EP1988973A1 - Sels de calcium de forme essentiellement plate difficilement solubles dans l'eau et/ou materiaux composites les comprenant - Google Patents

Sels de calcium de forme essentiellement plate difficilement solubles dans l'eau et/ou materiaux composites les comprenant

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Publication number
EP1988973A1
EP1988973A1 EP06818280A EP06818280A EP1988973A1 EP 1988973 A1 EP1988973 A1 EP 1988973A1 EP 06818280 A EP06818280 A EP 06818280A EP 06818280 A EP06818280 A EP 06818280A EP 1988973 A1 EP1988973 A1 EP 1988973A1
Authority
EP
European Patent Office
Prior art keywords
composite materials
calcium salts
protein
particles
acids
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06818280A
Other languages
German (de)
English (en)
Inventor
Lothar Kintrup
Burkhard Eschen
Martina Hermann
Holger Franke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Sustech GmbH and Co KG
Original Assignee
Henkel AG and Co KGaA
Sustech GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA, Sustech GmbH and Co KG filed Critical Henkel AG and Co KGaA
Publication of EP1988973A1 publication Critical patent/EP1988973A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
    • A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
    • A23G3/36—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by the composition containing organic or inorganic compounds
    • A23G3/362—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by the composition containing organic or inorganic compounds containing inorganic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
    • A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
    • A23G3/36—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by the composition containing organic or inorganic compounds
    • A23G3/44—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by the composition containing organic or inorganic compounds containing peptides or proteins
    • 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
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0254—Platelets; Flakes
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P19/00—Drugs for skeletal disorders
    • A61P19/08—Drugs for skeletal disorders for bone diseases, e.g. rachitism, Paget's disease
    • 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
    • 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
    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm

Definitions

  • the invention relates to sparingly water-soluble calcium salts and / or composite materials, comprising these, characterized in that 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 below 1000 nm, preferably below 300 nm, wherein the calcium salt particles are predominantly platelike.
  • the calcium salts and / or composite materials according to the invention, comprising these calcium salts are particularly suitable for promoting the restoration of bone and tooth material, in particular enamel and dentin, owing to their composition and fine structure.
  • Calcium phosphate salts have long been added to the dentifrice and dentifrice formulations both as abrasive components and to promote remineralization of the enamel. This is especially true for hydroxyapatite and fluorapatite as well as for amorphous calcium phosphates and for brushite (dicalcium phosphate dihydrate). Also calcium fluoride has been described several times as a component of dentifrices and as a component for strengthening the enamel and for caries prophylaxis.
  • the enamel and the supporting tissue of the bones consist predominantly of the mineral hydroxylapatite.
  • hydroxyapatite deposits in an orderly fashion on the protein matrix in the bone or tooth, which consists predominantly of collagen.
  • the formation of the hard and resilient mineral structures is controlled by the so-called matrix proteins, which are formed in addition to collagen by other proteins that attach to the collagen and so a structured mineralization process, which is also called biomineralization effect.
  • Bone substance is a combination of skieroproteins and platelet-like hydroxyapatite.
  • bone substitutes which promote the natural biomineralization process, play an important role.
  • Such agents are also required for coating implants in order to achieve cohesive connections between bone and implant, with which tensile forces can also be transmitted.
  • coatings with a high bioactivity resulting in a effective composite osteogenesis.
  • hydroxyapatite is usually applied to implants.
  • a disadvantage of this approach in addition to the often insufficient acceleration of the biomineralization process, the chipping of the hydroxyapatite layers and their unsatisfactory chemical stability.
  • liquid-applied bone replacement materials are needed.
  • a particularly small particle size is required, which can not be achieved in the conventional bone substitutes in a satisfactory manner.
  • the previously available liquid applicable bone replacement materials have at best a biocompatible, possibly resorbable action due to the coarsely crystalline inorganic components and the lack of bioanalogous organic components.
  • natural biomineralization and thus bone growth directly promoting, osteoinductive, osteoconductive or osteostimulating materials are desired.
  • Dentin is made up of about 30 percent protein (essentially collagen) and 70 percent of mineral substances (mainly hydroxyapatite), whereas enamel is about 95 percent hydroxyapatite and about 5 percent from proteins.
  • Composite materials of the type described are accessible by synthetic routes, such as. By B. Flautre et al. in J. Mater. See: Mater. Described in Medicine 7 (1996), 63. However, in these composites, the grain size of the calcium salts is above 1000 nm, which is too large to achieve a satisfactory biological effect as a remineralizer.
  • RZ Wang et al. J. Mater. Be. Lett. 14 (1995), 490 describes a preparation process for a composite material of hydroxyapatite and collagen in which hydroxyapatite having a particle size in the range of 2 to 10 nm is deposited in uniformly distributed form on the collagen matrix.
  • the composite material is said to have better biological effectiveness than other hydroxyapatite-collagen composites known in the art due to the finely divided hydroxyapatite.
  • RZ Wang et al. composite material described insufficient the need for composite materials which mimic the composition and the microstructure of natural bone and tooth material and are fully satisfactory for the remineralization of these natural materials.
  • 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 dispersion in the presence of the agglomeration inhibitor, eg a protective collide or surfactant, is redispersed.
  • an agglomeration inhibitor or dispersion in the presence of the agglomeration inhibitor eg a protective collide or surfactant
  • WO 01/01930 discloses composite materials which are composed of nanoparticulate sparingly soluble calcium salts and protein component and which have a remineralizing effect on enamel and dentin. Gelatins of type A or B are used for this purpose.
  • the invention relates to sparingly soluble calcium salts and / or composite materials comprising these, characterized in that 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, preferred less than 300 nm, and the particles are rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped.
  • the particles of the calcium salts, which are composed of individual crystallites according to the invention can be present in the form of platelets and / or rods depending on the conditions of the production process.
  • Predominantly platelet-shaped means that at least 50%, preferably at least 70%, particularly preferably at least 80% of the particles are present in the form of platelets. Particularly preferably, the particles have a substantially platelet-like form.
  • the calcium salts or composite materials according to the invention comprising these, with the predominantly platelet-like calcium particles of the structure of the bone substance in vivo, which is also composed of plates, are particularly similar.
  • This has the particular advantage that, because of the similarity of the form with the biological apatites (for example bone or dentin apatite), they have a particularly good ability for re-mineralization and neo-mineralization, so that the process of biomineralization can take place even faster and better.
  • a further advantage of the invention is that the sparingly water-soluble calcium salts or composite materials comprising these having a predominantly platelet-like structure of the calcium salts have improved biocompatibility.
  • the particle diameter is to be understood here as the diameter of the particles (crystallites or particles) in the direction of their greatest length expansion.
  • the mean particle diameter is to be understood as a value which is averaged over the total amount of the composite. It is according to the invention below 1000 nm, preferably below 300 nm.
  • the average particle diameter of the crystallites is in the range of 10 to 150 nm, and more preferably, the crystallites are in the range of 2 to 50 nm in thickness and 10 to 150 nm in length.
  • thickness is the smallest diameter the crystallites understand, by length their largest diameter.
  • the determination of the particle diameter of the crystallites can be determined by methods familiar to the person skilled in the art, in particular by the evaluation of the broadening of the reflections observed during X-ray diffraction.
  • the evaluation by Fit method for example, the Rietveld method.
  • the crystallites preferably have a thickness of 2 to 15 nm and a length of 10 to 50 nm; more preferably, a thickness of 3 to 11 nm and a length of 15 to 25 nm, on.
  • the calcium salts according to the invention and / or the composite materials comprising these with an average particle diameter of the particles in the range of less than 1000 nm, preferably less than 300 nm.
  • the 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 comprising these, platelet-shaped particles having a width in the range of 5 to 150 nm and a length in the range of 10 to 150 nm and a height (thickness) of 2 to 50 nm.
  • 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 tilt the image plane of the sample several times in different positions and to determine the dimensions of the particles in the setting which is characterized by the highest contrast / highest density and the smallest dimension of the particles. The shortest extent then corresponds to the height of the particles.
  • 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, more preferably between 1 and 2, for example 1, 2 (Length 60 nm, width 50 nm) or 1, 5 (length 80, width 40 nm).
  • the platelet-like shape of the particles is formed by the ratio of length to width. If the ratio between length and width is significantly greater than 4, rod-shaped particles are more likely.
  • the advantage of the platelet-shaped particles with a ratio of preferably 1 to 2 lies in the fact that these particles have a length to width ratio which is particularly similar to the natural bone material and therefore a particularly good and biocompatible re-or neomineralization of the tooth material (dentin and enamel). exhibit.
  • 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 * 1O '1S 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 ,
  • the area of the particles is determined according to the usual geometric calculation methods.
  • calcium salt should be understood as those salts which are soluble at 2O 0 C to less than 0.1 wt .-% (1g / l) in water.
  • suitable salts are, for example, calcium hydroxyphosphate (Ca 5 [OH (PO 4 ) 3 ]) or hydroxylapatite, calcium fluorophosphate (Ca 5 [F (PO 4 J 3 ]) or fluoroapatite, fluorine-doped hydroxylapatite of composition Ca 5 (PO 4 MOH 1 F) and calcium fluoride (CaF 2 ) or fluorite or fluorspar and other calcium phosphates such as di-, tri- or tetracalcium phosphate (Ca 2 P 2 O 7 , Ca 3 (PO 4 J 2 , Ca 4 P 2 O 9 , oxyapatite (Cai 0 (PO 4 ) 6 O) or non-stoichiometric hydroxyapatite (Ca 5 - * (
  • carbonate-containing calcium phosphates eg Ca 5 - V 5 (x + y + z> (PO 4) 3. X. Z (HPO 4) x (CO 3) z (OH) Vy), calcium hydrogen phosphate (eg CaH (PO 4) 2 H 2 O) and octacalcium phosphate (eg, Ca 8 H 2 (PO 4 ) 6 * 5H 2 O).
  • the calcium salt one or more salts in the mixture selected from the group of phosphates, fluorides and fluorophosphates, which optionally may additionally contain hydroxyl and / or carbonate groups, may preferably be contained in the composite materials according to the invention. Particularly preferred are hydroxyapatite and fluoroapatite.
  • the crystallites and / or particles of the calcium salts which are free or present in the composite materials according to the invention, may be enveloped by one or more surface modifiers.
  • the surface modifier is adsorbed on the surface of the crystallites and / or particles and changes them so that the dispersibility of the calcium salt increases and the agglomeration of the crystallites and / or particles is reduced or substantially prevented.
  • the structure of the sparingly water-soluble calcium salts and in particular of the composite materials and the loading of the polymer component with the calcium salt can be influenced by a surface modification. In this way, when applying the composite materials in remineralization processes, it is possible to influence the course and speed of the remineralization process.
  • Surface modifiers are to be understood as substances which physically adhere to the surface of the finely divided particles but do not react chemically with them.
  • the individual surfaces of the surface modifiers adsorbed on the surface are substantially free of intermolecular bonds with each other.
