4 in Formel VI. Insbesondere können die auf Polyethylenglycole gepfropften Vinylacetatcopolymeren und die auf Polyethylenglycole gepfropften Polymeren von Vinylacetat und Crotonsäure eingesetzt werden.
• – gepropfte und vernetzte Copolymere aus der Copolymerisation von i) mindesten einem Monomeren vom nicht-ionischen Typ, ii) mindestens einem Monomeren vom ionischen Typ, iii) von Polyethylenglycol und iv) einem Vernetzter Das verwendete Polyethylenglycol weist ein Molkeulargewicht zwischen 200 und mehreren Millionen, vorzugsweise zwischen 300 und 30.000, auf. Die nicht-ionischen Monomerer können von sehr unterschiedlichem Typ sein und unter diesen sind folgende bevorzugt: Vinylacetat, Vinylstearat, Vinyllaurat, Vinylpropionat, Allylstearat, Allyllaurat, Diethylmaleat, Allylacetat, Methylmethacrylat, Cetylvinylether, Stearylvinylether und 1-Hexen. Die nicht-ionischen Monomeren können gleichermaßen von sehr unterschiedlichen Typen sein, wobei unter diesen besonders bevorzugt Crotonsäure, Allyloxyessigsäure, Vinylessigsäure, Maleinsäure, Acrylsäure und Methacrylsäure in den Pfropfpolameren enthalten sind. Als Vernetzer werden vorzugsweise Ethylenglycoldimethacrylat, Diallylphthalat, ortho-, meta- und para-Divinylbenzol, Tetraallyloxyethan und Polyallylsaccharosen mit 2 bis 5 Allylgruppen pro Molekül Saccharin. Die vorstehend beschriebenen gepfropften und vernetzten Copoymere werden vorzugsweise gebildet aus: i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ, ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ, iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglycol und iv) 0,1 bis 8 Gew.-% eines Vernetzers, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.
• – durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltene Copolymere: i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren, ii) ungesättigte Carbonsäuren, iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols Unter kurzkettigen Carbonsäuren bzw. Alkoholen sind dabei solche mit 1 bis 8 Kohlenstoffatomen zu verstehen, wobei die Kohlenstoffketten dieser Verbindungen gegebenenfalls durch zweibindige Heterogruppen wie -O-, -NH-, -S_unterbrochen sein können.
• – Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester Diese Terpolymere enthalten Monomereinheiten der allgemeinen Formeln (II) und (IV) (siehe oben) sowie Monomereinheiten aus einem oder mehreren Allyl- oder Methallyestern der Formel VII:
  
  worin R³ für -H oder -CH₃, R² für -CH₃ oder -CH(CH₃)₂ und R¹ für -CH₃ oder einen gesättigten geradkettigen oder verzweigten C_1-6-Alkylrest steht und die Summe der Kohlenstoffatome in den Resten R¹ und R² vorzugsweise 7, 6, 5, 4, 3 oder 2 ist. Die vorstehend genannten Terpolymeren resultieren vorzugsweise aus der Copolymerisation von 7 bis 12 Gew.-% Crotonsäure, 65 bis 86 Gew.-%, vorzugsweise 71 bis 83 Gew.-% Vinylacetat und 8 bis 20 Gew.-%, vorzugsweise 10 bis 17 Gew.-% Allyl- oder Methallyletsre der Formel VII.
• – Tetra- und Pentapolymere aus i) Crotonsäure oder Allyloxyessigsäure ii) Vinylacetat oder Vinylpropionat iii) verzweigten Allyl- oder Methallylestern iv) Vinylethern, Vinylesterrn oder geradkettigen Allyl- oder Methallylestern
• – Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze
• – Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in alpha-Stellung verzweigten Monocarbonsäure.

Water-soluble anionic polymers suitable according to the invention include:

• - Vinyl acetate / crotonic acid copolymers, such as those under the names Resyn ^® (NATIONAL STARCH), Luviset ^® (BASF) and Gafset ^® (GAF) are commercially available. These polymers also have monomer units of the formula (II) above [-CH (CH ₃ ) -CH (COOH) -] _n (V)
• - vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is the VBM-35 (BASF) under the name Luviflex ^® available vinylpyrrolidone / acrylate terpolymers.
• - acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers sold for example under the name Ultrahold ^® strong (BASF).
• Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols. Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on polyalkylene glycols obtained by homogeneous polymerization in the heat by stirring the polyalkylene glycols in the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, in the presence of radical generator. Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and esters of acrylic acid or methacrylic acid, those with aliphatic alcohols of low molecular weight, ie in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are proven. Polypropylene glycols (abbreviated PPG) are polymers of propylene glycol which are of general formula VI
  
