WO2007051544A1 - Agents remineralisants concus pour le soin et le nettoyage de la bouche et des dents comrpenant un ou plusieurs silicates - Google Patents

Agents remineralisants concus pour le soin et le nettoyage de la bouche et des dents comrpenant un ou plusieurs silicates Download PDF

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WO2007051544A1
WO2007051544A1 PCT/EP2006/010238 EP2006010238W WO2007051544A1 WO 2007051544 A1 WO2007051544 A1 WO 2007051544A1 EP 2006010238 W EP2006010238 W EP 2006010238W WO 2007051544 A1 WO2007051544 A1 WO 2007051544A1
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Prior art keywords
weight
oral
shaped
dental care
platelet
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PCT/EP2006/010238
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German (de)
English (en)
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WO2007051544A8 (fr
Inventor
Ullrich Bernecker
Adolf Peter Barth
Christiane SCHÜLE
Tilo Poth
Holger Franke
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Henkel Ag & Co. Kgaa
Sus Tech Gmbh & Co. Kg
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Priority claimed from DE200510052372 external-priority patent/DE102005052372A1/de
Priority claimed from DE200610009800 external-priority patent/DE102006009800A1/de
Application filed by Henkel Ag & Co. Kgaa, Sus Tech Gmbh & Co. Kg filed Critical Henkel Ag & Co. Kgaa
Priority to EP06806500A priority Critical patent/EP1942990A1/fr
Publication of WO2007051544A1 publication Critical patent/WO2007051544A1/fr
Publication of WO2007051544A8 publication Critical patent/WO2007051544A8/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/20—Halogens; Compounds thereof
    • A61K8/21—Fluorides; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/24—Phosphorous; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm

Definitions

  • the invention relates to preparations for oral and Zahnfit- and -emotion, which have a remineralizing effect due to special ingredients, have a high cleaning performance without scratching the tooth surface or to be very abrasive and beyond prevent the development of halitosis and reduce bad breath
  • Dentifrices are available in various forms on the market and are primarily used to clean the tooth surface and prevent tooth and gum disease. They usually contain a combination of polishes, humectants, surfactants, binders, flavorings and fluoride and antimicrobial agents To play a subordinate role in their increased abrasiveness, dentifrices are mainly offered in paste, cream and translucent or transparent gel form In recent years, liquid or Flussig leopardcremes and mouthwashes have also become increasingly important
  • Phosphate salts of calcium have long been added to the formulations of dentifrices and dentifrices both as abrasive components and to promote remineralization of the enamel. This is especially true for hydroxyapatite and fluorapatite as well as for amorphous calcium phosphates and for brushite (dicalcium phosphate dihydrate) But calcium fluoride is also part of Tooth cleaning agents and as a component for strengthening the enamel and caries prophylaxis have been described several times
  • a dental care product for hypersensitive teeth which contains finely divided hydroxyapatite (Ca 5 [(PO 4 ) 3 ⁇ H]), the particle size of which is 6-8 ⁇ m (micrometers) Grinding hardly higher subtleties can be achieved
  • EP 1 139 995 A1 it is proposed to stabilize suspensions of calcium salts sparingly soluble in water in very finely divided form during precipitation or shortly thereafter by precipitation in the presence of an agglomeration inhibitor or by redispersing the dispersion in the presence of the agglomeration inhibitor in toothpastes, amounts above 0.1% by weight (based on the total composition and calculated as calium salt) are disclosed
  • the object of the present invention was to provide oral and dental care and -emerberstoff which Reminerahsieren the teeth and against make external influences less sensitive
  • nanoparticulate calcium salts are also effective and, in particular, in small amounts, in particular when the agents additionally contain sodium chloride (s)
  • the present invention is in a first embodiment, an oral and Zahnnosti- and -emerging agent containing - based on its weight - a) ⁇ 0.005 to ⁇ 0.1 wt -% Calc ⁇ umsalz (e) in the form of individual K ⁇ stalliten or in the form of particles comprising a plurality of said k ⁇ stallites, wherein a single k ⁇ stallit has a thickness in the range of 2 to 50 nm and a length in the range of 10 to 150 nm, wherein the particles are rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped, 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 ⁇ m,
  • Oral and dental care as well as oral and dental agents in the context of the invention are oral and dental powders, oral and toothpastes, liquid mouth and tooth creams and oral and dental gels are preferably suitable toothpastes and liquid tooth-reimmers
  • sparingly water-soluble calcium salts which are more preferably selected from phosphates, fluorides and fluorophosphates
  • sparingly water-soluble hereinafter also referred to as sparingly soluble, poorly soluble in water or sparingly soluble
  • those salts are to be understood which are soluble in water (or in a liquid suspension medium) to less than 1 g / l (20 ° C.).
  • suitable salts are Cal ⁇ umhydroxyphosphat (Ca 5 [OH (PO 4 ) 3 ]) or hydroxylapatite, calcium fluorophosphate (Ca 5 [F (PO 4 ) 3 ]) or fluoroapatite, F-doped hydroxyapatite the general composition Ca 5 (PO 4 ) 3 (OH, F) and calcium fluoride (Ca F 2 ) or fluorite (fluorspar)
  • the sparingly soluble calcium salt and in particular its composites are additionally able to precipitate out of the calcium and phosphate ions present in the natural saliva of humans in supersaturated concentrations.
  • This nucleation effect thus leads to the formation of new dental material (neommeralization) in particular of the enamel and / or of the dentin, from the body's own reservoirs.
  • a closure of the dental tubules is thereby achieved
  • oral and dental care and cleansing compositions according to the invention are preferred in which the or the calcium salt (s) in the form of individual K ⁇ stalliten or in the form of rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped particles, comprising a plurality of said K ⁇ stallite, wherein a single crystallite has a thickness in the range of 2 to 50 nm and a length in the range of 10 to 150 nm, is selected from the group hydroxyapatite, fluoroapatite and calcium fluoride
  • the precipitated silicas contained according to the invention as further constituents are preferably thickening silicates. Particularly preferred precipitated silicas can be described by further physical properties
  • precipitated silicic acids which can be used within the scope of the present invention have an even narrower particle size d50.
  • Preferred oral and dental care and cleansing compositions according to the invention are those which, based on their weight, have from 2.5 to 15 0, preferably from 3 to 5 12 5, more preferably 4.5 to 11, 0 and in particular 5.0 to 9.5% by weight of precipitated silica (s) having a particle size d50 (laser diffraction according to ISO 133-20-1) between> 1 and ⁇ 12 ⁇ m, preferably between> 2 and ⁇ 10 microns and in particular between> 3 and ⁇ 8 microns
  • the silicas used are preferably characterized by a specific surface area.
  • oral and dental care and cleaning compositions according to the invention have proven to be particularly suitable in which all precipitated silicas present 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 have
  • the oral and dental care and cleaning compositions according to the invention have proven to be particularly suitable, in which all precipitated silicas present in the middle have a dibutyl phthalate absorption (DBP absorption, measured in accordance with DIN 53601).
  • DBP absorption dibutyl phthalate absorption, measured in accordance with DIN 53601.
  • compositions according to the invention in particular toothpastes or liquid toothpastes, may preferably contain one or more polishes in an amount of from 5 to 50% by weight, provided that silicic acids or even precipitated silicas are used as polishes These are only then included in the calculation of the 2.0 to 25.0% by weight precipitated silica (s) according to the invention if their particle size d 50 (laser diffraction according to ISO 133-20-1) is ⁇ 15 ⁇ m
  • suitable polishing agent components are therefore silicas, aluminum hydroxide, aluminum oxide, Nat ⁇ um aluminum silicates, organic polymers or mixtures of such friction
  • calcium-containing poher components such as chalk, calcium pyrophosphate, dicalcium phosphate dihydrate can be present in amounts of up to 5% by weight
  • the total content of pesticides is preferably in the range of 5 to 50% by weight of the dentifrice
  • Suitable silicic acids are, for example, gel silicas, hydrogel silicas and precipitated silicas.
  • Gel silicas are prepared by reacting sodium silicate solutions with strong, aqueous mineral acids to form a hydrosol to hydrogel, washing and drying Drying under mild conditions to a water content of 15 to 35% by weight gives the so-called hydrogel silicic acids. Drying to water contents below 15% by weight results in an irreversible shrinkage of the previously loose structure of the hydrogel to the dense structure of the so-called xerogel
  • Aluminum oxide in the form of slightly calcined alumina containing alumina and aluminum oxide in an amount of about 1-5% by weight may also be present as further polishing component.