  • Surface modifiers are to be understood in particular as dispersants. Dispersants are also known to the person skilled in the art, for example, under the terms emulsifiers, protective colloids, wetting agents, detergents, etc.
  • Suitable surface modifiers are, for example, emulsifiers of the nonionic surfactant type from at least one of the following groups:
  • Fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products; - Alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs;
  • Partial esters based on linear, branched, unsaturated or saturated C 6/22 fatty acids
  • Lauryl glucoside and polyglucosides (eg, cellulose);
  • the addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products. These are homolog mixtures, whose average degree of alkoxylation corresponds to the ratio of the molar amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out.
  • C ⁇ / 18 alkyl mono- and oligoglycosides their preparation and their use are known in the art. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms.
  • glycoside radical both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of preferably approximately 8 are suitable.
  • the degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.
  • anionic emulsifiers are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, alkyl ether sulfates such as fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, Mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfo-succinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarc
  • zwitterionic surfactants can be used as emulsifiers.
  • Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylamino-propyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and Alkyl-3-carboxylmethyl-3-hydroxyethylimidazoline having in each case 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethyl- hydroxyethylcarboxymethylglycinat.
  • betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylamino-propyl-N, N-dimethylammonium glycinates
  • fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.
  • ampholytic surfactants are surface-active compounds which, apart from a C / i ⁇ alkyl or acyl group containing 8 in the molecule at least one free amino group and at least one -COOH or -SO3H group and are capable of forming inner salts.
  • ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group.
  • Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12 / 18-acylsarcosine.
  • quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.
  • suitable protective colloids are z.
  • B. natural water-soluble polymers such as gum arabic, starch, water-soluble derivatives of water-insoluble polymeric natural products such.
  • cellulose ethers such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose or modified carboxymethyl cellulose, hydroxyethyl starch or hydroxypropyl guar, and synthetic water-soluble polymers such.
  • polyvinyl alcohol polyvinylpyrrolidone, polyalkylene glycols, polyaspartic acid and polyacrylates.
  • the surface modifiers are used in a concentration of 0.1 to 50, but preferably 1 to 20 wt .-%, based on the calcium salts.
  • Particularly suitable surface-modifying agents are, above all, the nonionic surfactants in an amount of from 1 to 20% by weight, based on the weight of the calcium salt.
  • the nonionic surfactants of the type of the alkyl C 8 -C 16 (oligo) glucosides and of the ethoxylates of the hardened castor oil have proved to be particularly effective.
  • the composite materials according to the invention comprise a. sparingly soluble calcium salts in water, wherein the calcium salts are in the form of individual crystallites or in the form of particles comprising a plurality of said crystallites, having an average particle diameter in the range of less than 1000 nm, preferably less than 300 nm, and b. a polymer component, wherein the particles in the composite material are rod-shaped and / or platelet-shaped, preferably predominantly platelet-shaped.
  • Composite materials are composites which comprise the components mentioned under a) and b) and represent microscopically heterogeneous, macroscopically homogeneous aggregates, and in which the crystallites or particles of the calcium salts are associated with the framework of the polymer component.
  • the proportion of the polymer components in the composite materials in the composite material is between 0.1 and 80 wt .-%, preferably between 10 and 60, in particular between 30 and 50 wt .-% based on the total weight of the composite material.
  • the composite materials according to the invention are thus structured composite materials, in contrast to that described in R. Z. Wang et al. described composite of hydroxyapatite and collagen, in which evenly distributed hydroxyapatite nanoparticles are present.
  • Another significant difference between the subject matter of the present invention and the prior art is the size and morphology of the inorganic component.
  • the methods described in R. Z. Wang et al. Hydroxylapatite particles present in the described hydroxyapatite-collagen composite have a size of 2-10 nm. Hydroxylapatite particles in this size range are assigned to the range of amorphous or partially X-ray amorphous substances.
  • composite materials are that they do not tend to aggregate so much that they can be better processed in the production process. In particular, an improved dispersibility of the composite is observed.
  • the polymer component is selected from a protein component, polyelectrolytes and polysaccharides.
  • a preferred embodiment of the invention is that polyelectrolytes are used as the polymer component.
  • Suitable polyelectrolytes for the purposes of the invention are polyacids and polybases, it being possible for the polyelectrolytes to be biopolymers or else synthetic polymers.
  • the inventive compositions contain, for example, one or more polyelectrolytes selected from
  • Polyamino acids such as. B. polyaspartic acids
  • Nucleic acids such as. B. DNA and RNA
  • Polyvinylamines and derivatives of the aforementioned substances in particular amino and / or carboxyl derivatives.
  • polymers bearing carboxylate groups are suitable.
  • Particularly preferred 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.
  • glucuronic acid preferably D-glucuronic acid, and / or iduronic acid, in particular L-iduronic acid.
  • a constituent of the carbohydrate skeleton is formed by glucuronic acid or iduronic acid.
  • the iduronic acid isomeric to glucuronic acid has the other configuration at the C5 carbon atom of the ring.
  • Glucuronic acid and / or iduronic acid-containing polysaccharides are preferably to be understood as meaning those polysaccharides which contain glucuronic acid and / or iduronic acid in a molar ratio of 1:10 to 10: 1, in particular from 1: 5 to 5: 1, particularly preferably 1: 3 to 2: 1, based on the sum of the other monosaccharide building blocks of the polysaccharide.
  • 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 referred to as mucopolysaccharides), microbially produced xanthan gum or welan or gum arabic, which is obtained from acacia.
  • An advantage of the composite materials according to the invention is the particular stability in aqueous systems even without the addition of dispersing aids such as, for example, polyhydric alcohols (such as glycerol or polyethylene glycols).
  • dispersing aids such as, for example, polyhydric alcohols (such as glycerol or polyethylene glycols).
  • the polymer component is selected from a protein component, preferably from proteins, protein hydrolysates and their derivatives.
  • proteins are basically all proteins, irrespective of their origin or their production.
  • proteins of animal origin are keratin, elastin, collagen, fibroin, albumin, casein, whey protein, placental protein.
  • Preferred according to the invention from these are collagen, keratin, casein, whey protein, proteins of plant origin such as wheat and wheat germ protein, rice protein, soy protein, oat protein, pea protein, potato protein, almond protein and yeast protein may also be preferred according to the invention.
  • 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.
  • proteins such as, for example, collagen, elastin, casein, keratin, almond, potato, wheat, rice and soy protein
  • hydrolytic enzymes are suitable, such as. B. alkaline proteases.
  • Further suitable enzymes and enzymatic hydrolysis processes are described, for example, in K. Drauz and H. Waldmann, Enzyme Catalysis in Organic Synthesis, VCH Verlag, Weinheim 1975.
  • gelatin which may have molecular weights in the range of 15000 to 250000 D.
  • Gelatin is a polypeptide obtained primarily by hydrolysis of collagen under acidic (gelatin type A) or alkaline (gelatin type B) conditions.
  • the gel strength of the gelatin is proportional to its molecular weight, that is, a more hydrolyzed gelatin gives a lower viscosity solution.
  • the gel strength of the gelatin is given in Bloom numbers. In the enzymatic cleavage of the gelatin, the polymer size is greatly reduced, resulting in very low Bloom numbers.
  • the protein hydrolysates used in cosmetics are preferably those having an average molecular weight in the range from 600 to 4000, particularly preferably from 2000 to 3500.
  • Overviews of the preparation and use of protein hydrolyzates are described, for example, by G. Schuster and A. Domsch in soaps oils Fette Wachse 108, (1982) 177 and Cosm.Toil. 99, (1984) 63, by H.W. Steisslinger in Parf.Kosm. 72, (1991) 556 and F. Aurich et al. in Tens.Surf.Det. 29, (1992) 389 appeared.
  • protein hydrolysates of collagen, keratin, casein and vegetable proteins are used, for example those based on wheat gluten or rice protein, the production of which is described in German Patent DE 19502167 C1 and DE 19502168 C1 (Henkel).
  • protein hydrolyzate derivatives are to be understood as meaning chemically and / or chemoenzymatically modified protein hydrolyzates, for example those with the INCI names Sodium Cocoyl Hydrolyzed Wheat Protein, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein, Potassium Cocoyl Hydrolyzed Collagen, Potassium Undecylenoyl Hydrolyzed Collagen and Laurdimonium Hydroxypropyl Hydrolyzed Collagen Known compounds.
  • Preferably derivatives of protein hydrolysates of collagen, keratin and casein and vegetable protein hydrolysates are used according to the invention such.
  • B. Sodium Cocoyl Hydrolyzed Wheat Protein or Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein.
  • the protein component can be formed in each of the composite materials according to the invention by one or more substances selected from the group of proteins, protein hydrolysates and protein hydrolyzate derivatives.
  • Preferred protein components are all structure-forming proteins, protein hydrolyzates and protein hydrolyzate derivatives, which are understood as meaning protein components which due to their chemical constitution form specific three-dimensional spatial structures familiar to the person skilled in the art of protein chemistry under the terms secondary, tertiary or even quaternary structure are.
  • the protein component of the composite materials is selected from collagen, gelatin, casein and their hydrolysates, preferably gelatin, particularly preferably gelatin of the type A, B or AB, in particular gelatin of the acid bone type.
  • gelatins of the type AB can be used, which are also known under the name “acid-bone” or “acid process ossein” gelatine, and are prepared from ossein by highly acidic process conditions.
  • Ossein as a collagen-containing starting material for the preparation of gelatin of type AB "acid bone” or “acid process Ossein", is prepared as an extract from minced bones, especially bovine bone, possibly after degreasing and drying for one or more days (preferably at least one Week and more) in aqueous solution, preferably cold acid, preferably dilute acid (eg hydrochloric acid), are incorporated to remove the inorganic bone components, especially hydroxyapatite and calcium carbonate.
  • aqueous solution preferably cold acid, preferably dilute acid (eg hydrochloric acid)
  • the ossein collagen is denatured and released by a digestion process in which the material is treated under strongly acidic conditions.
  • the preparation of the gelatin from said raw materials takes place by multiple extraction with aqueous solutions.
  • the pH of the solution can be adjusted before the extraction process.
  • Particularly preferred are several extraction steps with water or aqueous solutions with increasing solvent temperature.
  • Composite materials which can be obtained from a sparingly water-soluble calcium salt with gelatin of the type AB (acid-bone) are particularly suitable for use in applications according to the invention.
  • the composite materials containing AB type gelatin, "acid bone” have a particularly strong neomineralization: composite materials which can be obtained from a sparingly water-soluble calcium salt with AB-type gelatin (acid-bone) thus particularly suitable for use in bones and teeth (see examples) .
  • the composite materials according to the invention are therefore in comparison to the said composites preferred for use in particular for the rapid closure of dentinal tubules, for remineralization of the tooth material, for use in teeth and bones for the prevention and / or treatment of damage to external influences, in particular body-related, chemical, physical and / or microbiological Art are, for example, erosion, primary lesions and initial caries and caries prophylaxis, to improve the resistance to mechanical stress and generally suitable for improving the cleaning properties of the teeth and dental health generally.