  satisfy, where n can assume values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycols, ie the representatives with n = 2, 3 and 4 in formula VI. In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.
• - grafted and crosslinked copolymers from the copolymerization of i) at least one nonionic-type monomer, ii) at least one ionic-type monomer, iii) polyethylene glycol, and iv) a crosslinker. The polyethylene glycol used has a molecular weight of between 200 and several millions. preferably between 300 and 30,000, on. The nonionic monomers may be of very different types and of these preferred are vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene. The non-ionic monomers may equally be of very different types, among which particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the grafting polymers. The crosslinking agents used are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose having 2 to 5 allyl groups per molecule of saccharin. The grafted and crosslinked copolymers described above are preferably formed from: i) from 5 to 85% by weight of at least one nonionic-type monomer, ii) from 3 to 80% by weight of at least one ionic-type monomer, iii) from 2 to 50% by weight, preferably from 5 to 30% by weight of polyethylene glycol, and iv) from 0.1 to 8% by weight of a crosslinker, the percentage of the crosslinker being determined by the ratio of the total weights of i), ii) and iii) is formed.
• Copolymers obtained by copolymerization of at least one monomer of each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, ii) unsaturated carboxylic acids, iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or Esters of the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 -alcohols short-chain carboxylic acids or alcohols are to be understood as meaning those having 1 to 8 carbon atoms, the carbon chains of these compounds being optionally substituted by divalent hetero groups such as O-, -NH-, -S_ may be interrupted.
• Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester These terpolymers contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyl esters of the formula VII:
  
  wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight or branched C _1-6 alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2. The abovementioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% allyl or Methallyletsre of formula VII.
• - tetra- and pentapolymers from i) crotonic acid or allyloxyacetic acid ii) vinyl acetate or vinyl propionate iii) branched allyl or methallyl esters iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
• Crotonic acid copolymers with one or more monomers from the group of ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts
• Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic alpha-branched monocarboxylic acid.

• – quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Verbindungen Celquat^® H 100, Celquat^® L 200 und Polymer JR^® 400 sind bevorzugte quaternierte Cellulose-Derivate.
• – Polysiloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning^® 929 Emulsion (enthaltend ein hydroxyl-amino-modifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil^®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; di-quaternäre Polydime-thylsiloxane, Quaternium-80),
• – Kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia^® Guar und Jaguar^® vertiebenen Produkte,
• – Polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^® 100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat^® 550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• – Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^® 734 und Gafquat^® 755 im Handel erhältlich.
• – Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat^® angeboten werden.
• – quaternierter Polyvinylalkohol

sowie die unter den Bezeichnungen

• – Polyquaternium 2,
• – Polyquaternium 17,
• – Polyquaternium 18 und
• – Polyquaternium 27

bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette. Die genannten Polymere sind dabei nach der sogenannten INCI-Nomenklatur bezeichnet, wobei sich detaillierte Angaben im CTFA International Cosmetic Ingredient Dictionary and Handbook, 5^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, finden, auf die hier ausdrücklich Bezug genommen wird.Further polymers which are preferably usable in the invention according to the invention are cationic polymers. Among the cationic polymers, the permanent cationic polymers are preferred. According to the invention, "permanently cationic" refers to those polymers which have a cationic group independently of the pH. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, such as those under the names Celquat ^® and Polymer JR ^® commercially available. The compounds Celquat ^® H 100, Celquat L 200 and Polymer JR ^{® ®} 400 are preferred quaternized cellulose derivatives.
• Quaternary group polysiloxanes, such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® quat 3270 and 3272 (manufacturer: Th Goldschmidt; di-quaternary Polydime-thylsiloxane, quaternium-80).,
• - cationic guar derivatives, in particular the vertiebenen under the trade names Cosmedia® ^® Guar and Jaguar ^® products,
• - Polymers Dimethyldiallylammoniumsalze and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminomethacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially available.
• - Vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, such as those offered under the name Luviquat ^® .
• - Quaternized polyvinyl alcohol

as well as those under the designations

• - Polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27

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

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

The Suspension has preferred oral and dental care and cleaning agents this embodiment preferably pH values between 5 and 7, more preferably between 5.5 and 6.9, in particular between 6 and 6.6, on. Preferred viscosities of Suspension are in the range of 500 to 20,000 mPas, so that preferred according to the invention Oral and dental care and detergents are characterized in that the suspension at 20 ° C a viscosity (after 7 days storage at 20 ° C, measured at 20 ° C and an air pressure of 1 bar, Brookfield Viscometer RVDV II +, with Helipath at a shear rate of 4 rpm) of 500 to 20,000 mPas, preferably from 750 to 15,000 mPas and in particular from 1000 to 10,000 mPas.

The can be used according to the invention Suspensions can by precipitation reactions from aqueous solutions more water-soluble Calcium salts and aqueous solutions water Phosphate or fluoride salts are prepared. The precipitation is in Presence of water-soluble Surfactants or water-soluble performed polymeric protective colloids. This can e.g. in the Done manner that the surfactants or protective colloids of the aqueous Phosphate or fluoride salt solution or the solution of the calcium salt are added before the reaction. Alternatively, you can the watery Calcium chloride solution simultaneously with the phosphate or fluoride salt solution in an aqueous one Surfactant or protective colloid solution be entered.