  • a suitable alumina is marketed under the trade name "Poliertonerde P10 feinst” (Giulini Chemistry) available
  • polishing agents are all friction bodies known for toothpastes, such as, for example, sodium aluminum silicates, such as, for example, Zeohth A, organic polymers, such as polymethacrylate, or mixtures of these and the abovementioned friction bodies.
  • sodium aluminum silicates such as, for example, Zeohth A
  • organic polymers such as polymethacrylate, or mixtures of these and the abovementioned friction bodies
  • 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 Zeohth A, organic polymers, in particular polymethacrylates or mixtures of these friction bodies, preferably in amounts of from 1 to 30% by weight, preferably from 2.5 to 25% by weight and in particular from 5 to 20% by weight, in each case based on the total agent
  • 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 Zeohth A, organic polymers, in particular polymethacrylates or mixtures of these friction bodies, preferably in amounts of from 1 to 30% by weight, preferably from 2.5 to 25% by weight and in particular from 5 to 20% by weight, in each case based
  • the oral and dental care and cleaning compositions according to the invention may additionally contain carboxymethylcellulose, this is desired in view of the theological properties of the agents, in addition, an increase in the activity of the Calc ⁇ umsalz (e) in the form of individual crystallites or in the form of particles comprising a plurality of said fragments, wherein a single k ⁇ stallit 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 according to the invention contain carboxymethylcellulose
  • the carboxymethylcellulose (CMC for short) is generally the sodium salt of the glycolic acid ether of cellulose.
  • CMC can be described by the formula below in which the radicals R are selected from H, CH 2 -COONa
  • CMC is technically produced by reacting alkahcellulose with monochloroacetic acid or its sodium salt.
  • the resulting CMC contains, as a result of production, common salt and sodium glycolate and diglycolate.
  • Commercially available CMC is a colorless powder or granules and is provided with degrees of substitution of about 0.5-1.5 and a wide range of solution viscosities offered
  • Preferred oral and dental care and cleaning agents according to the invention are characterized in that they contain, based on their weight, from 0 25 to 2.0% by weight, preferably from 0.5 to 1, 75% by weight and in particular from 0.75 to 1 , 5% by weight of carboxymethycellulose (CMC)
  • oral and dental care and cleaning compositions according to the invention which contain a Na-CMC whose 2% strength by weight solution in water has a viscosity (after 7 days) are particularly preferred Storage at 20 0 C, measured at 20 0 C and an air pressure of 1 bar, Brookfield RVDV II + viscometer, with helipath at a shear rate of 4 U / mm) of 200 to 1000 mPas, preferably from 300 to 800 mPas and in particular of 350 to 700 mPas
  • calcium salts in nanoparticulate form can mouth the invention and dental care and cleaning more calcium salts that do not necessarily have to be nanoparticulate
  • calcium glycerophosphate proven which is marketed under the trade name Furdentyl ®
  • Oral and dental care and cleaning agents which are particularly preferred according to the invention are characterized in that, in addition to the calcium salt (s) in the form of individual crystallites or in the form of rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped particles comprising a plurality of said Knstallite, wherein a single K ⁇ stallit has a thickness in the range of 2 to 50 nm and a length in the range of 10 to 150 nm, wei ⁇ tere (S) Calc ⁇ umsalz (s), preferably calcium glycerophosphate
  • the oral and dental care and cleaning compositions according to the invention may contain the nanoparticulate calcium salts in different forms.
  • the calcium salts are stabilized against agglomeration
  • the oral and dental care compositions according to the invention comprise the calcium salt (s) in the form of individual crystallites or in the form of rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped particles comprising a plurality of said k ⁇ stallites, wherein a single clastite 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% by weight, preferably 0.1 to 10% by weight and in particular 0 5 to 7.5% by weight of at least one water-soluble surfactant and / or at least one water-soluble polymeric protective colloid, b) 0.01 to 15% by weight, 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 rod-shaped and / or platelet-shaped particles,
  • water is primarily suitable as the liquid medium in which the calcium salts can be dispersed.
  • the calcium salt particles isolated from an aqueous suspension for example by filtration or centrifugation, can also be redispersed in organic solvents and likewise provide suspensions
  • the primary particles in the nanometer range which hardly incline to agglomeration Suitable organic liquid media are, for example, water-soluble, lower alcohols and glycols, polyethylene glycols, glycerol or mixtures thereof with one another or with water
  • Particle particles are understood to mean the fragments, ie the individual crystals of the calcium salts mentioned.
  • the length is to be understood here as the diameter of the particles in the direction of their greatest length extension. Thickness is understood here to be the smallest diameter of the fragments (partial particles)
  • Determination of the corresponding different diameters of the fragments can be determined by methods familiar to the person skilled in the art, in particular by the evaluation of the broadening of the X-ray diffraction observed Reflexes Preferably, the evaluation by Fit method, for example, the Rietveld method
  • the k ⁇ stallite preferably have a thickness of 2 to 15 nm and a length of 10 to 50 nm, more preferably a thickness of 3 to 11 nm and a length of 15 to 25 nm on
  • the shape of a single K ⁇ stallits is rather rod-shaped
  • the particles of calcium salts which are composed of individual Knstalliten invention, depending on the conditions of the preparation process platelet and / or rod-shaped
  • Predominantly platelike means that at least 50%, preferably at least 70%, particularly preferably at least 80% of the particles are present in the form of platelets
  • the particles have a substantially platelet-like shape
  • the calcium salts or composite materials according to the invention comprising these, with the predominantly platelet-like calcium particles of the structure of the bone substance in vivo, which is also composed of plates, particularly similar
  • This has the particular advantage that they due to the similarity of the form with the biological Apatiten (z B bone or dentine apatite) have a particularly good ability to re-and neomineralization, so that the process of biomineralization can take place even faster and better
  • a further advantage of the invention is then that the calcium salts, in particular the sparingly water-soluble calcium salts, or composite materials, comprising these, have an improved biocompatibility with a predominantly platelet-like structure of the calcium salts
  • the calcium salts used according to the invention and / or the composite materials, including these having an average particle diameter of the particles in the range of less than 1000 nm, preferably less than 300 nm
  • the determination of the particle diameter of the particles can be determined by methods familiar to the person skilled in the art, in particular by the evaluation of imaging methods, in particular transmission electron microscopy.
  • the sparingly water-soluble calcium salts and / or the composite materials according to the invention comprise platelet-shaped particles having a width in the range from 5 to 150 nm and a length in the range from 10 to 150 nm and a height (thickness) from 2 to 50 nm.
  • the platelet-shaped particles are present as more or less irregularly shaped particles, sometimes as rather round particles, in some cases more angular particles with rounded edges.
  • the platelet-shaped particles often also overlap several times in such samples. Overlapping particles are typically imaged at the points of overlap with greater blackening than non-overlapping particles.
  • the specified lengths, widths and heights are preferably determined (measured) on non-overlapping particles of the sample.
  • the height of the platelet-shaped particles can preferably be obtained from such images by determining the dimensions of the particles having their largest surface perpendicular to the image plane.
  • the perpendicular to the image plane standing particles are characterized by a particularly high contrast (high density) and appear rather rod-like.
  • These platelet-shaped particles, which are perpendicular to the image plane can be identified as actually standing perpendicular to the image plane if they show a broadening of the dimension (at least in one spatial direction) and a decrease in the density of the image when the image plane is tilted.
  • the height of the particles it is particularly suitable to repeatedly tilt the image plane of the sample in different positions and to determine the dimensions of the particles in the setting which is characterized by the highest contrast / highest density and the smallest dimension of the particles Expansion then corresponds to the height of the particles.
  • the average length of the particles is preferably 30 to 100 nm
  • the width of these particles is preferably in the range between 10 and 100 nm
  • the ratio of length to width is between 1 and 4, preferably from 1 to 3, particularly preferably between 1 and 2, for example 1, 2 ( Length 60 nm, width 50 nm) or 1, 5 (length 80, width 40 nm).
  • the platelet-like shape of the particles is formed by the ratio of length to width. If the ratio between length and width is significantly greater than 4, rod-shaped particles are more likely
  • platelet-shaped particles with a ratio of preferably 1 to 2 have a natural bone material particularly similar length to width ratio and therefore have a particularly good and biocompatible Re- or Neommeralleiter the dental material (dentin and enamel) ,
  • the particles have a surface area of 0.1 * 10 "15 m 2 to 90 * 10 '15 m 2, preferably an area of 0.5 * 10" 15 m 2 to 50 * 10 "15 m 2 , more preferably 1, 0 * 10 15 m 2 to 30 * 10 "15 m 2 , most preferably 1, 5 * 10 " 15 m 2 to 15 * 10 "15 m 2, for example 2 * 10 '15 m 2
  • Area of the particles is the area of the plane, spanned by the length and the vertical width, determined by the usual geometric calculation methods.