  • the sparingly water-soluble calcium salts and composite materials according to the invention comprising these, can be prepared by precipitation reactions from aqueous solutions of water-soluble calcium salts and aqueous solutions of water-soluble phosphate and / or fluoride salts, the precipitation in the case of the composite materials according to the invention being carried out in the presence of polymer components.
  • the preparation of the composite materials according to the invention is preferably carried out in such a way that the polymer components in pure, dissolved or colloidal form of the neutral or alkaline aqueous phosphate and / or fluoride salt solution or the neutral or alkaline solution of the calcium salt are added before the precipitation reaction.
  • the polymer components may be presented in pure, dissolved or colloidal form and then added sequentially in any order or simultaneously with the neutral or alkaline calcium salt solution and the neutral or alkaline phosphate and / or fluoride salt solution.
  • Neutral solutions are understood to mean solutions having a pH of between about 6.5 and about 7.5.
  • the assembly of the individual components can in principle be carried out in all possible orders.
  • the alkalizing agent used is preferably ammonia.
  • a further variant of the preparation process according to the invention comprises precipitation from an acidic solution of a water-soluble calcium salt together with a stoichiometric amount of a water-soluble phosphate and / or fluoride salt or of an acidic solution of hydroxyapatite having a pH below 5 at a pH below 3, by raising the pH with aqueous alkali or ammonia in the presence of the polymer components.
  • a further variant of the process consists of nanoparticulate calcium salts in pure or dispersed form or dispersions of nanoparticulate calcium salts prepared by precipitation reactions from aqueous solutions of water-soluble calcium salts and aqueous solutions of water-soluble phosphate and / or fluoride salts with the polymer components, the latter preferably in dissolved or dispersed form, added, wherein the addition of any order can be selected.
  • the solution or dispersion of the polymer component is initially charged and a dispersion of the nanoparticulate calcium salt is added.
  • the resulting dispersion of the composite material as required by those skilled in known methods such. B. filtration or centrifugation from the solvent and the other constituents of the reaction mixture and separated by subsequent drying, for. B. by freeze-drying, be isolated in solvent-free form.
  • water is preferably used in all manufacturing processes, but in individual steps of the production, organic solvents such.
  • organic solvents such as mono- or polyhydric alcohols having 1 to 4 carbon atoms or glycerol can be used.
  • the preparation of the calcium salts or composite materials according to the invention comprising these, and in particular those composite materials with a protein component selected from collagen, casein or gelatin, preferably AB type gelatin, with surface-modified crystallites and / or particles of the calcium salts, can be prepared by analogous precipitation methods as described above however, the precipitation of the nanoparticulate calcium salts or the composite materials occurs in the presence of one or more surface modifiers.
  • the surface-modified nanoparticulate calcium salts are preferably first produced by a precipitation reaction between aqueous solutions of calcium salts and aqueous solutions of phosphate and / or fluoride salts in the presence of the surface modifiers. These can then be purified from by-products of the reaction mixture, eg. B. by concentration under reduced pressure and subsequent dialysis. By removing the solvent, a dispersion of the surface-modified calcium salt having a solid content can be additionally prepared as desired.
  • the Composite material formed from surface-coated calcium salt and polymer components is not critical, and if necessary afterreaction at elevated temperature, preferably in the range between 50 and 100 0 C and for a period of 1 to 100 minutes, the Composite material formed from surface-coated calcium salt and polymer components.
  • the precipitation of the calcium salt or of the composite material is carried out at a pH of between 5 and 9, preferably between 6 and 8, more preferably around 7.
  • a solution of a calcium salt with the polymer component is preferably initially introduced to form the preferred composite material according to the invention, and a phosphate solution is slowly added, the pH being between 5 and 9, preferably between 6 and 8, particularly preferably around 7.
  • the pH is kept constant during the addition of the phosphate solution by adding appropriate amounts of aqueous base.
  • the calcium salts or composite materials according to the invention comprising these, and in particular such composite materials with a protein component selected from collagen, casein or gelatin, particularly preferably gelatin of type A, B or AB, in particular gelatin of the acid bone type, in particular those of hydroxyapatite, fluorapatite and Calcium fluoride, are useful as a mineralizing component for the preparation of compositions for cleaning and / or care of the teeth.
  • the structured form in particular of the preferred composites, and the particle size of the calcium compounds contained therein, the effect of strengthening of the enamel and the closure of lesions and dentinal tubules can be done very quickly and completely.
  • calcium salts or composite materials according to the invention including these, and in particular such composite materials with a protein component selected from collagen, casein or gelatin, more preferably gelatin of the type A, B or AB 1, in particular gelatin of the acid bone type, as neo- or remineralizing Components are used in compositions for strengthening the enamel.
  • calcium salts or composite materials comprising these, and in particular of such composite materials with a protein component selected from collagen, casein or gelatin, more preferably gelatin of the type A, B or AB, in particular gelatin of the acid bone type, is effected as the biomineralization-inducing or promoting component for the treatment of tooth or bone defects.
  • the calcium salts or composite materials according to the invention comprising these, and in particular such composite materials with a protein component selected from collagen, casein or gelatin, particularly preferably gelatin of type A, B or AB, in particular gelatin of the acid bone type, or compositions containing these also to be used for coating implants.
  • a use of the calcium salts or composite materials according to the invention, comprising these, and in particular those composite materials having a protein component selected from collagen, casein or gelatin, particularly preferably gelatin of the type A, B or AB, in particular gelatin of the acid bone type, or compositions containing at least this, for smoothing the surface of teeth and / or bone is also preferred.
  • the calcium salts or composite materials according to the invention comprising these, and in particular those composite materials having a protein component selected from collagen, casein or gelatin, particularly preferably gelatin of the type A, B or AB, in particular gelatin of the acid bone type, in particular of hydroxyapatite and fluorapatite, can induce or promote biomineralization in bone tissue. They are therefore further suitable as a biomineralizing component for the preparation of compositions for the recovery or new formation of bone material, such as. B. of compositions for the treatment of bone defects and bone burs as well as to promote the ingrowth of implants.
  • the invention further relates to the use of the calcium salts or composite materials according to the invention, comprising these, and especially those composite materials having a protein component selected from collagen, casein or gelatin, particularly preferably gelatin of the type A, B or AB, in particular gelatin of the acid type bone, for the protection and / or for the therapeutic and / or preventive treatment of teeth and / or bones before or in case of damage due to external influences, in particular body-related, chemical, physical and / or microbiological nature, in particular for prevention and repair of erosions on bones and teeth, in particular enamel, care of the enamel, as well as for the protection of the teeth from attack by acids, in particular by bacterial activity or by action of acids from food, to protect against demineralization of the teeth, to seal fissures, to protect in front and / or for repairing primary lesions and / or initial caries in the enamel, as well as for smoothing the tooth surface, for caries prevention, for improving the cleanability, for the mechanical resistance of the teeth and for dental health in general.
  • the calcium salts according to the invention and preferably the composite materials comprising them, and in particular such composite materials with a protein component selected from collagen, casein or gelatin, particularly preferably gelatin of the type A, B or AB, in particular gelatin of the acid bone type, used against attacks by acids.
  • the term acids is to be understood here as meaning both the intrinsic acids and the extrinsic acids.
  • the damage caused by intrinsic acids relates in particular to medical conditions associated with contact of gastric acid with the oral region especially in case of belching, regurgitation, heartburn or vomiting, also in connection with pathological eating disorders, such as bulimia in particular.
  • Particularly suitable is the use in attack by extrinsic acids, in particular due to bacterial activity or the action of acids from food.
  • the calcium salts according to the invention and preferably the composite materials comprising them, and in particular such composite materials with a protein component selected from collagen, casein or gelatin, more preferably gelatin type A, B or AB, in particular gelatin type acid bone, are therefore also therapeutically the repair of damage, in particular of erosions, on bones and teeth, especially on the enamel.
  • the calcium salts according to the invention and preferably the composite materials comprising these, and in particular such composite materials with a protein component selected from collagen, casein or gelatin, more preferably gelatin type A, B or AB, in particular gelatin type acid bone, for protection and / or for repairing primary lesions and / or initial caries in enamel and for sealing fissures.
  • fissures i.e., the crevasse-like recesses on the chewing surfaces of the molars and molars
  • fissures i.e., the crevasse-like recesses on the chewing surfaces of the molars and molars
  • the use of the calcium salts according to the invention, and preferably the composite materials comprising these, in particular those with a protein component selected from collagen, casein or gelatin, more preferably gelatin type A, B or AB, in particular gelatin of the type acid bone, leads to a better mechanical resistance, in particular that the extent of micro-scratches, craters or mechanical abrasion is reduced.
  • the use of the invention leads to a better resistance to mechanical stress of the teeth, which can be caused in addition to chewing in particular by vigorous brushing. Damage or erosion of softened enamel can thus be avoided.
  • the composite materials preferably the composite materials, in particular those with a protein component selected from collagen, casein or gelatin, more preferably gelatin type A, B or AB, in particular gelatin of the type Acid bone, these are themselves or compositions containing them, thus generally used for improving the cleanability of teeth and dental health.
  • compositions for cleaning and care of the teeth can be present for example in the form of pastes, liquid creams, gels or mouthwashes. Even in liquid preparations, the composite materials according to the invention are readily distributed, remain stably dispersed and do not tend to sediment.
  • the content of the sparingly water-soluble calcium salts and / or the composite materials comprising these, preferably the composite materials, in particular those with a protein component selected from collagen, casein or gelatin, particularly preferably gelatin of the type A, B or AB, in particular gelatin of the acid bone type, in the oral and dental care compositions according to the invention is 0.01 to 10 wt .-%, preferably 0.01 to 2 wt .-%, based on the total weight of the composition.
  • the oral and dental care compositions according to the invention can furthermore contain 0.1 to 9% by weight, in particular 2 to 8% by weight, of at least one cleaning agent.
  • Cleaning agents are among the essential ingredients of a toothpaste and, depending on their intended function, are present alone or in combination with other cleansers or polishes. They are used for the mechanical removal of the uncalcified plaque and should ideally lead to the gloss of the tooth surface (polishing effect) with minimal abrasion (abrasion effect) and damage to the enamel and the dentin.
  • the abrasion behavior of the polishing agents and cleaning bodies is essentially determined by their hardness, particle size distribution and surface structure. When selecting suitable cleaning bodies, those which have a minimum abrasion effect, in particular, are therefore preferably selected.
  • cleaning materials are predominantly used which have small particle sizes, are largely free of sharp corners and edges and whose hardness and mechanical properties do not stress the tooth or the tooth substance too much.
  • polishing agents are used as cleaning or polishing agents.
  • Particularly advantageous is the use of very finely divided polishing agent having a mean particle size of 1 - 200 .mu.m, preferably 1-50 .mu.m and in particular 1-10 microns.
  • the polishing agents according to the invention may be selected from silicic acids, aluminum hydroxide, aluminum oxide, silicates, organic polymers or mixtures thereof.
  • so-called metaphosphates, alkaline earth metal carbonates or hydrogencarbonates and also calcium-containing polishing components to be present in the compositions according to the invention.