A Another variant of the method consists in that the precipitation a strongly acid solution of a water-soluble Calcium salt and a stoichiometric Amount of a water-soluble Phosphate salt with a pH below 3 by raising the pH with aqueous Alkali or ammonia in the presence of water-soluble surfactants or water-soluble performs polymeric protective colloids.

to Preparation of suspensions according to the invention in other liquid Media is conveniently used of aqueous according to the invention Suspensions, freed by filtration or centrifugation from the watery Phase, optionally dries the nanoparticles and redispersed they in organic solvents. This is a new addition of surfactants or protective colloids no longer necessary because the nanoparticles are used to inhibit the Agglomeration required amounts of stabilizers adsorbed on the surface contain. Fineness and stability of such suspensions is therefore with the aqueous Suspensions comparable. Another possibility is the aqueous Suspension with a higher boiling Solvent, e.g. with glycerin, to mix and remove the water by distillation. As organic liquid Medium is suitable, especially with regard to use in dentifrices, especially glycerin and its liquid mixtures with sorbitol and possibly with water.

alternative to the above embodiment or in addition can do this the mouthpiece according to the invention and dental care and cleanser the nanoparticulate calcium salts also in the form of composite materials.

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

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

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

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

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 primary particles the calcium salts to the framework Associated with the polymer component The proportion of polymer components in the composite materials from 0.1 to 80 wt .-%, preferably from 10 to 60 wt .-% and in particular from 30 to 50% by weight, based on the total weight of the composite materials.

According to one particularly preferred embodiment is the polymer component of, in the remineralizing product contained composite material 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/oder Carboxyl-Derivaten. Bevorzugt werden im Rahmen der vorliegenden Erfindung Polyelektrolyte eingesetzt, die zur Salzbildung mit zweiwertigen Kationen geeignete Gruppen tragen. Insbesondere eignen sich Carboxylat-Gruppen tragende Polymere.Suitable polyelectrolytes for the purposes of the invention are polyacids and polybases, it being possible for the polyelectrolytes to be biopolymers or else synthetic polymers. Thus, the inventive compositions contain, for example, one or more polyelectrolytes selected from

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

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

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

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

Another preferred embodiment of the invention is that polysaccharides are selected as the polymer component. In particular, these polysaccharides are selected from glucuronic acid and / or iduronic acid-containing polysaccharides. These are to be understood as meaning those polysaccharides which are composed inter alia of glucuronic acid, preferably D-glucuronic acid, and / or iduronic acid, in particular L-iduronic acid. A constituent of the carbohydrate skeleton is formed by glucuronic acid or iduronic acid. The iduronic acid isomeric to glucuronic acid has the other configuration at the C5 carbon atom of the ring. Preferred among glucuronic acid and / or iduronic acid-containing polysaccharides are those Polysaccharides to understand the glucuronic and / or iduronic in a molar ratio of 1:10 to 10: 1, in particular from 1: 5 to 5: 1, more preferably 1: 3 to 2: 1, based on the sum of the other Monosaccharide building blocks of polysaccharide, included. 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).

• a) 0,1 bis 80 Gew.-%, vorzugsweise 10 bis 60 Gew.-% und insbesondere 30 bis 50 Gew.-% Proteinkomponenten ausgewählt aus Proteinen, Proteinhydrolysaten und Proteinhydrolysat-Derivaten;
• b) 0,01 bis 80 Gew.-%, vorzugsweise 10 bis 75 Gew.-% und insbesondere 30 bis 65 Gew.-% des bzw. der Calciumsalze(s) in Form von einzelnen Kristalliten oder in Form von vorwiegend plättchenförmigen Partikeln, umfassend eine Mehrzahl besagter Kristallite, wobei ein einzelner Kristallit eine Dicke im Bereich von 2 bis 50 nm und eine Länge im Bereich von 10 bis 150 nm aufweist, enthalten.

Here, oral and dental care and cleaning agents according to the invention are preferred which contain the calcium salt (s) in the form of individual crystallites or in the form of predominantly platelet-shaped particles comprising a plurality of said crystallites, wherein a single crystallite has a thickness in the range of 2 to 50 nm and has a length in the range of 10 to 150 nm, in the form of composite materials, which - based on the weight of the composite material -

• a) 0.1 to 80 wt .-%, preferably 10 to 60 wt .-% and in particular 30 to 50 wt .-% protein components selected from proteins, protein hydrolysates and protein hydrolyzate derivatives;
• b) from 0.01 to 80% by weight, preferably from 10 to 75% by weight and in particular from 30 to 65% by weight, of the calcium salt (s) in the form of individual crystallites or in the form of predominantly platelet-shaped particles, comprising a plurality of said crystallites, wherein a single crystallite has a thickness in the range of 2 to 50 nm and a length in the range of 10 to 150 nm.

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

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 wax 108, (1982) 177 or Cosm. Toil. 99, (1984) 63, by HW Steisslinger in Part. Kosm. 72, (1991) 556 and F. Aurich et al. in tens. Surt. 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 19502167 C1 and DE 19502168 C1 (Henkel) is described.