  • the suspensions used in this preferred embodiment of the present invention contain (based on the weight of the suspension) 0.01 to 15% by weight, preferably 0.1 to 10% by weight and in particular 0.5 to 7.5% by weight the calcium salt (s) in the form of individual crystallites or in the form of rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped particles comprising a plurality of said k ⁇ stallites, 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.
  • Another ingredient of the suspension are (based on the suspension) from 0.01 to 15% by weight, preferably 0.1 to 10% by weight and in particular 0 5 to 7 5% by weight of at least one water-soluble surfactant and / or at least one water-soluble polymeric protective colloid
  • Surfactants which form adsorption layers on top and boundary surfaces or which can aggregate in volume phases to micellar colloids or lyotropic mesophases are understood as surfactants.
  • An anionic surfactant consisting of a hydrophobic radical and a negatively charged hydrophilic head group amphoteric surfactants, which are both negative and hydrophobic also carry a compensating positive charge, cationic surfactants, which in addition to a hydrophobic radical have a positively charged hydrophilic group, and nonionic surfactants which have no charges but strong dipole moments and are highly hydrated in aqueous solution
  • Suitable anionic surfactants (E1) in formulations of the invention are all suitable for use on the human body anionic surfactants These are characterized by a water-solubilizing, anionic group such as a carboxylate, sulfate, sulfonate or phosphate group and a In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.
  • anionic surfactants are, in each case in the form of the sodium, potassium and ammonium - and the mono-, di- and T ⁇ alkanolammoniumsalze with 2 to 4 carbon atoms in the alkanol group, linear and branched fatty acids having 8 to 30 carbon atoms (soaps),
  • Ethercarbon Acid 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,
  • Sulfobernsteinklamono- and dialkyl ester having 8 to 24 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester having 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 8 to 24 carbon atoms, linear alpha-olefinsulfonates with 8 to 24 carbon atoms,
  • Alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 C atoms are alpha-sulfofatty 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 hydroxyalkylpolyethylene 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 addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide onto fatty alcohols having 8 to 22 C atoms, alkyl and / or alkenyl ether phosphates of the formula (E1-I),
  • 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
  • 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, is a sulfated fatty acid alkylene glycol ester of the formula (E1-II) R 7 CO (AlkO) n SO 3 M (EMI) in the R 7 CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 C atoms, Alk for CH 2 CH 2 , CHCH 3 CH 2 and / or CH 2 CHCH 3 , n is from 0.5 to 5 and M is a cation, monoglycene sulfates and monoglycen
  • R 8 CO is a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z in total for O or for numbers from 1 to 30, preferably 2 to 10, and X is an alkali or alkaline earth metal
  • im Monoglyceride (ether) sulfates are the reaction products of Launnklaremonoglycerid, Kokosfett Maschinenremonoglyce ⁇ d, Palmitinklaremonoglyce ⁇ d, Stearinklaremonoglyce ⁇ d, ölkla- remonoglyce ⁇ d and Talgfettklaremonoglyce ⁇ d and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of Nat ⁇ umsalze
  • monoglycene sulfates of the formula (E1-III) are used in which R 8 CO is a linear acyl radical having 8 to 18 carbon atoms, amide-ether carboxylic acids,
  • Condensation products of C 8 - C 30 - fatty alcohols with protein hydrolysates and / or amino acids and their derivatives are known which the person skilled in as protein fatty acid condensates, such as Lamepon ® - types Gluadin ® - types Hostapon ® KCG or Amisoft ® - Types
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethylester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, Monoglycerdisulfate, alkyl and Alkenyl
  • Zwitterionic surfactants are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO * " or -SO 3 W group.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammoniumglycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example, cocoacylammopropyldimethylammoniumglycinate, and Alkyl-3-carboxymethyl-3-hydroxyethyl imidazoline having in each case 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 Cocamido
  • 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
  • suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylaminopyrlyglycines, N-alkyltarns, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylamino - Acetic acids each having about 8 to 24 carbon atoms in the alkyl group
  • Particularly preferred ampholytic surfactants are N-Kokosalkylam ⁇ noprop ⁇ onat, Kokosacylaminoethylaminopropionat and C
  • Nonionic surfactants (E4) contain, for example, a polyol group, as a hydrophilic group
  • Such compounds are, for example
  • alkylphenols having 8 to 15 carbon atoms in the alkyl group such as the type available under the commercial names Dehydol ® LS, Dehydol ® LT (Cognis), C 12 -C 3 o-Fettsauremono- and diesters of addition products of 1 to 30 moles of ethylene oxide to Glyce ⁇ n,
  • polyol fatty acid esters such as the commercial product Hydagen ® HSP (Cognis) or Sovermol - types (Cognis), alkoxylated triglycerides, alkoxylated fatty acid alkyl esters of formula (E4-I)
  • R 1 CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms
  • R 2 is hydrogen or methyl
  • R 3 is a linear or branched alkyl radical having 1 to 4 carbon atoms and w is a number from 1 to 20 stands,
  • 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
  • p is a number from 1 to 10
  • the alkyl and Alkenylohgoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably from glucose.
  • the preferred alkyl and / or alkenylohgoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the alkyl or alkenyl radical R 15 can furthermore also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myripyl 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 may be obtained as described above are preferably also alkyl oligoglucosides based on hydrogenated C12 / alkylpolyhydroxyalkylam ⁇ de fatty acid-N-i 4 coconut alcohol with a DP of 1 to 3 Sugar surfactants of the type, a nonionic surfactant of the formula ( 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
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups
  • the fatty acid N-alkylpolyhydroxyalkylamides 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 is derived N-alkylpolyhydroxyalkylamides of reducing sugars having 5 or 6 carbon atoms, in particular from the glucose
  • the preferred fatty acid-N-alkylpolyhydroxyalkylamide therefore represent fatty acid-N-alkylglucam ⁇ de, as represented by the formula (E4-IV)
  • Glucamides of the formula (E4-IV) in which R 8 is hydrogen or an alkyl group and R 7 CO for the acyl radical of caproic acid, caprylic acid, capnic acid, lamic acid, palmitic acid, palmitic acid, stearic acid are preferably used as the fatty acid N-alkylpolyhydroxyalkylamides , Fatty acid, linoleic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or technical mixtures thereof are particularly preferred are fatty acid N-alkylglucam ⁇ de of the formula (E4-IV) by reductive amination of glucose with methylamine and at- closing acylation with Lau ⁇ nklare or C12 / 14-coconut fatty acid or a corresponding derivative are obtained Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatmose
  • the preferred nonionic surfactants are the alkylene oxide addition products of saturated linear fatty alcohols and fatty acids having in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations with excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycine as nonionic surfactants
  • the alkyl radical R contains 6 to 22 carbon atoms and may be both linear and branched. Preferred are primary linear and 2-methyl-branched aliphatic radicals Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1- Lauryl, 1-My ⁇ styl, 1-cetyl and 1-stearyl Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-Myr ⁇ styl When using so-called "oxo-alcohols" as starting materials predominate compounds having an odd number of carbon atoms in the alkyl chain
  • nonionic surfactants are the sugar surfactants. These may preferably be present in the agents used according to the invention in amounts of from 0.1 to 20% by weight, based on the total agent. Quantities of from 0.5 to 15% by weight are preferred. and very particular preference is given to amounts of from 0.5 to 7.5% by weight
  • the compounds used as surfactant with alkyl groups may each be uniform substances However, it is generally preferred to start from the production of these substances from native plant or animal raw materials, so that one obtains substance mixtures with different, depending on the particular raw material alkyl chain lengths
  • Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trimethylmethylammonium chloride, for example cetyltrimethylammonium chloride, stearyltin methylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride.
  • alkyltrimethylammonium chlorides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trimethylmethylammonium chloride, for example cetyltrimethylammonium chloride, stearyltin methylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride.
  • chlo ⁇ d and Tricetylmethylammoniumchlo ⁇ d as well as the known under the INCI names Quatermum- 27 and Quatern ⁇ um-83 imidazolium compounds
  • the long alkyl chains of the above surfactants preferably have 10 to 18 carbon atoms
  • QAV with behenyl radicals
  • behenyl radicals in particular the substances known as behinium ammonium chloride or bromide (docosanyltrimethylammonium chloride or bromide).