  • silicas as polishing agents in toothpastes or liquid dentifrices.
  • silicic acid polishing agents a distinction is generally made between gel silicic acids, hydrogel silicic acids and precipitated silicas.
  • Precipitated and gel silicas are particularly preferred according to the invention, since they can be widely varied in their preparation and are particularly well tolerated with fluoride active ingredients. They are also particularly suitable for the production of gel or liquid toothpastes.
  • Gel silicas are produced by the reaction of sodium silicate solutions with strong, aqueous mineral acids to form a hydrosol, aging to the hydrogel, washing and subsequent drying. If the drying takes place under mild conditions to water contents of 15 to 35 wt .-%, so-called hydrogel silicic acids are obtained, as described for example in US 4,153,680. Drying of these hydrogel silicic acids to water contents below 15% by weight results in an irreversible shrinkage of the previously loose structure to the dense structure of the so-called xerogel. Such Xerogelkieselklaren are known for example from US 3,538,230.
  • a second, preferably suitable group of silica polishing agents are the precipitated silicas. These are obtained by precipitation of silica from dilute alkali silicate solutions by addition of strong acids under conditions where aggregation to the sol and gel can not occur. Suitable processes for the preparation of precipitated silicas are described, for example, in DE-OS 25 22 586 and in DE-OS 31 14 493.
  • Particularly suitable according to the invention is a precipitated silica prepared according to DE-OS 31 14 493 with a BET surface area of 15-110 m 2 / g, a particle size of 0.5 to 20 ⁇ m, where at least 80% by weight of the primary particles are below 5 intended to be within microns and a viscosity in a 30% glycerin-water (1: 1) dispersion 30 to 60 Pa s (2O 0 C) in an amount of 10-20 wt .-% of the tooth paste.
  • Particularly suitable precipitated silicas of this type have rounded corners and edges and are, for example, under the trade designation Sident 12 DS ® from Degussa.
  • the silicas of the type Zeodent ® Huber Corp., Tixosil® Rhodia and other Sorbosil® types are used in the agents are particularly preferred Zeodent ® 113 Tixosil ® 123 and Sorbos ⁇ l ® AC39
  • S ⁇ pernat ® 22 LS or S ⁇ pemat ® 320 DS by Degussa be mentioned
  • As alumina polishing agent is preferably a weakly calcined clay having a content of ⁇ - and ⁇ -Alum ⁇ n ⁇ umox ⁇ d in an amount of about 0.01 to 5 wt -%, preferably 0.1 to 2 wt -%, based on the total weight of through
  • Suitable weakly calcined clays are prepared by calcination from aluminum hydroxide aluminum hydroxide is calcined in the at temperatures above 1200 0 C thermodynamically stable Ct-Al 2 O 3 on occurring at temperatures between 400 and 1000 ° C, thermodynamically unstable Al 2 O 3 -Mod ⁇ fikat ⁇ onen is referred to as gamma forms (cf. Ullmann, Enzyclopadie der ischen Chemie, 4 Edition (1974), Volume 7, page 298) By selecting the temperature and the time period in the calcination can be the degree of calcination, ie the conversion into the thermodynamically stable Ct -Al 2 O 3 is adjusted to any desired level.
  • the dentin abrasion (RDA) of the less calcined aluminas to be used according to the invention with a proportion of 10-50% by weight of ⁇ -Al 2 O 3 is only 30-60% of the dentin abrasion of a strongly calcined, pure Ct-Al 2 O 3 (measured in a standard toothpaste with 20% by weight of clay as the sole polishing agent)
  • the ⁇ -Al 2 O 3 can be stained red with an aqueous ammoniacal solution of Alizann S (1, 2-dihydroxy-9,10-anthraquinone-4-sulfonic acid) of the Dyeing as a measure of the degree of calcination or for the proportion of 5-Al 2 O 3 in a calcined clay choose:
  • Suitable weakly calcined alumina with a content of 10-50 wt .-% ⁇ -Al 2 O 3 can be prepared by this method, pale to deep pink stain.
  • Alumina abrasives of various degrees of calcination, fineness and bulk densities are commercially available, e.g. the "Poliertonerden” of the company Giulini-Chemie or ALCOA.
  • a preferred suitable grade "polishing clay P10 finest” has an agglomerate size of less than 20 ⁇ m, an average primary crystal size of 0.5-1.5 ⁇ m and a bulk density of 500-600 g / l.
  • silicates as polishing agent components may also be preferred according to the invention. They are used in particular in modern practice as a cleaning body.
  • silicates which can be used according to the invention are aluminum silicates and zirconium silicates.
  • the sodium aluminum silicate of the empirical formula Na 12 (AIO 2 ) 12 (SiO 2 ) i 2 ⁇ 7H 2 O may be suitable as a polishing agent, such as, for example, the synthetic zeolite A.
  • water-insoluble metaphosphates are especially sodium metaphosphate, calcium phosphate such as tricalcium phosphate, calcium hydrogen phosphate, calcium hydrogen phosphate dihydrate and calcium pyrophosphate.
  • magnesium carbonate, magnesium hydrogen phosphate, trimagnesium phosphate or sodium bicarbonate can be used as a polishing agent, in particular as a mixture with other polishing agents.
  • Calcium phosphate dihydrate (CaHPO 4 .2H 2 O). Calcium phosphate dihydrate occurs in nature as brushite and is available as a polishing agent commercially in suitable particle sizes of 1 to 50 microns.
  • oral and dental care preparations are preferred for supporting the remineralization process by the sparingly water-soluble calcium salt and / or the composite materials comprising these, in addition to 0.1 to 10 wt .-%, preferably 0.1 to 5 wt .-% and in particular 0.1 to 3 wt .-% of a Remineralisations dires component, each based on the total weight of the composition.
  • the Remineralisations foundeds component promotes remineralization of the enamel and the closure of dental lesions in the compositions of the invention and is selected from fluorides, microparticulate phosphate salts of calcium such.
  • Calcium glycerophosphate calcium hydrogen phosphate, hydroxyapatite, fluoroapatite, F-doped hydroxyapatite, dicalcium phosphate dihydrate and calcium fluoride.
  • magnesium salts such as magnesium sulfate, magnesium fluoride or magnesium monofluorophosphate have remineralizing.
  • Remineralization promoting components preferred according to the invention are magnesium salts.
  • Suitable embodiments of the oral and dental care products according to the invention are solid, liquid or semi-liquid toothpastes and tooth gels.
  • the oral and dental care products according to the invention contain additional toothpaste ingredients, such as surfactants, humectants, binders, flavorings and active substances against tooth and gum diseases.
  • surface-active surfactants or surfactant mixtures are usually used. They promote the rapid and complete dissolution and distribution of dental creams in the oral cavity and at the same time support the removal of mechanical plaque, especially in those places that are difficult to access with a toothbrush. In addition, they promote the incorporation of water-insoluble substances, such as aromatic oils, stabilize the polishing agent dispersion and support the Antikaries Angel of fluorides.
  • anionic surfactants zwitterionic and ampholytic surfactants, nonionic surfactants, cationic surfactants or mixtures of these compounds can be used as surfactants in toothpaste formulations.
  • toothpastes preferably contain at least one surfactant from the group of anionic surfactants.
  • the surfactant or the surfactant mixture is in the compositions of the invention usually in an amount of 0.1 to 10 wt .-%, preferably 0.3 to 7 wt .-% and in particular 1 to 5 wt .-%, based on the total weight of Composition, used.
  • Suitable surfactants with good foaming action are anionic surfactants which also have a certain enzyme-inhibiting effect on the bacterial metabolism of the dental plaque.
  • anionic surfactants which also have a certain enzyme-inhibiting effect on the bacterial metabolism of the dental plaque.
  • These include, for example, alkali or ammonium salts, in particular sodium salts, of C 8 -C 16 -alkanecarboxylic acids, of alkylpolyglycol ether sulfates having 12-16 C atoms in the linear alkyl group and 2 to 6 glycol ether groups in the molecule, of linear alkane (C 12 -C 18 ) Sulfonates, Sulfobernsteinsauremonoalkyl- (C 12 -C 18 ) esters, sulfated fatty acid monoglycerides, sulfated fatty acid alkanolamides, Sulfoessigklakyl- (C 12 -C 6 ) esters,
  • At least one anionic surfactant in particular a sodium lauryl alkyl sulfate having 12-18 C atoms in the alkyl group.
  • a surfactant is sodium lauryl sulfate which is commercially available for example under the name Texapon.RTM ® K12 G commercially.
  • Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example trimethylammonium glycinate,
  • Kokosalkyldimethylammoniumglycinat N-acylamino-propyl-N, N-dimethyl-ammoniumglycinate, for example Kokosacylaminopropyldimethyl-ammoniumglycinat, and 2-alkyl-3-carboxylmethyl-3-hydroxyethylimidazoline having in each case 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacylaminoethylhydroxyethylcarboxymethylglycinat.
  • Particularly preferred is the known under the CTFA name Cocamidopropyl Betaine fatty acid amide derivative.
  • Such products are available, for example under the name Tego betaine ® BL 215 and ZF 50 and Genagen ® CAB commercially.
  • Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C 8 -C 18 -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO 3 H group and are capable of forming internal salts.
  • ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodi propionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group.
  • Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C 2 -C 18 - acyl sarcosine.
  • quaternary emulsifiers are also suitable, with those of the esterquat type, preferably methyl-quaternized difatty acid-diethanolamine ester salts, being particularly preferred.
  • Nonionic surfactants are N-alky
  • Nonionic surfactants are particularly suitable according to the invention for promoting the cleaning action. Particular preference is given to those nonionic surfactants which are selected from at least one of the following groups:
  • Fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products; - Alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogues;
  • polyglycerol esters e.g. polyglycerolpolyricinoleate
  • Polyglycerol poly-12-hydroxy stearate or polyglycerol dimerate Polyglycerol dimerate.
  • Partial esters based on linear, branched, unsaturated or saturated C 6 -C 22 -fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol,
  • Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives; Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol and polyalkylene glycols.
  • the addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products and are preferred according to the invention. These are homolog mixtures whose mean degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the Addition reaction is carried out, corresponds. and diesters of addition products of ethylene oxide with glycerol are known from DE-PS 2024051 as refatting agents for cosmetic preparations.
  • C 8 -C 18 -Alkyl mono- and oligoglycosides their preparation and their use are known in the art, for example from US-A-3,839,318, DE-A-20 36 472, EP-A-77 167 or WO-A - 93/10132 known. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms.
  • the glycoside radical both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of preferably approximately 8 are suitable.
  • the degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.
  • An alkyl (oligo) glycoside of the formula RO (C 6 H 10 O) x -H in which R is an alkyl group having 12 to 14 C atoms and x is preferably suitable as the alkyl (oligo) glycoside Mean value of 1 to 4 has.
  • the nonionic surfactant may be mentioned, for example, PEG-glyceryl stearate, sold under the name Tagat ® S commercially.