In the context of the present invention, protein hydrolyzate derivatives are to be understood as meaning chemically and / or chemoenzymatically modified protein hydrolysates such as, for example, those listed under INCI-Be Sodium Cocoyl Hydrolyzed Wheat Protein, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein, Potassium Cocoyl Hydrolyzed Collagen, Potassium Undecylenoyl Hydrolyzed Collagen, and Laurdimonium Hydroxypropyl Hydrolyzed Collagen Known Compounds. Preferably derivatives of protein hydrolysates of collagen, keratin and casein and vegetable protein hydrolysates are used according to the invention such. B. Sodium Cocoyl Hydrolyzed Wheat Protein or Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein.

Further examples 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 may be present in any of the composite materials of the invention by one or more substances selected from the group of proteins, Protein hydrolysates and protein hydrolyzate derivatives are formed.

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

Especially Preferably, the protein component is selected from gelatin, casein and / or their hydrolysates.

According to one very particularly preferred embodiment is the protein component of, in the remineralizing product containing composite material 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 (AB).

In a further embodiment of the invention the nanoparticulate calcium salt primary particles present in the composite materials of one or more surface modifiers wrapped be.

Thereby For example, the production of composite materials in such make be facilitated, in which the nanoparticulate calcium salts difficult to disperse. The surface modifier becomes to the surface the nanoparticles adsorbs and alters them in such a way that the dispersibility of the calcium salt increases and the agglomeration the nanoparticle is prevented.

Furthermore can by a surface modification the structure of the composite materials as well as the loading of the protein component with the nanoparticulate Calcium salt affects become. This is the case when using the composite materials possible in remineralization processes, Influence on the course and the speed of the remineralization process to take.

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

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

Prefers becomes the formation of the inventively preferred composite material 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 The pH of the addition of the phosphate solution is through Addition of appropriate amounts of aqueous Base kept constant.

The or the composite materials are - depending on the exact composition of the respective composite material - used in such quantities, that the mouthpiece according to the invention and dentifrices and cleaners based on the weight of the By means of 0.005 to <0.1 Wt .-% calcium salt (s) in the form of individual crystallites or in Form of predominantly platelet-shaped particles, comprising a plurality of said crystallites, wherein a single Crystallite has a thickness in the range of 2 to 50 nm and a length in the range from 10 to 150 nm. According to the invention preferred Compositions are characterized by having 0.008 to 0.16 wt .-%, preferably 0.01 to 0.12 wt .-% and in particular 0.04 to 0.1 wt .-% composite material (a) included.

The mouthpiece according to and dentifrices and cleaners may be used in addition to those mentioned above essential ingredients other ingredients of oral cleansers, Oral hygiene products, dentifrices and / or dentifrices contain. The preferred further ingredients are below described.

The mouthpiece according to and dental care and cleaning agents, especially the toothpastes, z. B. antimicrobial substances as preservatives or as Anti-plaque agents contain. Such substances can z. B. selected being from p-hydroxybenzoic acid methyl, ethyl or propyl ester, sodium sorbate, sodium benzoate, bromochlorophen, Triclosan, phenyl salicylic acid ester, Biguanids z. As chlorhexidine, thymol, etc ..

According to the invention preferred Oral and dental care and cleaning products are characterized that in addition Antiplaque agents, preferably methyl, ethyl or propyl p-hydroxybenzoate, Sodium sorbate, sodium benzoate, bromochlorophene, triclosan, phenyl salicylic acid, 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.

A Another preferred group of ingredients that are used in the compositions of the invention may be included are the anticaries drugs. These can be, for example be selected from organic or inorganic fluorides, z. B. from sodium fluoride, potassium fluoride, sodium monofluorophosphate and sodium fluorosilicate. Also zinc fluoride, tin (II) fluoride are prefers. Preferably, an amount of 0.01-0.2% by weight of fluorine should be used be contained in the form of the compounds mentioned.

Mouthpiece according to the invention and dentifrices and cleaners which additionally contain anti-caries agents, preferably Fluorine compound (s), especially sodium fluoride, potassium fluoride, Sodium monofluorophosphate, zinc fluoride, tin fluoride and sodium fluorosilicate, preferably in amounts of 0.01 to 5 wt.%, Preferably of 0.1 to 2.5% by weight and in particular from 0.2 to 1.1% by weight, in each case to the entire agent, are preferred according to the invention.

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

According to the invention preferred Oral and dental care and cleaning products are characterized that in addition Phosphate (s), preferably alkali metal phosphate (s) and in particular Sodium tripolyphosphate, preferably in amounts of from 1 to 10% by weight, particularly preferably from 2 to 8% by weight and in particular from 3 to 7 wt .-%, each based on the total agent included.

When carrier for the Toothpastes, the setting of a suitable consistency for the dosage from tubes, dispensers or flexible bottles, For example, a combination of humectants, Binders and water.

Humectants are for example those contained in the compositions of the invention Sorbitol or glycerol or 1,2-propylene glycol. In addition to these substances, of which at least one in amounts of at least 10 wt .-% in the agents according to the invention is contained, are suitable as humectants preferably alcohols with at least 2 OH groups, preferably mannitol, xylitol, polyethylene glycol, polypropylene glycol and their mixtures.