  • Other preferred QACs have at least two behenyl radicals, with QAVs which are particularly preferred being two behenyl radicals on an imidazohium platelet
  • Genamin ® KDMP (Cla ⁇ ant)
  • Crodazosoft ® DBQ Crodazosoft ® DBQ
  • esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines such products are for example under the trademark Stepantex ®, Dehyquart ® and Armocare ® marketed products Armocare ® VGH-70, a N 1 N- B ⁇ s (2-Palm ⁇ toyloxyethyl) d ⁇ methylamrnon ⁇ umchlor ⁇ d, as well as Dehyquart ® F-75, Dehyquart ® C-4046, Dehyquart® ® L80 and Dehyquart® ® AU-35 are examples of such esterquats
  • Alkylamidoamine are usually naturally by amidation or synthetic fatty acids and fatty acid cuts made with dialkylaminoamines
  • An inventively particularly suitable compound from this group of substances that available under the name Tegoamid ® S 18 commercially stearamidopropyl dimethylamine is
  • Water-soluble polymeric protective colloids are understood as meaning high-molecular compounds which are adsorbed onto the surface of the nanoparticles and modify them so as to prevent them from coagulating and agglomerating.
  • Suitable polymeric protective colloids are, for example, natural water-soluble polymers such as gelatin, casein, albumin, starch , Plant gums and water-soluble derivatives of water-insoluble polymeric natural substances such as cellulose ethers (methylcellulose, hydroxyethylcellulose, carboxymethylcellulose), hydroxyethyl starch or hydroxy-propyl guar
  • Synthetic water-soluble polymers useful as protective colloids include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, polyaspartic acid, and others
  • the suspension comprises one or more of polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and derivatives thereof, especially MC, HEC, HPC , HPMC and / or CMC, and / or copolymers and mixtures thereof
  • PVAL polyvinyl alcohol
  • PVAL copolymers polyvinylpyrrolidone
  • polyethylene oxide polyethylene glycol
  • gelatin cellulose and derivatives thereof, especially MC, HEC, HPC , HPMC and / or CMC, and / or copolymers and mixtures thereof
  • polyvinyl alcohols are particularly preferred as water-soluble polymers
  • polyvinyl alcohols abbreviation PVAL, occasionally also PVOH
  • PVAL polyvinyl alcohols
  • polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100 000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol% thus still a residual content of acetyl groups
  • the polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity
  • the suspension comprises polyvinyl alcohols and / or PVAL copolymers whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%
  • compositions of this embodiment according to the invention in which the suspension comprises polyvinyl alcohols and / or PVAL copolymers whose molecular weight is in the range from 3 500 to 100 000 gmol '1 , preferably from 10 000 to 90 000 gmol 1 , more preferably from 12 000 to 80 000 gmol "1 and in particular from 13 000 to 70 000 gmol " 1
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clanant) are particularly suitable in the context of the present invention, polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88 Mowiol ® 5-88 and Mowiol ® 8-88
  • protective colloid for the suspension suitable polyvinyl alcohols are ELVANOL ® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ® 72 5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co), Gohsenol ® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK Also suitable are ERKOL types from Wacker
  • Polyvinylpyrrohdone are These are, for example, under the name Luviskol ® (BASF) sold Polyvmylpyrrolidone [poly (1-v ⁇ nyl-2-pyrrol ⁇ d ⁇ none)], abbreviated PVP, are Polymers of the general formula (I)
  • copolymers of vinylpyrrolidone with other monomers in particular Vinylpyrrohdon / vinyl ester copolymers, such as those sold under the trademark Luviskol ® (BASF) Luviskol ® VA 64 and Luviskol ® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers
  • the vinyl ester polymers are vinyl ester-accessible polymers having the moiety of the formula (II)
  • the polymerization of the vinyl esters is carried out free-radically by different processes (solution polymerization, suspension polymerization, emulsion polymerization,
  • Copolymers of vinyl acetate with vinylpyrrolidone contain monomer units of the formulas (I) and (II)
  • PEG polyethylene glycols
  • PEGs polyethylene glycol corresponding to the general formula (III)
  • H- (O-CH 2 -CH 2 ) n -OH (III) satisfy, where n can assume values between 5 and> 100,000
  • PEGs are prepared industrially by anionic ring-opening polymerization of ethylene oxide (oxirane) usually in the presence of small amounts of water Depending on the reaction conditions, they have molar masses in the range of about 200-5,000,000 g / mol, corresponding to degrees of polymerization of about 5 to> 100,000
  • PEG polyethylene glycols
  • PEOX 1 High molecular weight polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and therefore show only weak glycol properties
  • Gelatine is also preferably used together with other polymers.
  • Gelatine is a polypeptide (molar mass approx. 15,000 to> 250,000 g / mol) which is primarily produced by hydrolysis of the collagen contained in the skin and bones of animals is obtained under acidic or alkaline conditions
  • the amino acid composition of gelatin corresponds largely to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as water-soluble Hüllmate ⁇ al is particularly in pharmacy in the form of hard or soft gelatin capsules extremely widespread In the form of films, gelatine has little use because of its high price compared to the polymers mentioned above
  • Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methylhydroxypropyl cellulose, such as are for example sold under the trademark Culminal® ® and Benecel ® (AQUALON) Cellulose ethers can be described by the general formula (IV),
  • R in R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical
  • at least one R in formula (III) is -CH 2 CH 2 CH 2 -OH or -CH 2 CH 2 -OH
  • Cellulose ethers are technically produced 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 1, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose reacted with the etherification reagent or how much Hydroxyethylcelluloses are water-soluble above a DS of approx. 0.6 or an MS of approx.
  • hydroxyethyl or hydroxypropylcelluloses have degrees of substitution in the range of 0.85-1, 35 (DS) or 1, 5-3 (MS) Hydroxyethyl- and -propylcelluloses are described as yellowish-white, odorless and tasteless powders in very different poly marketed hydroxyethyl and propylcelluloses are soluble in cold and hot water and in some (aqueous) organic solvents, in contrast, insoluble in most (anhydrous) organic solvents, their aqueous solutions are relatively insensitive to changes in pH or electrolyte additive
  • the suspension comprises hydroxypropylmethylcellulose (HPMC) having a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) of from 1.0 to 2.0, preferably from 1.4 to 1.9, and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) from 0 1 to 0 3, preferably from 0.15 to 0.25
  • HPMC hydroxypropylmethylcellulose
  • suitable polymers are water-soluble amphopolymers
  • amphoteric polymers that is polymers containing in the molecule both free amino groups and free -COOH or SO3H groups and are capable of forming inner salts
  • zwitterionic polymers containing in the molecule quaternary ammonium groups and -COO - or -SO 3 ' groups
  • An example of an inventively employable amphopolymer is that under the name Amphomer ® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (I 1 1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters.
  • amphopolymers are composed of unsaturated Carboxylic acids (eg acrylic and methacrylic acid), cationically de ⁇ vatisiere n unsaturated carboxylic acids (for example acrylamidopropyl-t ⁇ methyl-ammoniumchlo ⁇ d) and optionally other ionic or nonionic monomers together, as shown for example in German Offenlegungssch ⁇ ft 39 29 973 and the prior art cited there are terpolymers of acrylic acid, methyl acrylate and Methacrylamidopropylt ⁇ moniumchlorid, as they are commercially available under the name Merquat ® 2001 N, particularly preferred according to the invention ampho polymers are further suitable amphoteric polymers are for example sold under the names Amphomer ® and Amphomer ® LV-71 (DELFT NATIONAL) available octylacrylamide / methyl methacrylate / tert - Butylammoethylmethacrylatß-hydroxypropy
  • Water-soluble anionic polymers which are suitable according to the invention are, inter alia
  • Vinyl acetate / crotonic acid copolymers as are, for example, under the names Resyn ® (NATIONAL STARCH), Luviset ® (BASF) and Gafset ® (GAF) in the trade These polymers have in addition to monomer units of the above formula (II) and monomer units of the general formula (V) on
  • Vmylpyrrolidone / vinyl acrylate copolymers available, for example, under the trademark
  • Luviflex ® (BASF) A preferred polymer is sold under the name Luviflex VBM-35 ®
  • Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers for example, under the
  • Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid are all or in admixture with other copolyme ⁇ sierbaren compounds
  • Polyalkylene glycols are obtained by homogeneous heat polymerization by reacting the polyalkylene glycols in the monomers of the vinyl esters, esters of
  • Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate,
  • Vmylbenzoat and as esters of acrylic acid or methacrylic acid those with ahphatician alcohols of low molecular weight, ie in particular ethanol,
  • Polypropylene glycols are polymers of propylene glycol which are of general formula VI
  • I CH 3 n where n may assume values between 1 (propylene glycol) and several thousand. Particularly important here are di-, tri- and tetra-propylene glycol, ie
  • 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 of the copolymerization of (i) at least one nonionic type monomer (i) at least one ionic type monomer (ii) Polyethylene glycol and iv) a crosslinker
  • the polyethylene glycol used has a molecular weight of between 200 and several million, preferably between 300 and 30,000
  • the nonionic monomers may be of very different types and among these are preferably the following: vinyl acetate, vinyl stearate, methyl laurate, vinyl propionate, allyl stearate, allylaurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene
  • the non-ionic monomers may equally be of very different types, among which particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the grafting polymers
  • Preferred crosslinkers are ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose having 2 to 5 allyl groups per molecule of saccharin
  • the grafted and crosslinked copolymers described above are preferably formed from ⁇ ) 5 to 85% by weight of at least one monomer of the nonionic type, n) 3 to 80% by weight of at least one monomer of the ionic type, in) 2 to 50% by weight.