  • Humectants are usually used in dental cosmetics to protect against dehydration and for consistency control and cold stability of the products. However, they can also serve for suspension mediation and to influence the taste or gloss.
  • humectants are toxicologically acceptable polyols such as sorbitol, xylitol, glycerol, mannitol, 1,2-propylene glycol, or mixtures thereof, but also polyethylene glycols having molecular weights of 400-2,000 can serve as humectant components in dentifrices.
  • the humectant or the mixture of humectants in the total composition in an amount of 10 to 85 wt .-%, preferably 15 to 70 wt .-% and in particular 25 to 50 wt .-% contained.
  • the agents according to the invention additionally comprise at least one binding or thickening agent in a preferred embodiment. These act to regulate consistency and continue to prevent the separation of the liquid and solid components.
  • Their amounts used in the compositions according to the invention are from 0.1 to 5% by weight, preferably from 0.1 to 3% by weight and in particular from 0.5 to 2% by weight.
  • Natural and / or synthetic water-soluble polymers such as alginates, carrageenans, agar agar, guar gum, gum arabic, succinoglycan gum, guar gum, locust bean gum, tragacanth, karaya gum, xanthan, pectins, cellulose and their ionic and nonionic derivatives such as carboxymethylcellulose, hydroxyethylcellulose or methylhydroxypropylcellulose, hydrophobically modified celluloses, starch and starch ethers.
  • alginates, carrageenans such as alginates, carrageenans, agar agar, guar gum, gum arabic, succinoglycan gum, guar gum, locust bean gum, tragacanth, karaya gum, xanthan, pectins, cellulose and their ionic and nonionic derivatives such as carboxymethylcellulose, hydroxyethylcellulose or methylhydroxypropylcellulose, hydrophobically modified cellulose
  • carboxyvinyl polymers for example Carbopol ® types
  • polyvinyl alcohol for example polyvinyl alcohol
  • polyvinylpyrrolidone for example polyvinyl alcohol
  • polyvinylpyrrolidone for example polyvinyl alcohol
  • polyvinylpyrrolidone for example polyvinyl alcohol
  • polyvinylpyrrolidone for example polyvinyl alcohol
  • polyvinylpyrrolidone polyvinylpyrrolidone
  • higher molecular weight polyethylene glycols particularly those having molecular weights of 10 2 - 10 6 D
  • phyllosilicates and finely divided silicas (Aerogelkieselklaren and fumed silicas) fulfill this function.
  • the oral and dental cleaning agent according to the invention contains additional active ingredients against tooth and gum diseases.
  • active substances are anticaries agents, antimicrobial agents, tartar inhibitors, flavorings or any combination of these substances.
  • Fluorine compounds preferably from the group of fluorides or monofluorophosphates in an amount of 0.1-0.5% by weight fluorine, are especially suitable for controlling and preventing caries.
  • Suitable fluorine compounds are, for.
  • Preparations preferred according to the invention are characterized in that they additionally have antiplaque active ingredients, preferably methyl, ethyl or propyl p-hydroxybenzoate, sodium sorbate, sodium benzoate, bromochlorophene, triclosan, phenyl salicylic acid ester, Biguanids z.
  • antiplaque active ingredients preferably methyl, ethyl or propyl p-hydroxybenzoate, sodium sorbate, sodium benzoate, bromochlorophene, triclosan, phenyl salicylic acid ester, Biguanids z.
  • antiplaque active ingredients preferably methyl, ethyl or propyl p-hydroxybenzoate, sodium sorbate, sodium benzoate, bromochlorophene, triclosan, phenyl salicylic acid ester, Biguanids z.
  • chlorhexidine, thymol preferably in amounts of 0.1 to 5 wt .-
  • antimicrobial component z As antimicrobial component z. As phenols, resorcinols, bisphenols, salicylanilides and amides and their halogenated derivatives, halogenated carbanilides and p-hydroxybenzoic acid esters.
  • antimicrobial components those which inhibit the growth of plaque bacteria are particularly suitable.
  • examples are halogenated diphenyl ethers, such as 2,4-dichloro-2'-hydroxydiphenyl ether, 4,4'-dichloro-2'-hydroxydiphenyl ether, 2,4,4'-tribromo-2'-hydroxydiphenyl ether, 2,4,4'-dichloro-2'-hydroxydiphenyl ether.
  • Trichloro-2'-hydroxydiphenyl ether Triclosan suitable as antimicrobial agents.
  • bisbiguanides such as chlorhexidine and alexidine, phenylsalicylic acid esters and 5-amino-1,3-bis (2-ethylhexyl) -hexahydro-5-methylpyrimidine (hexetidine)
  • zinc and copper ions also have an antimicrobial effect, with synergistic effects especially in combination with hexetidine and triclosan occur.
  • quaternary ammonium compounds such as.
  • cetylpyridinium chloride benzalkonium chloride, domiphen bromide and dequalinium chloride are used.
  • Octapinol, octenidine and sanguinarine have also proven to be effective as antimicrobial agents.
  • the antimicrobial agents are preferably used in amounts of 0.01 to 1 wt .-% in the inventive compositions.
  • Irgacare ® MP is particularly preferred in an amount from 0.01 to 0.3 wt .-% is used.
  • Tartar is mineral deposits that are very similar to natural tooth enamel.
  • substances are added to the dentifrices according to the invention which specifically intervene in crystal nucleation and prevent existing germs from growing on.
  • These are, for example, condensed phosphates, which are preferably selected from the group of tripolyphosphates, pyrophosphates, trimetaphosphates or mixtures thereof. They are used in the form of their alkali metal or ammonium salts, preferably in the form of their sodium or potassium salts.
  • Aqueous solutions of these phosphates typically react alkaline, so that the pH value of the dentifrice according to the invention is adjusted to values of 7.5-9, if appropriate by addition of acid.
  • acids can be z.
  • citric acid phosphoric acid or acid salts, for. B. NaH 2 PO 4 can be used.
  • the desired pH of the dentifrice can also by addition of acidic salts of the condensed phosphates, ie z. B. K 2 H 2 P 2 O 7 , can be adjusted.
  • organophosphonates such as 1-azacycloheptane-2,2-diphosphonate (Na salt), 1-hydroxyethane-1, 1-diphosphonate (Na salt) and Zinkeitrat.
  • the agents of the invention further contain hypersensitive tooth active agents selected from potassium and strontium salts such as potassium chloride, potassium sulfate, potassium bicarbonate, potassium citrate, potassium acetate, potassium nitrate, strontium chloride, strontium nitrate, strontium citrate, strontium acetate and strontium lactate and eugenol.
  • potassium and strontium salts such as potassium chloride, potassium sulfate, potassium bicarbonate, potassium citrate, potassium acetate, potassium nitrate, strontium chloride, strontium nitrate, strontium citrate, strontium acetate and strontium lactate and eugenol.
  • the eugenol may be mixed with aromatic oils in the oral and dental care products. Preferably, it is included in the compositions in the form of clove bud oil.
  • the oral and dental care products of the invention contain at least 0.5% by weight of potassium or strontium ions in the form of a dissolved salt and at least 0.01% by weight of eugenol in pure form or in the form of clove bud oil.
  • compositions of the invention contain flavorings to which z. Sweetening and / or flavoring oils.
  • Suitable sweeteners are, for example, saccharinates (in particular sodium saccharinate), cyclamates (in particular sodium cyclamate) and also sucrose, lactose, maltose or fructose.
  • Aromatic oils are all natural and synthetic flavors used for oral and dental care. Natural flavors can be used both in the form of the essential oils (mixture) isolated from the drugs and in the form of the individual components isolated therefrom. Preferably at least one aromatic oil should be selected from the group of peppermint oil, spearmint oil, aniseed oil, star aniseed oil, caraway oil, eucalyptus oil, fennel oil, cinnamon oil, clove oil, geranium oil, sage oil, pimento oil, thyme oil, marjoram oil, basil oil, citrus oil, Gaultheria oil or one or more thereof or synthetic produced components of these oils may be included. The most important components of the oils mentioned are z.
  • Other suitable flavors are z.
  • other common adjuvants may be included to improve the stability and sensory properties of the oral and dental care products. Such aids are, for example:
  • vitamins eg. Retinol, biotin, tocopherol, ascorbic acid and their derivatives (eg, esters, salts);
  • pigments eg., titanium dioxide or zinc oxide
  • Colored pigment particles for example colored silica particles, as described e.g. B. under the sales name Sorbosil BFG 51 ®, BFG 52 and BFG 53 or Sorbosil ® 2352 are commercially available. Mixtures of differently colored pigment particles can also be used. Such, z. B. strongly orange, red or blue colored gel silica particles may be present in amounts of 0.1 to 1, 0 wt .-% in the inventive compositions;
  • Bleaching agents such as hydrogen peroxide and hydrogen peroxide precursors
  • pH adjusting agents and buffer substances eg. Sodium, sodium bicarbonate or potassium and sodium phosphates
  • Preservatives e.g. methyl, ethyl or propyl p-hydroxybenzoate, sodium sorbate, sodium benzoate, bromochlorophene or triclosan;
  • Mineral salts such as zinc, magnesium and manganese salts, for example sulphates.
  • All of these optional dentifrice ingredients are contained together in an amount of about 2 to 10 wt .-%, based on the total weight, in the inventive compositions.
  • Preparations to be used according to the invention 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.
  • preferred oral and dental care and cleaning agents are characterized in that they 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, particularly preferably from 1.0 to 15% by weight, more preferably from 2.5 to 10% by weight and in particular from 4.0 to 8.0% by weight, in each case based on the total agent included.
  • 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, particularly preferably from 1.0 to 15% by weight, more preferably from 2.5 to 10% by weight and in particular from 4.0 to 8.0% by weight, in each case based on the total agent included.
  • preparations in particular oral and dental care and - cleansing agents, 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% by weight %, more preferably from 1.0 to 15 wt .-%, more preferably from 2.5 to 10 wt .-% and in particular from 4.0 to 8.0 wt .-%, each based on the total agent included ,
  • 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% by weight %, more preferably from 1.0 to 15 wt .-%, more preferably from 2.5 to 10 wt .-% and in particular from 4.0 to 8.0 wt .
  • Oral and dental care and cleaning agents to be used particularly preferably according to the invention are characterized in that they contain from 0.2 to 20% by weight, preferably from 0.4 to 14% by weight, particularly preferably from 0.5 to 3% by weight. % and in particular 0.6 to 2 wt .-% of at least one bioactive glass.
  • the oral and dental care and cleaning agents of this embodiment to be used in the present invention include bioactive glass or glass powder or glass ceramic powder or composite materials comprising such a bioactive glass.
  • bioactive glass or glass powder or glass ceramic powder or composite materials comprising such a bioactive glass.
  • glass powders are also understood as meaning granules and glass beads.
  • the glass powder should be particularly pure.
  • the burden of heavy metals is preferably low.
  • the maximum concentration in the range of cosmetic formulations is preferably for Pb ⁇ 20 ppm, Cd ⁇ 5 ppm, As ⁇ 5 ppm, Sb ⁇ 10 ppm, Hg ⁇ 1 ppm, Ni ⁇ 10 ppm.