Under These compounds are those having 2 to 12 OH groups and in particular those with 2, 3, 4, 5, 6 or 10 OH groups are preferred.

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

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

When preferred further humectants may, for. Xylitol, propylene glycols, Polyethylene glycols, especially those with average molecular weights be used by 200-800.

The or the additional Humectants can in the inventive compositions be used in varying amounts. While in dependence from the rest optional ingredients amounts of a few% (for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 wt.%, Each based on the total Means) may be included There are also formulations that have significantly higher humectant levels exhibit. The total dampening solution content (including the in the inventive compositions contained sorbitol, glycerol and 1,2-propylene glycols) is for example 50, 55, 60, 65, 70, 75 wt.%, In each case based on the total agent. Usual and preferred are agents according to the invention, the (including of the agents according to the invention contained sorbitol, glycerol and 1,2-propylene glycol) between Contain 10 and 75 wt.% Humectant. Content between 15 and 70, preferably between 20 and 60 wt.%, in each case based on the entire remedy, can be preferred.

As a consistency regulator (or binder) serve z. As natural and / or synthetic water-soluble polymers such as alginates, carrageenan, tragacanth, starch and starch ethers, cellulose ethers such. As carboxymethyl cellulose (Na salt), hydroxyethyl cellulose, methyl hydroxypropyl cellulose, guar, Akaziengum, agar-agar, xanthan gum, succinoglycan gum, locust bean flour, pectins, water-soluble carboxyvinyl polymers (eg. Carbopol ^® types), polyvinyl alcohol, polyvinyl pyrrolidone, Polyethylene glycols, in particular those having molecular weights of 1 500-1 000 000.

Further Substances that are used for viscosity control are suitable, z. B. phyllosilicates such. B. montmorillonite clays, colloidal thickening silicas such as B. airgel silicas, fumed silicas or finely ground precipitated silicas. It can also viscosity-stabilizing additions from the group of cationic, zwitterionic or ampholytic nitrogen-containing surfactants, the hydroxypropyl-substituted hydrocolloids or the polyethylene glycol / polypropylene glycol copolymers having a average molecular weight of 1000 to 5000 or a combination of mentioned compounds are used in the toothpastes. The mouth- and dentifrices, especially the toothpastes, may also 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. According to the invention 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 from 0.5 to 20% by weight, 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.%, In each case based on the entire remedy, included.

The agent according to the invention, especially the toothpastes, can also in addition further wound healing and anti-inflammatory Fabrics, e.g. B. agents for gingivitis included. such Substances can z. B. selected from allantoin, azulene, chamomile extracts, tocopherol, panthenol, bisabolol, Sage extracts.

When non-cationic, bactericidal component are useful e.g. phenols, Resorcinols, bisphenols, salicylanilides and their halogenated derivatives, halogenated carbanilides and p-hydroxybenzoic acid esters. Particularly preferred antimicrobial components are halogenated diphenyl ethers, e.g. 2,4-dichloro-2'-hydroxydiphenyl ether, 4,4'-dichloro-2'-hydroxydiphenyl ether, 2,4,4'-tribromo-2'-hydroxydiphenyl ether and 2,4,4'-trichloro-2'-hydroxydiphenyl ether (Triclosan). They are preferred in amounts of 0.01-1 wt .-% in the dentifrice according to the invention used. Triclosan is particularly preferred in an amount of 0.01-0.3 wt .-% used.

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

Retinol (3,7-dimethyl-9- (2,6,6-trimethyl-1-cyclohexenyl) -2,4,6,8-nonatetraen-1-ol is the international common name for vitamin A1, but may also be used instead of retinol one of its derivatives having similar biological activity, for example an ester or the retinoic acid (tretinoin), one of its salts or its esters is preferably used, a retinol ester, in particular a fatty acid ester of a fatty acid having 12-22 C atoms When using a retinol ester, eg retinol palmitate with an activity of 1.7 × 10 ⁶ IU / g, an amount of 0.001-0.1% by weight is preferred. Derivatives is recommended for a use amount corresponding to a concentration of 10 ³ to 10 ⁶ IE (International Units) per 100 g.

Preferred dentifrices according to the present invention preferably contain, in addition to polishing agents, fluorine compounds, humectants and binders
0.01-1 wt .-% of a halogenated diphenyl ether
0.05-5 wt.% Panthenol or a salt of pantothenic acid and
0.01-0.1% by weight of a retinol ester, preferably retinol palmitate.

The agent according to the invention, especially the toothpastes, can also substances to increase the containing mineralizing potential, for example, calcium-containing Substances such. Calcium chloride, calcium acetate and dicalcium phosphate dihydrate. The concentration of the calcium-containing substance depends on the solubility the substance and the interaction with others in the mouth and Dentifrice contained substances.