  • Carbon atoms, where the carbon chains of these compounds may optionally be interrupted by divalent hetero groups such as -O-, -NH-, -S_
  • 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
  • R 3 is -H or -CH 3
  • R 2 is -CH 3 or -CH (CH 3 ) 2
  • R 1 is -CH 3 or a saturated straight-chain or branched d. 6 alkyl and the sum of the
  • Carbon atoms in the radicals R 1 and R 2 is preferably 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
  • Tetra- and pentapolymers from i) crotonic acid or allyloxyacetic acid) vinyl acetate or vinyl propionate in) branched allyl or methallyl esters (v) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
  • cationic polymers which are preferably usable in the invention according to the invention are cationic polymers.
  • the cationic polymers the permanently cationic polymers are preferred.
  • "permanently cationic” refers to those polymers which have a cationic group independently of the pH.
  • polymers which are a quaternary nitrogen atom, for example in the form of an ammonium group Preferred contain cationic polymers, for example, quaternized cellulose Denvate, as are obtainable under the names of Celquat ® and polymer JR ® commercially the compounds Celquat ® H 100, Celquat ® L 200 and polymer JR ® 400 are preferred quaternized cellulose Denvate Polysiloxanes with quaternary groups, such as the commercially available products Q2-7224 (manufacturer Dow Corning; a stabilized T ⁇ methylsilylamodimethicon), Dow Corning ® 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM 2059 (.
  • Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid the products available under the designations Merquaf ® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers.
  • quaternized derivatives of dialkylamino and methacrylate such as diethyl sulfate quaternized vinylpyrrolidone dimethylaminomethacrylate copolymers.
  • Such compounds are sold under the names Gafquat ® 734 and Gafquat ® 755 commercially.
  • Vinylpyrrolidone-Methoimidazoliniumchlo ⁇ d copolymers such as those available under the name Luviquat ® quaternized polyvinyl alcohol and known under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 polymers with quaternary nitrogen atoms in the main polymer chain
  • the polymers mentioned are according to the so-called INCI Nomenclature, details of which are found in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, which are incorporated herein by reference
  • cationic polymers are quaternized cellulose De ⁇ vate and polymeric dimethyldiallylammonium salts and their copolymers Cationic cellulose De ⁇ vate, in particular the commercially available product ® Polymer JR 400, cationic polymers are particularly preferred
  • the suspension preferably has pH values between 5 and 7, more preferably between 5.5 and 6.9, in particular between 6 and 6.6.
  • Preferred viscosities of the suspension are Range of 500 to 20,000 mPas, so that according to the invention preferred oral and dental care and cleaning agents are characterized in that the suspension at 2O 0 C has a viscosity (after 7 days storage at 20 0 C, measured at 20 ° C and a Air pressure of 1 bar, Brookfield RVDV II + viscometer, with Helipath at a shear rate of 4 U / min) of 500 to 20,000 mPas, preferably from 750 to 15,000 mPas and in particular from 1,000 to 10,000 mPas
  • the suspensions which can be used according to the invention can be prepared by precipitation reactions from aqueous solutions of water-soluble calcium salts and aqueous solutions of water-soluble phosphate or fluo ⁇ dsalze.
  • the precipitation is carried out in the presence of water-soluble surfactants or water-soluble polymeric protective colloids This can for example be done in such a way that the surfactants or protective colloids
  • the aqueous calum salt solution may be introduced simultaneously with the phosphate or fluoride salt solution into an aqueous surfactant or protective colloid solution
  • a further variant of the method consists in that the precipitation from a strongly acidic solution of a water-soluble calcium salt and a stochiomet ⁇ schen amount of a water-soluble phosphate salt having a pH below 3 by raising the pH with ⁇ ß ⁇ gem alkali or ammonia in the presence of water-soluble surfactants or water-soluble polymeric protective colloids performs
  • the aqueous suspensions according to the invention are expediently removed from the aqueous phase by filtration or centrifugation, the nanoparticles are optionally dried and redispersed in organic solvents Since the nanoparticles adsorb the amounts of stabilizers required to inhibit agglomeration on the surface, fineness and stability of such suspensions are therefore comparable with the aqueous suspensions.
  • Another possibility is to add the aqueous suspension with a higher-boiling solvent, for example glycerol Mix and remove the water by distillation
  • a higher-boiling solvent for example glycerol Mix
  • the oral and dental care and cleaning compositions according to the invention may also contain the nanoparticulate calcium salts in the form of composite materials
  • the composite materials according to the invention comprise calcium salts which are sparingly soluble in water, the calcium salts being present in the form of individual fragments or in the form of particles comprising a plurality of said fragments with a mean particle diameter in the range below 1000 nm, preferably below 300 nm
  • b is a polymer component, wherein the particles in the composite material are rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped
  • Composite materials are understood as meaning composites which comprise the components mentioned under a) and b) and represent microscopically heterogeneous, macroscopically homogeneous aggregates, and in which the primary particles / kstallites of the calcium salts are associated with the framework of the polymer component.
  • the proportion of polymer components in the composite materials is from 0.1 to 80% by weight, preferably from 10 to 60% by weight and in particular from 30 to 50% by weight, based on the total weight of the Kompositmate ⁇ alien
  • the polymer component of the composite material contained in the remineralizing product is selected from a protein component, polyelectrolytes and polysaccharides
  • polyelectrolytes may be polyacids and polybases, it being possible for the polyelectrolytes to be biopolymers or else synthetic polymers.
  • the compositions according to the invention contain one or more polyelectrolytes selected from
  • Polyammo acids such as polyaspartic acids
  • Nucleanic acids such as DNA and RNA
  • polyvinylamines and derivatives of the abovementioned substances in particular amino and / or carboxyl derivatives
  • polyelectrolytes are used in the context of the present invention which bear suitable groups for salt formation with divalent cations.
  • Polymers bearing carboxylate groups are particularly suitable
  • polyelectrolytes within the meaning of the invention are polyaspartic acids, alginic acids, pectins, deoxyribonucleic acids, ribonucleic acids, polyacrylic acids and polymethacrylic acids
  • polyaspartic acids having a molecular weight in the range between about 500 and 10,000 daltons, in particular 1000 to 5000 daltons
  • polysaccharides are selected as the polymer component.
  • these polysaccharides are selected from glucuronic acid- and / or iduronic acid-containing polysaccharides.
  • These polysaccharides are understood as meaning, inter alia, glucuronic acid, preferably D-glucuronic acid, and / or A constituent of the carbohydrate skeleton is thereby formed by glucuronic acid or iduronic acid.
  • the iduronic acid isomeric to glucuronic acid has the other configuration at the C5 carbon atom of the ring.
  • Glucuronic acid- and / or iduronic acid-containing polysaccharides are to be understood as meaning such polysaccharides , the glucuronic acid and / or iduronic acid 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 Monosaccha ⁇ dbausteine of the polysaccharide
  • 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.
  • suitable polysaccharides are the glucuronic acid and / or iduronic acid-containing glycosaminoglycans (also Mucopolysaccha ⁇ de), microbially produced xanthan gum or gum arabic, which is obtained from acacia
  • glucuronic acid and / or iduronic acid-containing glycosaminoglycans also Mucopolysaccha ⁇ de
  • microbially produced xanthan gum or gum arabic which is obtained from acacia
  • dispersing aids such as, for example, polyhydric alcohols (such as glycerol or polyethylene glycols).
  • proteins are basically all proteins regardless of their origin or their production.