  • the unfused starting glass which is contained directly in the preferred compositions according to the invention or is optionally used for the production of a glass ceramic which can be used according to the invention, contains SiO 2 as a network former, preferably between 35-80% by weight. At lower concentrations, the spontaneous tendency to crystallize increases greatly and the chemical resistance decreases sharply. At higher SiO 2 values, the crystallization stability may decrease and the processing temperature is significantly increased, so that the hot-forming properties deteriorate. Na 2 O is used as a flux during melting of the glass. At concentrations of less than 5%, the melting behavior is adversely affected.
  • Sodium is a constituent of the phases which form during the ceramization and, if high crystalline phase proportions are to be set by the ceramization, must be present in the glass in correspondingly high concentrations.
  • K 2 O acts as a flux when melting the glass.
  • 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 release of ions in aqueous media.
  • P 2 O 5 is network images.
  • the P 2 O 5 content is preferably between 0 and 80 wt .-%.
  • 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.
  • the antibacterial properties of the glass-ceramic antimicrobial acting ions such as Ag, Au, I, Ce, Cu, Zn in concentrations less than 5 wt .-% may be included.
  • Coloring ions such as Mn, Cu 2 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 done either with a glass block or Glasribbons or with glass powder. After ceramization, the glass ceramic blocks or ribbons must be ground to powder. If the powder has been ceramified, it may also be necessary to re-mill to remove agglomerates formed during the ceramification step.
  • the grinding can be carried out both dry and in aqueous or non-aqueous grinding media.
  • 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%.
  • 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 .-%.
  • 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%.
  • SiO 2 35 to 60% by weight, preferably 40 to 60% 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 wt .-%, preferably 0 to 5 wt .-%,
  • B 2 O 3 0 to 25 wt .-%, preferably 0 to 5 wt .-%,
  • 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, more preferably from 1 to 2 microns having.
  • a preferred embodiment are toothpastes with a content of silica, polishing agents, humectants, binders and flavors, the 0.00001 to 10, in particular 0.01 to 4 wt .-%, preferably 0.01 to 2 wt .-% of composite materials according to the invention with contain nanoparticulate calcium salts from the group hydroxylapatite, fluorapatite and calcium fluoride.
  • the composite materials according to the invention can be applied, for example, by the standard methods of dip coating or plasma spraying known to those skilled in the art.
  • the composite materials according to the invention may be combined with suitable further substances, such as. As glycosaminoglycans or proteins, and with suitable solvents and adjuvants such.
  • suitable further substances such as. As glycosaminoglycans or proteins, and with suitable solvents and adjuvants such.
  • Another object of the present invention relates to candy containing the inventive sparingly water-soluble calcium salts and / or composite materials, comprising these. At least 0.000001% by weight of at least one sparingly water-soluble calcium salt and / or composite material according to the invention, comprising these, is preferably contained.
  • the sweets in particular the composite materials according to the invention described below, particularly preferably contain from a sparingly water-soluble calcium salt according to the invention and a protein component which is preferably selected from collagen, gelatin, casein and their hydrolysates, preferably gelatin, particularly preferably type A, B or gelatin AB, in particular gelatin of the acid bone type.
  • a protein component which is preferably selected from collagen, gelatin, casein and their hydrolysates, preferably gelatin, particularly preferably type A, B or gelatin AB, in particular gelatin of the acid bone type.
  • the candy is selected from the group of sugar confectionery.
  • Sugar confectionery is a diverse group of foods that usually have a distinctly sweet taste due to sugar and / or other common sugars, sugar or other sweeteners or other sweet ingredients, according to the Confectionery Directive of the Federation of the German Confectionery Industry.
  • Sugar confectionery is also filling, Glaze or confectionery masses, as well as layers, coatings or fillings of confectionery or pastries.
  • the sugar confectionery also includes sugar-free sugar confectionery. In these, the sweet taste is achieved by sugar alcohols and / or sweeteners.
  • Preferred confectionery products are, in particular, hard and soft caramels, gumdrops, jelly products, marshmallows, licorice products, dragees, lozenges and candied fruits.
  • Caramels also called candies
  • Caramels generally obtain their character by boiling a solution of sugars and / or sugar alcohols and are prepared using odorous and flavoring substances, coloring and / or texture affecting substances with or without filling in various forms.
  • the texture of the caramel ranges from hard caramels, e.g. Drops up to the soft caramels, which differ in particular by their residual water content. This can be up to about 5% by weight for hard caramels and up to about 15% by weight for soft caramels.
  • Soft caramels are, for example, the elastic-chewing gum-like chewy candy or the soft, easily chewable, z.T. sticky toffees.
  • Depending on the method of production e.g. distinguished sliced, embossed, cast and laminated candies.
  • Jelly products in the spirit of the present invention are elastic-soft confectionery confections (e.g., jelly fruits).
  • sweets according to the invention are gumdrops, e.g. Fruit gums, gummy bears, wine gums or gum pastilles. They are tough-elastic and chewable-firm and, like the jelly products, are made from sugars and / or sugar alcohols, gelling agents (such as agar, pectin or gum arabic), gelatin and / or starch (modified if necessary).
  • Waxes or vegetable oils can additionally be used as a separating and brightening agent.
  • Licorice products are made from a mixture of sugars and / or sugar alcohols, gelatin and / or (also modified) starch and / or flour and / or gelling and thickening agents as well as various flavors.
  • licorice products contain as a characteristic ingredient at least 3% licorice juice (Succhus liquiritiae, in the commercial dry form).
  • Dragees consist of a smooth or curly top made with sugar types and / or sugar alcohols, chocolate types and / or other glazes in a coating process and a liquid, soft or firm core.
  • a saturated sugar solution is finely distributed from a nozzle to the rotating in Dragierkesseln core sprayed.
  • the sugar crystallizes through the simultaneously injected warm air and gradually forms many thin layers around the core. If the sugar layer does not contain any residual moisture, the candy is called harddragee, whereas in the case of softdrages it can be about 6 to 12, in particular be given 8 to 10 wt .-% residual moisture.
  • Dragees are externally often provided with a thin release and gloss layer, wherein the gloss layer by treatment with waxy substances, such as, for example, carnauba wax arises.
  • waxy substances such as, for example, carnauba wax arises.
  • influencing substances such as starch and coloring, odor and flavoring substances are used.
  • Compresses or pastilles are produced by the tableting or powder casting or extrusion process and may contain, in addition to the sugars and / or sugar alcohols, small amounts of binders and lubricants.
  • the candy is a hard or soft caramel or a dragee.
  • These sweets have the advantage that they are kept in the mouth for a long time and the calcium salt or composite materials of the invention contained in the candy are released only gradually. The mineralizing, and in particular the neomineralizing effect is thereby particularly promoted.
  • the active ingredient can advantageously be incorporated directly into the melt. Surprisingly, this does not lead to a crystallization of the sugar in the melts, which leads to the addition of conventional, ground apatite to a polycrystalline, difficult to process mass. The gritty taste of coarse-grained apatite could not be determined either.
  • the hard caramels such as e.g. Sweets, drops, candy canes or lollipops, which remain in the mouth for a particularly long time, whereby the stepwise release of the calcium salt or the composite material according to the invention is optimally given.
  • the consumption of the candy according to the invention leads, in addition to the enjoyment experience, to dental care and tooth preservation as well as, in addition, to the mineralization of the enamel and / or of the dentin.
  • dental care and tooth preservation as well as, in addition, to the mineralization of the enamel and / or of the dentin.
  • toothbrush, toothpaste and / or mouthwash can be dispensed with without damage to the teeth by the consumption of sweets.
  • Sugar alcohols which are preferred according to the invention are sorbitol or sorbitol syrup, mannitol, xylitol, lactitol, isomalt, maltitol or maltitol syrup. These substances have the advantage that they contain less calories per 100 g and, moreover, the degradation of the sugar alcohols to acids by some bacteria of the oral cavity takes place so slowly that they do not have a cariogenic effect.
  • the inventive addition of composite materials according to the invention in sweeteners containing sugar substitutes causes a Mineralization of the teeth during and / or after the consumption of the candy and thus contributes particularly to the maintenance of healthy teeth.
  • the candy according to the invention is filled.
  • Sweets with a solid, gel or liquid core allows i.a. the addition of other flavor components in this core.
  • it can thereby be incorporated active ingredients which can not be incorporated in a direct manner (for example by admixing) without reducing or losing their effect.
  • candies u.a. Vitamins or alcohol are incorporated into such fillings.
  • the filling contains the calcium salts and / or composite materials according to the invention, comprising these.
  • the material according to the invention contained in the filling can thus also be incorporated into such sweets in which the risk of loss of effect by the properties of the candy or the production thereof consists.
  • This filling may in particular be a suspension, a gel or a syrup.
  • the suspensions or gels may be water-based to ensure good compatibility.
  • An addition of food-grade dispersants or wetting agents can serve to keep the composite materials according to the invention in suspension.
  • Particularly suitable gel formers are organic thickeners and their derivatives.
  • synthetic organic thickeners particularly natural organic thickeners, in particular agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein are suitable. Modified natural products are also preferred, in particular carboxymethylcellulose and other cellulose ethers, hydroxyethylcellulose and hydroxypropylcellulose, and gum ethers.
  • Synthetic organic thickeners e.g. Polyethers or inorganic thickeners such as polysilicic acids and / or clay minerals (e.g., montmorillonites, zeolites or silicas) can also be used in the present invention.
  • the candy is a chewing gum.
  • the chewing gum additionally promotes the salivation by the executed chewing motion.
  • the caries causing acids are diluted and so naturally the health of the body
  • Tooth-care and -supporting chewing gums contain sugar substitutes, in particular sugar alcohols.
  • Chewing gums consists of sugars and / or sugar alcohols, sweeteners, flavors, other odor and taste or consistency-giving ingredients, dyes and a water-insoluble gum which becomes plastically chewing.
  • the chewing gums may also contain separating and coating agents (such as talcum).
  • Kaumassen are mixtures of consistency-giving substances, the natural gums, which are solidified juices (exudates) from tropical plants such as chicle, gum arabic, gutta-percha, karaya gum and tragacanth, rubber and the thermoplastics butadiene-styrene copolymers, isobutylene-isoprene copolymers, Polyethylene, polyisobutylene, polyvinyl esters of the unbranched fatty acids of C 2 to C 18 and polyvinyl ethers.
  • Plasticizers are resins and balsams.
  • the natural substances include benzoin, dammar resin, rosin, mastic, myrrh, olibanum, balsam of Peru, Sandarrak, shellac and tolu balsam, the synthetic coumarone-indene resin, glycerol pentaerythritol ester of the rosin acid of the rosin and their hydrogenation products.
  • Paraffins Natural and synthetic and waxes are used to influence the elasticity.
  • waxes there are those from the plant sector such as Carnabau wax and animal origin such as beeswax or wool wax, next to those from the mineral field such as microcrystalline waxes, as well as chemically modified or synthetic waxes.