Next said compulsory components can the dentifrices of the invention contain further, known per se auxiliaries and additives. there is an additive that has long been known as a toothpaste component is, in the dentifrices according to the invention particularly effective: calcium glycerophosphate, the calcium salt of Glycerol-1-phosphoric acid or glycerol-2-phosphoric acid or to the glycerol-1-phosphoric acid enantiomeric glycerol-3-phosphoric acid or a mixture of these Acids. The compound has a remineralizing in dentifrices Effect of providing both calcium and phosphate ions. In the dentifrices according to the invention Calcium glycerophosphate is preferably used in amounts of 0.01-1% by weight. used. Overall, you can the dentifrices according to the invention conventional auxiliaries and additives in amounts up to 10 wt .-%.

The dentifrice according to the invention can e.g. by adding aromatic oils and sweeteners be improved in their organoleptic properties.

When aromatic oils can all for Oral and dental care usual natural and synthetic flavors. Natural flavors can be both in the form of the natural essential oils isolated from drugs as well as those isolated from them Be contained individual components.

suitable Flavors are e.g. Peppermint oil, spearmint, Eucalyptus oil, anise oil, Fennel oil, Caraway oil, menthyl acetate, Cinnamaldehyde, anethole, vanillin, thymol and mixtures of these components.

suitable sweeteners are e.g. Saccharin sodium, sodium cyclamate, sucrose, lactose, Meltose, fructose.

• – Oberflächenaktive Stoffe, bevorzugt anionische, zwitterionische, amphotere, nichtionische Tenside oder eine Kombination mehrerer verschiedener Tenside
• – Lösungsmittel und Lösungsvermittler, z.B. niedere einwertige oder mehrwertige Alkohole oder Ether, z.B. Ethanol, 1,2-Propylenglycol, Diethylenglycol oder Butyldi-glycol
• – Pigmente, wie z.B. Titandioxid
• – Farbstoffe
• – Puffersubstanzen, z.B. primäre, sekundäre oder tertiäre Alkaliphosphate oder Citronensäure-/Na-Citrat
• – weitere wundheilende oder entzündungshemmende Stoffe, z.B. Allantoin, Harnstoff, Azulen, Kamillewirkstoffe, Acetylsalicylsäurederivate oder Rhodanid
• – weitere Vitamine wie z.B. Ascorbinsäure, Biotin, Tocopherol oder Rutin
• – Mineralsalze wie z.B. Mangan-, Zink- oder Magnesiumsalze.

Further customary auxiliaries and additives for toothpastes are

• - Surface-active substances, preferably anionic, zwitterionic, amphoteric, nonionic surfactants or a combination of several different surfactants
• - Solvents and solubilizers, for example, lower monohydric or polyhydric alcohols or ethers, for example, ethanol, 1,2-propylene glycol, diethylene glycol or butyl di-glycol
• - pigments, such as titanium dioxide
• - Dyes
• - Buffer substances, such as primary, secondary or tertiary alkali metal phosphates or citric acid / Na citrate
• - other wound-healing or anti-inflammatory substances, eg allantoin, urea, azulene, chamomile substances, acetylsalicylic acid derivatives or rhodanide
• - Other vitamins such as ascorbic acid, biotin, tocopherol or rutin
• - Mineral salts such as manganese, zinc or magnesium salts.

A another important group of ingredients used in the compositions of the invention may be included are the so-called bioactive glasses.

Of the Term "bioactive Glasses "covered in the frame the present application glasses, which are biologically active and / or biologically active. The biological Effectiveness of a glass, for example, in its antimicrobial Properties show biologically active glass is different from conventional Lime-sodium-silicate glasses by binding living tissue. Biologically active glass called For example, a glass that has a strong bond with body tissue enters, wherein a hydroxyl apatite layer is formed. Under bioactive glass is also understood to be a glass that is antimicrobial and / or anti-inflammatory Effect shows. The glass powder show against bacteria, fungi as well Viruses have a biocidal or a biostatic effect; are in contact skin-friendly with humans, toxicologically safe and especially suitable for consumption.

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

The mouthpiece according to and dental care and cleaning agents 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 when melting the glass. At concentrations of less than 5%, the melting behavior is adversely affected. Sodium is a constituent of the phases which form during the ceramization and, if high crystalline phase fractions are to be adjusted by the ceramization, must be present in the glass in correspondingly high concentrations. K ₂ O acts as a flux when melting the glass. In addition, potassium is released in aqueous systems. If high potassium concentrations are present in the glass, potassium-containing phases such as calcium silicates are also eliminated. The P ₂ O 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 Phospaht glasses, P ₂ O _{5 is} network images. The P ₂ O ₅ content is preferably between 0 and 80 wt .-%. In order to improve the meltability, the glass may contain up to 25% by weight of B ₂ O ₃ . Al ₂ O ₃ is used to adjust the chemical resistance of the glass.

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

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

Usually, the glass or the glass ceramic is used in powder form. The ceramization can 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 both dry and in aqueous or non-aqueous Rough grinding media are performed. Usually, the particle sizes are less than 500 microns. As appropriate, particle sizes <100 microns or <20 microns have been found. Particularly suitable are particle sizes <10 microns and less than 5 microns and less than 2 microns, see below.

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

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

Particularly preferred oral and dental care and cleaning agents according to the invention are characterized in that the bioactive glass - based on its weight - has the following composition:

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.