  • proteins of animal origin are keratin, elastin, collagen, fibroma, albumin, casein, whey protein, placental protein
  • collagen, keratin, Casein, whey protein, proteins of plant origin such as wheat and wheat germ protein, rice protein, soy protein, oat protein, pea protein, potato protein, almond protein and yeast protein may also be preferred according to the invention
  • protein hydrolysates are degradation products of proteins such as, for example, collagen elastin, casein, keratin, almond, potato, wheat, rice and soy protein, which are formed by acidic, alkaline and / or enzymatic hydrolysis of the proteins themselves or their degradation products such as gelatin are obtained for the enzymatic degradation are all hydrolytic enzymes suitable, such as alkaline proteases Other suitable enzymes and enzymatic hydrolysis are described for example in K Drauz and H Waldmann, Enzyme Catalysis in Organic Synthesis, VCH-Verlag, Weinheim 1975 In the degradation of the proteins are cleaved into smaller subunits, the degradation over the stages of the polypeptides on the oligopeptides can go to the individual amino acids Among the less degraded protein hydrolysates, for example, within the present invention, preferred gelatin, which Gelatin is a polypeptide obtained primarily by hydrolysis of collagen under acidic (gelatin type A) or alkaline (gelatin type
  • gelatin strength of gelatin is proportional to its molecular weight, ie, a more hydrolyzed gelatin gives a lower viscosity solution
  • Gelatin gel strength is reported in Bloom numbers. In enzymatic cleavage of the gelatin, the polymer size is greatly reduced, resulting in very low Bloom numbers
  • 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 hydrolysates are, for example, from G Schuster and A Domsch in soaps oils Fette Wachse 108, (1982) 177 or Cosm Toil 99, (1984) 63, by HW Steisslmger in Parf Kosm 72, (1991) 556 and F Aurich et al in Tens Surf Det 29, (1992) 389 appeared
  • Protein hydrolysates from collagen, keratin, casein and vegetable proteins used for example, those based on wheat gluten or rice protein, the preparation of which is described in the two German Patent DE 19502167 C1 and DE 19502168 C1 (Henkel)
  • protein hydrolyzate derivatives are understood as meaning chemically and / or chemoenzymatically modified protein hydrolysates such as, for example, the INCI names Sodium Cocoyl Hydrolyzed Wheat Protein, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein, Potassium Cocoyl Hydrolyzed Collagen, Potassium Undecylenoyl Hydrolyzed Collagen and Laurdimonium Hydroxypropyl Hydrolyzed Collagen Known Compounds Derivatives of protein hydrolysates of collagen, keratin and casein and plant protein hydrolysates are preferably used according to the invention, for example sodium cocoyl hydrolyzed wheat protein or laurdimonium hydroxypropyl hydrolyzed wheat protein
  • the protein component can be formed in each of the composite materials according to the invention by one or more substances selected from the group of proteins, protein hydrolysates and protemhydrolyzate derivatives
  • Preferred protein components are all structure-forming proteins, protein hydrolyzates and protein hydrolyzate denvates, which are understood to mean those protein components which, due to their chemical constitution, form specific three-dimensional spatial structures the person skilled in protein chemistry under the terms secondary, tertiary or quaternary structure are familiar
  • the protein component is particularly preferably selected from gelatin, casein and / or its hydrolysates
  • the protein component of the composite material contained in the remineralizing product is selected from collagen, gelatin, casein and their hydrolyzates, preferably gelatin, particularly preferably gelatin of the type A, B or AB, in particular gelatin of the acid bone (AB) type.
  • the nanoparticulate calcium salt primary particles (k ⁇ stallites) present in the composite materials can be enveloped by one or more surface modifiers
  • the preparation of composite materials in cases where the nanoparticulate calcium salts are hard to disperse can be facilitated.
  • the surface modifier is adsorbed on the surface of the nanoparticles and changed so that the dispersibility of the calcium salt increases and the agglomeration of the nanoparticles is prevented
  • a surface modification can influence the structure of the composite materials as well as the loading of the protein component with the nanoparticulate calcium salt. In this way it is possible to influence the course and the speed of the remineralization process in the application of the composite materials in remineralization processes
  • Surface modifiers are substances which physically adhere to the surface of the finely divided particles but do not react chemically with them.
  • the individual surface modifier molecules adsorbed on the surface are essentially free of intermolecular bonds.
  • Surface modifiers are especially dispersants. Dispersants are well-known to those skilled in the art for example, also known under the terms emulsifiers, protective colloids, wetting agents, detergents etc ..
  • a solution of a calcium salt with the polymer component is preferably initially charged and a phosphate solution slowly added, the pH being between 5 and 9, preferably between 6 and 8, particularly preferably around 7 Value is kept constant by adding appropriate amounts of aqueous base when adding the phosphate solution
  • Such calcium salt particles which have an elongated, in particular rod or needle-like, form can be produced in particular by methods according to the invention in which the precipitation of the composite material is at a pH of between about 9.5 and 14, preferably between 10 and 12, preferably about pH 11 is performed
  • the composite material (s) are used in amounts such that the oral and dental care and cleaning compositions of the invention contain 0.005 to ⁇ 0.1% by weight of calcium salt (s) in relation to the weight of the composition
  • the oral and dental care and cleaning compositions of the invention contain 0.005 to ⁇ 0.1% by weight of calcium salt (s) in relation to the weight of the composition
  • the composite material in the form of individual k ⁇ stallites or in the form of rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped particles, comprising a plurality of said k ⁇ stallites, wherein a single K ⁇ stallit has a thickness in the range of 2 to 50 nm and a length in the range of 10 to 150 nm
  • Compositions which are preferred according to the invention are characterized in that they contain 0.008 to 0.16% by weight, preferably 0.01 to 0.12% by weight and in particular 0.04 to 0.1% by weight of composite material (ein)
  • oral and dental care and cleaning compositions of the present invention may contain, in addition to the foregoing essential ingredients, other ingredients of mouthwash, oral care, dentifrice and / or dentifrice.
  • Other ingredients of mouthwash, oral care, dentifrice and / or dentifrice are described below
  • the oral and dental care and cleaning compositions according to the invention may also contain antimicrobial substances as preservatives or as antiplaque agents.
  • antimicrobial substances may be selected, for example, from methyl, ethyl or propyl p-hydroxybenzoate, sodium sorbate, sodium benzoate , Bromchlorophen, T ⁇ closan, phenyl salicylic, biguanides z B chlorhexidine, thymol, etc
  • Oral and dental care and cleaning agents which are preferred according to the invention are characterized in that they additionally have antiplaque active ingredients, preferably methyl- or propyl p-hydroxybenzoate, sodium sorbate, sodium benzoate, bromochlorophene, toclosan, phenylsalicylic acid esters, biguanides, for example chlorhexidine, thymol , preferably in amounts of from 0.1 to 5% by weight, preferably from 0.25 to 2.5% by weight and in particular from 0.5 to 1, 5% by weight, in each case based on the total agent
  • a further preferred group of ingredients which may be contained in the agents according to the invention are the antisense agents.
  • fluorine may be selected, for example, from organic or inorganic fluorides, for example from sodium fluoride, potassium fluoride, sodium monofluorophosphate and sodium fluorosilicate.
  • organic or inorganic fluorides for example from sodium fluoride, potassium fluoride, sodium monofluorophosphate and sodium fluorosilicate.
  • zinc fluoride, zinc (II) Fluorine are preferred.
  • an amount of 0.01-0.2% by weight of fluorine should be present in the form of the compounds mentioned
  • Oral and dental care and cleaning compositions according to the invention which additionally contain anti-caking agents, preferably fluoride compound (s), in particular sodium fluoride, potassium fluoride, sodium monofluorophosphate, zinc fluoride, tin fluoride and sodium fluorosilicate, preferably in amounts of from 0.01 to 5% by weight, preferably from 0, 1 to 2.5% by weight and in particular from 0.2 to 1.1% by weight, in each case based on the total agent, are preferred according to the invention
  • the oral and dental care and cleaning agents may also contain, for example, substances which are effective against tartar.
  • substances may be, for example, chelating agents such as ethylenediaminetetraacetic acid and its sodium salts, pyrophosphate salts such as the water-soluble dialkali or tetraalkahmetal pyrophosphate.
  • Salts for example 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 which For example, it may be selected from water-soluble alkali metal polyphosphates, such as sodium tripolyphosphate and potassium t-polyphosphate
  • Oral and dental care and cleaning agents which are preferred according to the invention are additionally characterized in that they additionally contain phosphate (s), preferably alkali metal metal phosphate (s) and in particular sodium polyphosphate, 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% by weight, in each case based on the total agent
  • phosphate preferably alkali metal metal phosphate (s) and in particular sodium polyphosphate
  • a carrier for the toothpastes which allows the setting of a suitable consistency for the dosage from tubes, dispensing containers or flexible bottles, is for example a combination of humectants, binders and water
  • Humectants are, for example, the sorbitol or glycine or 1,2-propylene glycol present in the compositions according to the invention.