  • Plasticizers are emulsifiers (e.g., lecithins or mono- and diglycerides of fatty acids) and esters such as glycerol acetate as well as glycerine.
  • vegetable hydrocolloids such as agar-agar, alginic acid and alginates, guar gum, locust bean gum or pectin are added.
  • fillers are carbonates of calcium or magnesium, oxides, such as alumina, silica and silicates of calcium or magnesium.
  • Stearic acid and its calcium and magnesium salts are used to reduce the adhesiveness of the chewing gum to enamel.
  • gum comprising about 20-35% represents (but at least 15%) of the final chewing gum, heating to 50-60 0 C.
  • the chewing gum is enveloped by at least one layer, this layer comprising at least one inventive calci composite material.
  • the composite materials are simply added to the chewing gum.
  • a coated chewing gum can also be produced in which the enveloping layer contains the two essential ingredients of the contains products according to the invention.
  • the active ingredients ie the calcium salt and / or its composites, are simply added and stirred to a solution and / or dispersion from which the coating is produced.
  • the chewing gum of the present invention is a sugar-containing chewing gum.
  • “sugars” or “sugars” include products such as sucrose, purified crystalline sucrose, for example in the form of refined sugar, raffinates, refined white sugar, white sugar or semi-white sugar, aqueous solutions of sucrose, for example in the form of Liquid sugar, aqueous solutions of partially inverted by hydrolysis inverted sucrose, for example, invert sugar, syrup or invert sugar, glucose syrup, dried glucose syrup, dextrose containing water of crystallization, dextrose free of water of crystallization and other starch saccharification products and trehalose, trehalulose, tagatose, lactose, maltose, fructose, leucrose, isomaltulose (palatinose) , condensed Palatinose and hydrogenated condensed Palatinose understood.
  • the sugar-containing chewing gum according to the invention is therefore characterized in that either the chewing gum itself or the enveloping layer or both sweeteners sucrose, invert sugar, invert sugar syrup, glucose, glucose syrup, polydextrose, trehalose, trehalulose, tagatose, lactose, maltose, fructose, leucrose, Isomaltulose (palatinose), condensed Palatinose, hydrogenated condensed Palatinose or mixtures thereof.
  • sugar-containing chewing gum according to the invention can, in addition to the aforementioned types of sugar, also sugar substitutes, in particular sugar alcohols such as lactitol, sorbitol, XyNt, mannitol, maltitol, erythritol, 6-O- ⁇ -D-glucopyranosyl-D-sorbitol (1,6-GPS).
  • sugar substitutes in particular sugar alcohols such as lactitol, sorbitol, XyNt, mannitol, maltitol, erythritol, 6-O- ⁇ -D-glucopyranosyl-D-sorbitol (1,6-GPS).
  • 1-O- ⁇ -D-glucopyranosyl-D-sorbitol (1, 1-GPS), 1-O- ⁇ -D-glucopyranosyl-D-mannitol (1, 1-GPM), maltitol syrup, sorbitol syrup , Fructo-oligosaccharides or mixtures thereof and mixtures of sugar alcohols and sugar species.
  • the chewing gum according to the invention is a sugar-free chewing gum.
  • a "sugar-free chewing gum” is understood to mean a chewing gum in which both the chewing gum itself and the enveloping layer as sweetener contain none of the abovementioned types of sugar, ie neither sucrose, invert sugar sugar, invert sugar syrup, dextrose, glucose - syrup, trehalose, trehalulose, tagatose, lactose, maltose, fructose, leucrose, isomaltulose (palatinose), condensed palatinose, hydrogenated condensed palatinose nor mixtures thereof, but sugar substitutes.
  • the sugar-free chewing gum according to the invention is a chewing gum having a maximum content of the abovementioned sugar species of 0.5% by weight, based on the dry weight.
  • sugar substitutes includes all substances other than the abovementioned types of sugar that can be used to sweeten foods.
  • sugar substitutes includes in particular substances such as hydrogenated mono- and disaccharide sugar alcohols, for example lactitol, xylitol, sorbitol, mannitol, maltitol, erythritol, isomalt, 1, 6-GPS, 1, 1-GPS, 1, 1-GPM, Sorbitol syrup, maltitol syrup, and fructo-oligosaccharides.
  • the sugarless chewing gums according to the invention are characterized in that both the chewing gum itself and the coating layer are sweeteners lactose, maltose, fructose, leucrose, palatinose, condensed palatinose, hydrogenated condensed palatinose, fructo-oligosaccharides, lactitol, sorbitol, xylitol, mannitol, maltitol , Erythritol, 1, 6-GPS, 1, 1-GPS, 1, 1-GPM 1 sorbitol syrup, maltitol syrup or mixtures thereof.
  • Sugar alcohols such as sorbitol or sorbitol syrup, mannitol, xylitol, lactitol, maltitol or maltitol syrup, 1, 1-GPS, 1, 6-GPS, 1, 1-GPM or mixtures thereof are preferred according to the invention.
  • Sugar alcohols have the advantage that they contain less calories per 100 g and, moreover, that they are degraded by acids of the oral flora only very slowly or not at all to acids, so that they do not have a cariogenic effect.
  • a preferred mixture of 1,6-GPS and 1,1-GPM is isomalt, in which 1,6-GPS and 1, 1-GPM are present in equimolar or nearly equimolar amounts.
  • 1, 6-GPS-enriched mixtures of 1, 6-GPS and 1, 1-GPM with a 1, 6-GPS Content of 57% by weight to 99% by weight and a 1, 1-GPM content of 43% by weight to 1% by weight 1, 1-GPM-enriched mixtures of 1, 6-GPS and 1, 1 -GPM with a 1, 6-GPS content of 1 wt .-% to 43 wt .-% and a 1, 1 - GPM content of 57 wt .-% to 99 wt .-% and mixtures from 1, 6-GPS, 1, 1 -GPS and 1, 1 -GPM can be used as a sweetener.
  • 1, 6-GPS-enriched mixtures and 1, 1 -GPM-enriched mixtures of 1, 6-GPS and 1, 1 -GPM are disclosed in DE 195 32 396 C2, the disclosure of this document with respect to the description and provision of the 1, 6-GPS enriched and 1, 1-GPM enriched sweetener mixtures are fully incorporated in the disclosure of the present teachings.
  • 1, 1-GPS-containing mixtures of 1, 6-GPS and 1, 1 -GPM are disclosed for example in EP 0 625 578 B1, the disclosure content of this document with regard to the description and provision of the 1, 1-GPS, 1 , 6-GPS and 1, 1-GPM-containing sweetener mixtures are fully incorporated in the disclosure of the present teaching.
  • Another inventively preferred mixture which can be used in the chewing gums according to the invention, in particular sugar-free chewing gums, is a syrup with a dry matter of 60 to 80%, consisting of a mixture of hydrogenated starch hydrolyzate syrup and isomalt powder or isomalt syrup, wherein the Dry matter of the syrup from 7 to 52% (w / w) 1, 6-GPS, 24.5 to 52% (w / w) 1, 1-GPM, 0 to 52% (w / w).
  • the sugar-free chewing gum of the present invention coated with at least one layer comprising composite material according to the present invention may be, for example, a hard coated sugarless chewing gum containing a sugarless gum core and a sugarless hard coating containing a substantially hygroscopic sugar free sweetener. wherein the chewing gum core has a water content of less than about 2.5% by weight, based on the weight of the core.
  • the substantially hygroscopic sweetener may be, for example, sorbitol or hydrogenated isomaltulose.
  • Such sugar-free, hard-coated chewing gums are described in WO 88/08671, the disclosure of which is incorporated herein by reference for describing and providing the hard-coated sugar-free chewing gums in its entirety.
  • both the sugar-containing chewing gums according to the invention and the sugar-free chewing gums according to the invention in the chewing gum itself and / or in the layer enveloping it can additionally contain one or more intensive sweeteners in addition to the abovementioned types of sugar and / or sugar substitutes .
  • intensive sweeteners are compounds that are characterized by an intense sweet taste with low or negligible nutritional value.
  • the intensive sweetener cyclamate used in the chewing gum according to the invention for example sodium cyclamate, saccharin, for example saccharin sodium, aspartame, glycyrrhizin, neohesperidin dihydrochalcone, thaumatin, monellin, acesulfame, steviosides, alitame, sucralose or a mixture thereof is.
  • saccharin for example saccharin sodium, aspartame, glycyrrhizin, neohesperidin dihydrochalcone, thaumatin, monellin, acesulfame, steviosides, alitame, sucralose or a mixture thereof is.
  • the proportion of sugar species can be reduced, and nevertheless the predominantly sweet taste can be obtained.
  • the chewing gum according to the invention comprises not only an enveloping layer, in particular a sugar-coated layer, comprising a sparingly soluble calcium salt and / or its composites, but at least 2 to about 100 such enveloping layers, in particular coated layers.
  • the individual layers have the same sweetener or sweeteners.
  • the individual layers may also contain different sweeteners.
  • Such gummed chewing gum products are thus enveloped by layers of different sweetener composition.
  • the chewing gum of the present invention may initially be coated with from 1 to about 45 coated layers containing the 1, 1-GPM-enriched mixture of 1, 6-GPS and 1, 1-GPM. Subsequently, 1 to about 45 layers of the 1, 6-GPS-enriched mixture of 1, 6-GPS and 1, 1 -GPM are applied to these layers.
  • a sugar-coated chewing gum is characterized by an overall higher sweetening power compared to chewing gums coated with hydrogenated isomaltulose, for example, because of the higher solubility and greater sweetening power of the 1, 6-GPS-enriched mixture forming the outer layer.
  • Such a layer sequence is described in DE 195 32 396 C2, the disclosure content of this document being fully incorporated into the disclosure content of the present teaching with regard to the description and provision of chewing gum with this layer sequence.
  • the chewing gum of the present invention may be a hard-coated chewing gum, the dragee covering having multiple layers containing from about 50% to about 100% xylitol and multiple layers containing from about 50% to about 100% hydrogenated isomaltulose.
  • Such chewing gums are disclosed in WO 93/18663, wherein the disclosure content of this document with regard to the description and provision of chewing gum with this sequence of layers is fully included in the disclosure content of the present teaching.
  • the individual, coated the chewing gum coated layers contain the same calcium salt and / or the same composites thereof.
  • the individual layers which encase the chewing gum contain different calcium salts and / or different composites thereof.
  • individual layers contain no calcium salt or no composites thereof.
  • the layer surrounding the chewing gum which comprises the sparingly water-soluble calcium salt, advantageously results in that the release of the calcium salt is easier than in the direct incorporation of the salts into the chewing gum mass in which the incorporated calcium salts remain strongly adhered to the sticky matrix of the chewing gum ,
  • the layer surrounding the chewing gum dissolves very quickly when chewing in the mouth and can thus make available the necessary amount of active substance in the mouth, which advantageously ensures effective mineralization of the teeth.
  • the addition of the calcium salts and / or composites thereof does not affect the crunch, ie the crispness of the chewing gum.