The compositions according to the invention of this embodiment are outstandingly suitable for tooth cleaning and care. They gently cleanse the teeth and have the additional benefit of smoothing the tooth surface. For scratch value determinations (treatment of teeth under standardized conditions with different compositions and comparison of the surfaces versus treatment of a standard polishing agent), the compositions according to the invention have distinct advantages:
The compositions of the invention have further advantageous properties when their rheological properties are optimized. In particular, the effect of the compositions according to the invention can be further increased by the adjustment of a suitable viscosity. Here, oral and dental care and cleaning compositions according to the invention are preferred which have a viscosity (after 7 days storage at 20 ° C, measured at 20 ° C and an air pressure of 1 bar, Brookfield RVDV II + viscometer, with Helipath at a shear rate of 4 rpm) from 450,000 to 1,000,000 mPas, preferably from 500,000 to 700,000 mPas and in particular from 550,000 to 650,000 mPas.

Claims (24)

Oral and dental care and cleaning products, containing - related on his weight - a) ≥ 0.005 to <0.1% by weight of calcium salt (e) in the form of individual crystallites or in the form of particles, comprising a plurality of said crystallites, wherein a single crystallite a thickness in the range of 2 to 50 nm and a length in the range from 10 to 150 nm; b) 2.0 to 25.0 wt .-% precipitated silica (s) with a particle size d50 (laser diffraction according to ISO 133-20-1) <15 μm, in which the particles are chopped and / or platelet-shaped, preferably are predominantly platelet-shaped. Oral and dental care and cleaning agents after Claim 1, characterized in that the predominantly platelet-shaped particles a length from 10 to 150 nm and a width of 5 to 150 nm, preferably one length of 30 to 100 nm and a width of 10 to 100 nm. Oral and dental care and cleaning agents after Claim 1 or 2, characterized in that the particles a relationship of length to width from 1 to 4, preferably from 1 to 3, particularly preferred between 1 to 2. Oral and dental care and cleaning agent according to any 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 ^{Have -15} m ² . Oral and dental care and cleaning agents after one of the preceding claims, characterized in that - based on its weight - 0.01 to 0.09 wt .-%, preferably 0.02 to 0.08 wt .-%, more preferably 0.03 to 0.075 wt .-%, more preferably 0.04 to 0.07 wt .-% and in particular 0.05 to 0.065 wt .-% calcium salt (s) in the form of individual Crystallites or in the form of predominantly platelet-shaped particles comprising a plurality of said crystallites, wherein a single crystallite a thickness in the range of 2 to 50 nm and a length in the range of 10 to 150 nm, preferably a thickness of 2 to 15 nm and a length of 10 to 50 nm; more preferably, a thickness of 3 to 7 nm and a length of 15 to 25 nm. Oral and dental care and cleaning agents after one of the preceding claims, characterized in that the or the calcium salt (s) in the form of individual crystallites or in the form of predominantly platelet-shaped particles, comprising a plurality of said crystallites, wherein a single Crystallite has a thickness in the range of 2 to 50 nm and a length in the range from 10 to 150 nm, is selected from the group Hydroxyapatite, fluorapatite and calcium fluoride. Oral and dental care and cleaning agents after one of the preceding claims, characterized in that - based on its weight - 2.5 to 15.0, preferably 3.5 to 12.5, more preferably 4.5 to 11.0 and in particular 5.0 to 9.5 wt .-% precipitated silica (s) with a particle size d50 (laser diffraction according to ISO 133-20-1) between> 1 and <12 μm, preferably between> 2 and <10 μm and in particular between> 3 and <8 microns. Oral and dental care and cleaning agents after one of the preceding claims, characterized in that it except the precipitated silicas mentioned each other silicas contains. Oral and dental care and cleaning agent according to one of the preceding claims, characterized in that all precipitated silicas present in the middle have a specific surface area (N ₂ , measured according to ISO 5794-1, Annex D)> 60 m ² / g, preferably> 100 m ² / g, more preferably> 150 m ² / g, particularly preferably> 175 m ² / g and in particular> 185 m ² / g. Oral and dental care and cleaning agents after one of the preceding claims, characterized in that all precipitated silicas contained in the middle of a Dibutyl phthalate absorption (DBP absorption, measured according to DIN 53601)> 150 g / 100 g, preferably> 200 g / 100 g, especially preferably> 235 g / 100g and in particular> 250 g / 100g. Oral and dental care and cleaning agents after one of the preceding claims, characterized in that all precipitated silicas contained in the middle of a Tamping density (not sieved, measured according to ISO 787-11) between> 50 and <400 g / l, preferably between> 75 and <350 g / l, particularly preferred between> 80 and <120 g / l and in particular between> 85 and <100 g / l. Oral and dental care and cleaning agents after one of the preceding claims characterized in that - based on its weight - 0.25 to 2.0 wt .-%, preferably 0.5 to 1.75 wt .-% and in particular 0.75 to 1.5 wt% carboxymethycellulose (CMC). Oral and dental care and cleaning agent according to claim 12, characterized in that the agent contains a Na-CMC whose 2 wt .