  • at least one of which is contained in the agents according to the invention in amounts of at least 10% by weight are suitable humectants OH groups, preferably mannitol, xylitol, polyethylene glycol, polypropylene glycol and mixtures thereof
  • the (n, n + 1) - or (n, n + 2) -D ⁇ ole with non-terminal OH groups can also be used
  • Xylitol, propylene glycols, polyethylene glycols, in particular those having average molecular weights of 200-800, can be used as preferred further humectants
  • the or the additional humectants can be used in the inventive compositions in varying amounts While depending on the other optional ingredients amounts of a few% (for example, 1, 2, 3, 4 5, 6 7, 8, 9, 10% by weight, respectively Formulations containing significantly higher humectant contents also exist.
  • the total dampening solution content (including the sorbitol, glycene and 1,2-propylene glycols contained in the agents according to the invention) is 50:55, for example , 60, 65, 70, 75% by weight, in each case based on the total agent.
  • compositions according to the invention which (including the sorbitol, glycene and 1,2-propylene glycols contained in the compositions according to the invention) are between 10 and 75% by weight of humectant contain contents between 15 and 70, preferably between 20 and 60 wt%, in each case based on the total mean, can bevo be dressed
  • consistency regulators (or binders) z serve natural and / or synthetic water-soluble polymers such as alginates, Carragheenate, tragacanth, starch and starch ethers, cellulose ethers such as carboxymethylcellulose (Na-SaIz), hydroxyethylcellulose methylhydroxypropylcellulose, guar, acacia, agar, xanthan Gum succinoglycan gum, locust bean flour, pectins, water-soluble carboxyvinyl polymers (eg Carbopol® types) polyvinyl alcohol, polyvinylpyrrolidone polyethylene glycols, in particular those with molecular weights of 1 500-1 000 000
  • compositions which are suitable for viscosity control are, for example, layered shats such as montmorillonite clays, colloidal thickening silicas such as airgel silicas, fumed silicas or finely ground precipitated silicas Viscosity stabilizing additives from the group of cationic, zwitterionic or ampholytic nitrogenous surfactants, of the hydroxypropyl-substituted hydrocolloids or the polyethylene glycol / polypropylene glycol copolymers having an average molecular weight of 1,000 to 5,000 or a combination of said compounds in the toothpastes
  • the oral and dental care products, in particular the toothpastes may also contain the insensitivity of the teeth-enhancing substances, for example potassium salts such as potassium nitrate, potassium citrate, potassium chloride, potassium bicarbonate and potassium oxalate oral and dental care and cleaning agents according to the invention are characterized in that they the insensitivity of the teeth-enhancing substances, preferably potassium salts, particularly preferably potassium nitrate and /
  • the agents according to the invention may additionally contain other wound-healing and anti-inflammatory substances, eg anti-gingivitis agents.
  • Such substances may be selected, for example, from allantoin, azulene, chamomile extracts, tocopherol, panthenol, bisabolol, sage extracts
  • Suitable non-cationic, bactericidal components are, for example, phenols, resorcinols, bisphenols, salicylanilides and their halogenated derivatives, halogenated carbanilides and p-hydroxybenzoic acid esters.
  • Particularly preferred antimicrobial components are halogenated diphenyl ethers, for example 2-diphenyl-2'-hydroxydiphenyl ether , 4'-D-chloro-2'-hydroxydiphenyl ether 2,4,4'-tribromo-2'-hydroxydiphenyl ether and 2,4,4'-trichloro-2'-hydroxydiphenyl ether (triclosan) They are preferably used in amounts of 0.01 - 1% by weight is used in the dentifrices according to the invention. Ticlosan is particularly preferably used in an amount of 0.01-0.3% by weight
  • pantothenic acid (R - (+) - N - (2 , 4-D ⁇ hydroxy-3,3-dimethylbutyryl-ß-alan ⁇ n) is a precursor in the biosynthesis of coenzyme A and is to V ⁇ tam ⁇ n-B complex (B3) counted
  • the dentifrices according to the invention preferably contain 0.05-5% by weight of panthenol or a salt of pantothenic acid
  • Retinol (3,7-dimethyl-9- (2,6,6-tri-methyl-1-cyclohexenyl) -2,4,6,8-nonatetraene-1-ol is the international common name for vitamin A1
  • the retinol can also one its derivatives having a similar biological activity, for example an ester or the retinoic acid (tretinoin), one of its salts or its esters are preferably used.
  • a retinol ester in particular a fatty acid ester of a fatty acid having 12-22 C atoms is used.
  • Retinol is particularly preferred - Palmitate suitable
  • a retinol ester for example Retmol palmitate with an activity of 1.7 10 6 IU per g
  • an amount of 0.001 to 0.1% by weight is preferred.
  • Preferred dentifrices according to the present invention preferably contain, in addition to polishing agents, fluorine compounds, humectants and binders
  • panthenol or a salt of pantothenic acid 0.05 - 5% by weight of panthenol or a salt of pantothenic acid
  • a retmol ester preferably retinol palmitate
  • the agents according to the invention may also contain substances for increasing the mummifying potential, for example calcium-containing substances such as calcium chloride, calcium acetate and dicalcium phosphate dihydrate.
  • concentration of the calcium-containing substance depends on the solubility of the substance and the interaction with others in the mouth and dentifrices contained substances
  • the dentifrices according to the invention may contain further adjuvants and additives known per se.
  • An additive which has been known for a long time as a toothpaste component is particularly effective in the dentifrices according to the invention for calcium glycerophosphate, the calcium salt of glycerol-1 Phosphoric acid or glycerol-2-phosphoric acid or glycerol-3-phosphoric acid glycerol-3-phosphoric acid or a mixture of these acids.
  • the compound has a remercentric effect in dentifrices, since it supplies both calcium and phosphate ions
  • Dental dentifrices are preferably used in quantities of 0.01-1% by weight of calcium glycerophosphate.
  • the dentifrices according to the invention may contain customary auxiliaries and additives in quantities of up to 10% by weight
  • the dentifrices according to the invention can be improved, for example, by adding aromatic oils and sweeteners in their organoleptic properties
  • Aromatic oils can be any of the natural and synthetic aromas that are common in oral and dental care. Natural aromas can be present both in the form of the natural essential oils isolated from drugs and the individual components isolated from them
  • Suitable flavors are, for example, peppermint oil, spearmint oil, eucalyptus oil, aniseed oil, fennel oil, clover oil, menthyl acetate, cinnamic aldehyde, anethole, vanillin, thymol, and mixtures of these components
  • Suitable sweeteners include sodium saccharin, sodium cyclamate, sucrose, lactose meltose, fructose Further customary auxiliaries and additives for toothpastes are
  • Solvents and solubilizers for example, lower monohydric or polyhydric alcohols or ethers, for example, ethanol, 1,2-propylene glycol, diethylene glycol or butyldi- glycol
  • Pigments such as titanium dioxide
  • Buffer substances for example primary, secondary or tertiary alkali metal phosphates or citric acid / Na citrate further wound-healing or anti-inflammatory substances, for example allantoin, urea,
  • Mineral salts such as manganese, zinc or magnesium salts
  • compositions of the invention Another important group of ingredients that may be included in the compositions of the invention are the so-called bioactive glasses.
  • bioactive glasses includes glasses which are biologically active and / or biologically active.
  • the biological effectiveness of a glass can be demonstrated, for example, in its antimicrobial properties.
  • Biologically active glass differs from conventional lime-sodium silicate. Glass by bonding living tissue
  • Biologically active glass refers, for example, to a glass which forms a firm bond with body tissue, whereby a hydroxyl apatite layer is formed.
  • Bioactive glass is also understood to mean a glass which exhibits antimicrobial and / or anti-inflammatory action Glass powders have a biocidal or biostatic effect against bacteria, fungi and viruses, are skin-friendly in contact with humans, are toxicologically safe and are especially suitable for human consumption
  • Oral and dental care and cleaning agents which are particularly preferred according to the invention are characterized in that they contain 0.2 to 20% by weight, preferably 0.4 to 14% by weight, more preferably 0.5 to 3% by weight and in particular 0, 6 to 2% by weight of at least one bioactive glass
  • the oral and dental care and cleaning agents according to the invention of this embodiment contain bioactive glass or glass powder or glass ceramic powder or composite materials which comprise such a bioactive glass.
  • glass powders are also understood as meaning granules and glass beads Due to the requirements of the toxicological safety of the glass and its suitability for consumption, the glass powder should be particularly pure.
  • the heavy metal exposure is preferably low.