  • the layer enclosing the chewing gum according to the invention contains sugar and / or sugar alcohols.
  • sugars mono-, di- and oligosaccharides such as, for example, dextrose, fructose and sucrose, glucose syrup, liquid sugars and related products, dried glucose syrup and other starch saccharification products, as well as sugar substitutes, in particular sugar alcohols.
  • the layer containing sugar and / or sugar alcohols dissolves particularly quickly in the mouth.
  • it can also be applied particularly well to a chewing gum core core.
  • the consumption of the chewing gum according to the invention leads, in addition to the enjoyment experience, to dental care and tooth preservation as well as, moreover, to the mineralization of the enamel and / or of the dentin.
  • dental care and tooth preservation as well as, moreover, to the mineralization of the enamel and / or of the dentin.
  • toothbrush, toothpaste and / or mouthwash can be waived so without damage for the teeth.
  • Sugar alcohols which are preferred according to the invention are sorbitol or sorbitol syrup, mannitol, xyNt, lactitol, isomalt, maltitol and maltitol syrup. These substances have the advantage that they contain less calories per 100 g and, moreover, the degradation of the sugar alcohols to acids by some bacteria of the oral cavity takes place so slowly that they do not have a cariogenic effect.
  • the addition according to the invention of composites according to the invention in sugar-substitute-containing chewing gums causes a mineralization of the teeth during and / or after the consumption of the chewing gum and thus contributes particularly to the maintenance of healthy teeth.
  • the sugar alcohols are particularly suitable for the production of thin layers, especially in the coating process due to their physico-chemical properties.
  • Particularly preferred is the use of isomalt in the enveloping layer, since this sugar alcohol has a comparatively high glass transition temperature, which particularly facilitates the processing.
  • the layer enveloping the chewing gum may be prepared in different ways, e.g. by dipping the chewing gum kernel several times into an appropriate solution and / or dispersion.
  • At least one layer enclosing the chewing gum is a sugar-coated layer, ie the layer is applied to the chewing gum in the coating process.
  • the coating layer (blanket) consists of a smooth or curled, with sugars and / or sugar alcohols, types of chocolate and / or other glazes applied around a liquid, soft or solid core by means of the coating method (as described above).
  • the chewing gum is a filled chewing gum.
  • Chewing gums which contain composite materials incorporated into the chewing mass, however, release only small amounts of the active substance because of their sticky consistency.
  • the composite material according to the invention which is contained in the filling, is released directly in the mouth and can thus work better than in conventional chewing gums.
  • the filled chewing gum may also comprise at least one layer containing the chewing gum containing the composite materials according to the invention.
  • the candy comprises a dissolving component.
  • This component or matrix dissolves in the mouth by contact with the saliva.
  • the dissolution can also be achieved by a longer residence time in the mouth (in particular of over five minutes) and / or sucking.
  • a component or matrix is here, for example, the sugar matrix or the basic mass of a candy, a gummi candy or a filling to understand.
  • the dissolving component or matrix contains the calcium salts and / or composite materials according to the invention which are present in the candy according to the invention, comprising these. This advantageously leads to the fact that the dissolving component can release the active substance contained therein or contained in the mouth. In particular, this is important for such sweets in which the active ingredient is otherwise not released in large quantities.
  • the calcium salts and / or composite materials according to the invention are incorporated into a solid, gelatinous or liquid filling which exits from the chewing gum by biting on the chewing gum in the mouth and releases the active ingredient. In the case of a liquid filling this mixes with the saliva. It is also possible that the calcium salts of the invention and / or the composite materials comprising these, e.g. incorporated in granulated sugar pearls in a chewing gum.
  • the material of the invention can be applied to the candy as a fine powdery dust, for example together with separating agents on chewing gums (for example with talcum) or acidic drops (which are often dusted with powdered sugar as protection against sticking, for example).
  • the candy consists essentially of at least one dissolving component or matrix. According to the invention, it is particularly advantageous that there are no components of the candy to which the active ingredient, after sucking or dissing, can still be bound in the mouth and thus not available for the mineralization of the tooth material.
  • Corresponding sweets may be, for example, filled or unfilled caramels, gumdrops, jelly products, marshmallows, licorice, dragées or lozenges.
  • the candy contains flavorings, sweeteners, fillers and / or further auxiliaries (such as, for example, glycerol or mineral salts, for example Zn 2+ or Mg 2+ ).
  • auxiliaries such as, for example, glycerol or mineral salts, for example Zn 2+ or Mg 2+ ).
  • any natural or nature-identical flavoring agents such as e.g. Fruit flavors
  • These may be contained in particular in solid or liquid fruit preparations, fruit extracts or fruit powders.
  • Preference is given to pineapple, apple, apricot, banana, blackberry, strawberry, grapefruit, blueberry, raspberry, passion fruit, orange, sour cherry, red and blackcurrant, woodruff and lemon.
  • aroma oils such as e.g. Peppermint oil, spearmint oil, eucalyptus oil, aniseed oil, fennel oil, caraway oil and synthetic flavor oils can be used. This is particularly preferably done in herbal and / or cough sweets and chewing gum.
  • flavoring additives may u.a. Milk, yoghurt, cream, butter, honey, malt, caramel, licorice, wine, almonds, pistachio, hazelnut or walnut kernels and other protein-rich oilseed and peanut kernels, coconut, cocoa, chocolate, cola or vanilla.
  • agents such as e.g. Menthol and / or vitamins to be included in the candy of the invention.
  • organophosphonates e.g. i-hydroxyethane-1, 1-diphosphonic acid, phosphono-propane-1, 2,3-tricarboxylic acid (Na salt) or 1-azacycloheptane-2,2-diphosphonic acid (Na salt), and / or pyrophosphates that reduce the formation of tartar.
  • Sweeteners such as sodium saccharin, acesulfame-K, aspartame ®, sodium cyclamate, stevioside, thaumatin, sucrose, lactose, maltose, fructose or glycyrrhizin are also preferably contained. This can reduce the amount of sugar and still obtain the predominantly sweet taste.
  • preservatives it is possible to use all preservatives approved for foods, for example sorbic acid or benzoic acid and derivatives thereof, such as, for example, sodium benzoate and para-hydroxybenzoate (sodium salt), sulfur dioxide or sulfurous acid, sodium or Potassium nitrite. Dyes and pigments to achieve a pleasing appearance may also be included.
  • Another object of the present invention is the use of at least one composite material according to the invention in sweets, in particular sugar confectionery, as an ingredient with a positive effect on dental health.
  • the calcium salts and / or composite materials according to the invention are used for dental care and tooth preservation as well as, moreover, for the mineralization of the enamel and / or of the dentin.
  • a carious disease of the teeth can be counteracted by the use of materials according to the invention.
  • the candy according to the invention can be used in addition to the caries prophylaxis.
  • compositions according to the invention contain, in addition to the calcium salt according to the invention and / or the composite materials comprising these, additionally at least one fluoride salt.
  • fluoride leads to a synergistic enhancement of the nucleating effect of the composite materials according to the invention.
  • Particularly preferred is the addition of sodium and / or potassium fluoride. With the simultaneous addition of active compounds according to the invention and small amounts of fluoride, an approximately five-fold synergistic amplification is evident.
  • Preference is given according to the invention amounts of 0.05 to 0.15 wt .-%, in particular from 0.08 to 0.12 wt .-% fluoride based on the amount of fluoride ions.
  • compositions for inducing or promoting the formation of new bone tissue containing calcium salts according to the invention and / or their composite materials are compositions for inducing or promoting the formation of new bone tissue containing calcium salts according to the invention and / or their composite materials.
  • compositions according to the invention in particular in the form of a toothpaste, a particularly smooth, good mouthfeel and perceived as particularly clean by test persons results.
  • apatite-gelatin composite 2000 is initially introduced into a thermostatically controlled at 25 0 C 4 I beaker in which 44.10 g (0.30 mol) of CaCl 2 -2H 2 O (Fisher Chemicals pa) are dissolved. Separately, 35 g of gelatin (type AB, DGF-Stoess, Eberbach) are dissolved at about 50 ° C. in 350 ml of demineralized water. Both solutions are combined and stirred vigorously with a propeller stirrer. The pH is adjusted to 7.0 with dilute aqueous base.
  • the dispersion is filled in centrifuge cups and the solids content separated by centrifugation from the solution.
  • the dry composite contains 43% by weight of organic, ie proteinaceous, components. This proportion is determined by ashing of the material at 800 ° C. for 3 hours or by the expert evaluation of a thermogravimetric measurement or by carbon combustion analysis (CHN) or by Kjeldal nitrogen analysis, whereby the proportion of the ammonium chloride contamination can be excluded in each case.
  • solutions A and B were prepared separately.
  • Plantacare® ® 1200 were combined and cooled to 0 0 C in an ice bath. Under education of a hydroxyapatite precipitate was added with vigorous stirring solution A to solution B. After removal of excess ammonia, the dispersion was purified by dialysis. The dispersion is then concentrated on a rotary evaporator by determination of the amount of water deposited so far that the solids content in the dispersion, calculated as hydroxylapatite, was 7.5% by weight.
  • This dispersion was added at room temperature to 100 ml of a 10% strength by weight aqueous solution of gelatin type AB (manufacturer: DGF Stoess) prepared analogously to Example 1.1, then heated to 80 ° C. and stirred at this temperature for 5 minutes. Subsequently, the mass was allowed to solidify to form the composite material at room temperature.
  • gelatin type AB manufactured analogously to Example 1.1
  • Plantacare ® 1200 C 12 -C 16 -AIkVIgIyCOSId about 50 wt -% in water supplier Cognis
  • Polywachs ® 1550 polyethylene glycol, MW 1,550 softening point 45 - 5O 0 C Manufacturer RWE / DEA

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Abstract

L'invention concerne des sels de calcium difficilement solubles dans l'eau et/ou des matériaux composites les comprenant, caractérisés en ce que les sels de calcium se présentent sous forme de cristallites individuelles ou sous forme de particules comprenant une pluralité desdites cristallites, avec une taille de particule moyenne inférieure à 1 000 nm, de préférence inférieure à 300 nm, lesdites particules de sel de calcium étant de forme essentiellement plate. Les sels de calcium et/ou les matériaux composites comprenant ces sels de calcium selon l'invention sont destinés, du fait de leur composition et de leur structure fine, à une utilisation notamment pour la régénération des os et des matériaux dentaires, notamment l'émail et la dentine.
EP06818280A 2006-03-01 2006-10-24 Sels de calcium de forme essentiellement plate difficilement solubles dans l'eau et/ou materiaux composites les comprenant Withdrawn EP1988973A1 (fr)

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DE102006009799A DE102006009799A1 (de) 2006-03-01 2006-03-01 Vorwiegend plättchenförmige schwer wasserlösliche Calciumsalze und/oder deren Kompositmaterialien, umfassend diese
PCT/EP2006/010235 WO2007101458A1 (fr) 2006-03-01 2006-10-24 Sels de calcium de forme essentiellement plate difficilement solubles dans l'eau et/ou materiaux composites les comprenant

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