-% - solution in water has a viscosity (after 7 days storage at 20 ° C, measured at 20 ° C and an air pressure of 1 bar, Brookfield Viscometer RVDV II +, with Helipath at a shear rate of 4 rpm) of from 200 to 1000 mPas, preferably from 300 to 800 mPas and in particular from 350 to 700 mPas. Oral and dental care and cleaning agents after one of the preceding claims, characterized in that in addition to the calcium salt (s) in the form of individual crystallites or in the form of predominantly platelet-shaped particles, comprising a plurality of said crystallites, wherein a single Crystallite has a thickness in the range of 2 to 50 nm and a length in the range from 10 to 150 nm, further calcium salt (s), preferably Calcium glycerophosphate, contains. Oral and dental care and cleaning agents after one of the preceding claims, characterized in that it or the calcium salt (s) in the form of individual crystallites or in the form of predominantly platelet-shaped particles, comprising a plurality of said crystallites, wherein a single Crystallite has a thickness in the range of 2 to 50 nm and a length in the range from 10 to 150 nm, in the form of a suspension containing on the weight of the suspension - a) 0.01 to 15 wt .-%, preferably 0.1 to 10 wt .-% and in particular 0.5 to 7.5 wt .-% of at least one water-soluble surfactant and / or at least a water-soluble polymeric protective colloid; b) 0.01 to 15 wt .-%, preferably 0.1 to 10% by weight and in particular 0.5 to 7.5% by weight of the calcium salt (s) in the form of individual crystallites or in the form of predominantly platelet-shaped particles a plurality of said crystallites, wherein a single crystallite a thickness in the range of 2 to 50 nm and a length in the range of 10 to 150 nm, contains. Oral and dental care and cleaning agents after Claim 15, characterized in that the suspension at 20 ° C has a viscosity (after 7 days storage at 20 ° C, measured at 20 ° C and an air pressure of 1 bar, Brookfield Viscometer RVDV II +, with helipath at a shear rate of 4 rpm) of 500 up to 20,000 mPas, preferably from 750 to 15,000 mPas and in particular from 1000 to 10,000 mPas. Oral and dental care and cleaning agents after one of the preceding claims, characterized in that it contains a composite material comprising a. sparingly soluble in water Calcium salts, wherein the calcium salts in the form of individual crystallites or in the form of particles comprising a plurality of said crystallites, with an average particle diameter in the range of less than 1000 nm, preferably below 300 nm, and b. a polymer component, in which the particles in the composite rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped. Oral and dental care and cleaning agents after Claim 17, characterized in that the polymer component the composite material contained is selected from a protein component, Polyelectrolytes and polysaccharides. Oral and dental care and cleaning agents after Claim 18, characterized in that said protein component selected is preferred from collagen, gelatin, casein and their hydrolysates Gelatin, more preferably gelatin of type A, B or AB, in particular Gelatin of the type Acid bone. Oral and dental care and cleaning agents after one of the preceding claims, characterized in that it or the calcium salt (s) in the form of individual crystallites or in the form of predominantly platelet-shaped particles, comprising a plurality of said crystallites, wherein a single Crystallite has a thickness in the range of 2 to 50 nm and a length in the range from 10 to 150 nm, in the form of composite materials containing on the weight of the composite material - a) 0.1 to 80% by weight, preferably 10 to 60 wt .-% and in particular 30 to 50 wt .-% protein components selected from proteins, protein hydrolysates and protein hydrolyzate derivatives; b) 0.01 to 80 wt .-%, preferably 10 to 75 wt .-% and in particular 30 to 65 wt .-% of the or the calcium salts (s) in the form of individual Crystallites or in the form of predominantly platelet-shaped particles comprising a plurality of said crystallites, wherein a single crystallite a thickness in the range of 2 to 50 nm and a length in the range of 10 to 150 nm, contains. Oral and dental care and cleaning agent according to one of the preceding claims, characterized ge characterized in that it is the insensitivity of the teeth-enhancing substances, preferably potassium salts, more preferably potassium nitrate and / or potassium citrate and / or potassium chloride and / or potassium bicarbonate and / or potassium oxalate, preferably in amounts of 0.5 to 20 wt.%, particularly preferably of 1.0 to 15 wt.%, More preferably from 2.5 to 10 wt .-% and in particular from 4.0 to 8.0 wt.%, Each based on the total agent contains. Oral and dental care and cleaning agents after one of the preceding claims, characterized in that it additionally contains 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. Oral and dental care and cleaning agents after one of the preceding claims, characterized in that it is 0.2 to 20 wt .-%, preferably 0.4 to 14 wt .-%, particularly preferably 0.5 to 3 wt.% And in particular Contains 0.6 to 2 wt .-% of at least one bioactive glass. Oral and dental care and cleaning agents after one of the preceding claims, characterized in that the agent has a viscosity (after 7 days storage at 20 ° C, measured at 20 ° C and an air pressure of 1 bar, Brookfield Viscometer RVDV II +, with helipath at a shear rate of 4 rpm) of 450,000 up to 1,000,000 mPas, preferably from 500,000 to 700,000 mPas and in particular from 550,000 to 650,000 mPas.