  • the maximum concentration in the range of cosmetic formulations is preferably Pb ⁇ 20 ppm, Cd ⁇ 5 ppm, As ⁇ 5 ppm, Sb ⁇ 10 ppm, Hg ⁇ 1 ppm, Ni ⁇ 10 ppm
  • the unkeraminstrumente starting glass which is contained directly in the preferred compositions of the invention or is optionally used for the preparation of a glass ceramic useful in the invention, contains SiO 2 as a network former, preferably between 35-80 wt -% At lower concentrations, the spontaneous tendency to cystallize strongly and the chemical Stability severely degrading At higher S ⁇ O 2 values, the K ⁇ stallisationsstabiltician 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 less than 5%, the melting behavior is negatively influenced sodium Part of the phases which form during the ceramization and, if high crystalline phase proportions are to be set by the ceramization, must be present in correspondingly high concentrations in the glass.
  • K 2 O acts as a flux
  • potassium is released in aqueous systems. If high potassium concentrations are present in the glass, potassium-containing phases such as calcium silicates are also precipitated.
  • the P 2 O 5 content of silicate glasses, glass ceramics or composites can reduce the chemical resistance of the glass and glass In the case of phosphated glass, P 2 O 5 network images
  • the P 2 O 5 content is preferably between 0 and 80% by weight
  • the glass can be up to 25% by weight
  • B 2 O 3 contain AI 2 O 3 is used to adjust the chemical resistance of the glass
  • antimicrobial ions such as Ag Au, I 1 Ce, Cu, Zn may be present in concentrations of less than 5% by weight
  • Coloring ions such as Mn, Cu, Fe, Cr, Co, V can be present individually or in combination, preferably in a total concentration of less than 1% by weight
  • the glass or the glass ceramic is used in powder form.
  • the ceramization can be carried out either with a glass block or glass ribbons or with glass powder. After ceramization, the glass ceramic blocks or ribbons must be ground to powder. If the powder has been ceramized, it may also have to be ground again to form agglomerates
  • the grindings can be carried out both dry and in aqueous or non-aqueous grinding media.
  • the particle sizes are less than 500 .mu.m Particle sizes ⁇ 100 ⁇ m or ⁇ 20 ⁇ m proved Particularly suitable are particle sizes ⁇ 10 ⁇ m and less than 5 ⁇ m and less than 2 ⁇ m, 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 O- 80% by weight, MgO 0-5% by weight, Ag 2 O 0-0.5% by weight, AgJ 0-0.5% by weight, NaJ 0-5% by weight, TiO 2 0-5% by weight %, K 2 O 0-35% by weight, ZnO 0-10% by weight, Al 2 O 3 0-25% by weight and B 2 O 3 0-25% by weight
  • the base glass according to the above composition can be used to obtain 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 up to
  • a further glass composition may be as follows SiO 2 35-80% by weight, Na 2 O 0-35% by weight, P 2 O 5 0-80% by weight, MgO 0-5% by weight , Ag 2 O 0-0.5% by weight, AgJ 0-0.5% by weight, NaJ 0-5% by weight, TiO 2 0-5% by weight, K 2 O 0-35% by weight, 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% by weight
  • SiO 2 35 to 60% by weight, preferably 40 to 60% by weight
  • K 2 O 0 to 35% by weight, preferably 0 to 20% by weight
  • P 2 O 5 O to 10% by weight, preferably 2 to 10% by weight
  • MgO 0 to 10% by weight, preferably 0 to 5% by weight
  • CaO 0 to 35% by weight, preferably 5 to 30% by weight
  • Al 2 O 3 0 to 25% by weight, preferably 0 to 5% by weight
  • TiO 2 0 to 10% by weight, preferably 0.1 to 5% by weight
  • the bioactive glass is preferably used in particulate form.
  • particularly preferred oral and dental care and cleaning compositions according to the invention are characterized in that the antimicrobial glass particle sizes ⁇ 10 .mu.m, preferably from 0.5 to 4 .mu.m, especially preferably from 1 to 2 microns
  • compositions according to the invention of this embodiment are outstandingly suitable for cleaning and care of teeth. They gently clean 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 the surfaces versus treatment of a standard polish), the compositions of the invention have significant advantages
  • compositions according to the invention have further advantageous properties if their rheological properties are optimized.
  • the effect of the compositions according to the invention can be further increased by the adjustment of a suitable viscosity.
  • 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 2O 0 C and an air pressure of 1 bar, Brookfield viscometer RVDV II +, with Helipath at a shear rate of 4 U / min) from 450 000 to 1 000 000 mPas, preferably 500 000th up to 700 000 mPas and in particular from 550 000 to 650 000 mPas
  • compositions according to the invention in particular in the form of a toothpaste, a particularly smooth, good mouthfeel which is perceived by test persons as being particularly clean results

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Abstract

La présente invention concerne des agents conçus pour le soin et le nettoyage de la bouche et des dents. Ces agents contiennent = 0,005 à < 0, 1 % en poids, par rapport à leur propre poids, de sel(s) de calcium se présentant sous forme de cristallites individuelles ou sous forme de particules comprenant une pluralité desdites cristallites. Une cristallite individuelle présente une épaisseur située entre 2 et 50 nm et une longueur située entre 10 et 150 nm. Les particules se présentent sous forme de baguettes et/ou de plaquettes, de préférence principalement sous forme de plaquettes. Lesdits agents contiennent également de 2,0 à 25,0 % en poids d'acide(s) silicique(s) de précipitation présentant une granulométrie d50 (diffraction laser selon ISO 133-20-1) < 15 µm. Ces agents reminéralisent les dents et les rendent moins sensibles aux influences extérieures.
PCT/EP2006/010238 2005-10-31 2006-10-24 Agents remineralisants concus pour le soin et le nettoyage de la bouche et des dents comrpenant un ou plusieurs silicates WO2007051544A1 (fr)

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EP06806500A EP1942990A1 (fr) 2005-10-31 2006-10-24 Agents remineralisants concus pour le soin et le nettoyage de la bouche et des dents comrpenant un ou plusieurs silicates

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DE102005052372.2 2005-10-31
DE200510052372 DE102005052372A1 (de) 2005-10-31 2005-10-31 Remineralisierende Mund- und Zahnpflege- und -reinigungsmittel mit Silikat(en)
DE200610009800 DE102006009800A1 (de) 2006-03-01 2006-03-01 Remineralisierende Mund- und Zahnpflege- und -reinigungsmittel mit Silikat(en)
DE102006009800.5 2006-03-01

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WO2007051544A8 WO2007051544A8 (fr) 2008-06-12

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012005593A2 (fr) 2010-07-09 2012-01-12 Stichting Glass For Health Compositions d'apatite

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3501432A1 (de) * 1984-03-08 1985-09-12 Lion Corp., Tokio/Tokyo Zahnpflegemittel
DE19858662A1 (de) * 1998-12-18 2000-06-21 Henkel Kgaa Feinteilige Suspensionen schwerlöslicher Calciumsalze und deren Verwendung in Zahnpflegemitteln
WO2002049578A1 (fr) * 2000-12-20 2002-06-27 Henkel Kommanditgesellschaft Auf Aktien Feuille adhesive dentaire remineralisante
WO2004058207A1 (fr) * 2002-12-20 2004-07-15 Sustech Gmbh & Co. Kg Matieres composites constituees de composes de calcium et de polysaccharides contenant de l'acide glucuronique et/ou de l'acide iduronique
DE10340542A1 (de) * 2003-09-01 2005-03-24 Henkel Kgaa Mund- und Zahnpflegemittel
WO2006133747A1 (fr) * 2005-06-15 2006-12-21 Henkel Kommanditgesellschaft Auf Aktien Agents a effet remineralisant destines au nettoyage et a l'hygiene des dents et de la bouche

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3501432A1 (de) * 1984-03-08 1985-09-12 Lion Corp., Tokio/Tokyo Zahnpflegemittel
DE19858662A1 (de) * 1998-12-18 2000-06-21 Henkel Kgaa Feinteilige Suspensionen schwerlöslicher Calciumsalze und deren Verwendung in Zahnpflegemitteln
WO2002049578A1 (fr) * 2000-12-20 2002-06-27 Henkel Kommanditgesellschaft Auf Aktien Feuille adhesive dentaire remineralisante
WO2004058207A1 (fr) * 2002-12-20 2004-07-15 Sustech Gmbh & Co. Kg Matieres composites constituees de composes de calcium et de polysaccharides contenant de l'acide glucuronique et/ou de l'acide iduronique
DE10340542A1 (de) * 2003-09-01 2005-03-24 Henkel Kgaa Mund- und Zahnpflegemittel
WO2006133747A1 (fr) * 2005-06-15 2006-12-21 Henkel Kommanditgesellschaft Auf Aktien Agents a effet remineralisant destines au nettoyage et a l'hygiene des dents et de la bouche

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012005593A2 (fr) 2010-07-09 2012-01-12 Stichting Glass For Health Compositions d'apatite

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