WO2010078936A1 - Dental materials comprising anti-microbial active substances for preventing plaque deposits - Google Patents

Dental materials comprising anti-microbial active substances for preventing plaque deposits Download PDF

Info

Publication number
WO2010078936A1
WO2010078936A1 PCT/EP2009/009125 EP2009009125W WO2010078936A1 WO 2010078936 A1 WO2010078936 A1 WO 2010078936A1 EP 2009009125 W EP2009009125 W EP 2009009125W WO 2010078936 A1 WO2010078936 A1 WO 2010078936A1
Authority
WO
WIPO (PCT)
Prior art keywords
dental material
material according
capsules
dental
active ingredient
Prior art date
Application number
PCT/EP2009/009125
Other languages
German (de)
French (fr)
Inventor
Klaus Ruppert
Mario Beyer
Sebastian Vogt
Original Assignee
Heraeus Kulzer Gmbh
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 Heraeus Kulzer Gmbh filed Critical Heraeus Kulzer Gmbh
Publication of WO2010078936A1 publication Critical patent/WO2010078936A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A61K6/69—Medicaments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the invention relates to dental materials containing antimicrobial agents for the prevention of plaque accumulation.
  • Polymeric dental materials in particular based on AcrylaWMethacrylat, which are introduced for permanent retention in the oral cavity, tend - especially in the absence of oral hygiene - plaque on the material surface.
  • Plaque is composed of various bacteria and yeasts which are fixed by proteins and carbohydrates to surfaces such as e.g. Anchoring teeth or dental materials. On this first bacterial layer then more bacteria can settle and thus form a three-dimensional colony. Due to certain substances being released by the bacteria, this "biofilm” is almost invulnerable to antibiotics In addition to the hygienic aspect, plaque in the advanced stage also leads to a strong discoloration, resulting in aesthetic impairments.
  • Reduction of plaque colonization can be achieved either by microbicides, by a, e.g. on poly (ethylene glycols) based, protein-repellent surface or by a hydrophobic coating of the dental materials, which makes the adhesion of the bacteria on the material difficult to take place.
  • quaternary ammonium salts as antimicrobial additives has long been known.
  • a silane with quaternary ammonium groups is produced as a functional group by Microbeshield and marketed for the antibacterial treatment of filters, textiles and wound dressings.
  • additives based on cationic oligomers known (Akacid®), poly- [2- (2-ethoxy) -ethoxyethyl] guanidinium chloride (CAS No .: 374572-91-5), from PoC POLYMER PRODUKTIONS GMBH 1 Vienna cf. eg EP1280766B1) as well as silver-containing additives (silver-containing glasses, salts, zeolites).
  • the aim of the present invention is to provide a method with which the colonization of plaque on dental materials can be permanently prevented or delayed without adversely affecting the product properties of the dental material.
  • the material should have no micropores and macropores after drug release, for aesthetics and to avoid cracking as starting points for plaque resettlement).
  • the active substance should be released in a retarding manner.
  • the active substance should be colorless and odorless.
  • H The active substance should have such a high release rate that antimicrobial efficacy is given, but no toxic or irritating / sensitizing effects occur.
  • the active substance must not interfere with the polymerization of the product and adversely affect the material properties; no phase separation (softening effect) must occur.
  • Such capsules preferably contain a dequalinium salt, an iminopyridinium derivative, in particular an octenidine salt, sanguinarine or Akacid®) [poly- [2- (2-ethoxy) ethoxyethyl) guanidinium chloride] (CAS no. : 374572-91-5).
  • the capsules are homogeneously distributed in the dental material prior to curing, so that the respective shaped body produced therefrom (for example inlay, filling or crown) likewise has a homogeneous distribution of the encapsulated active substance.
  • such materials for filling composites Verblendkomposite, denture materials, artificial teeth, impression materials, protective coatings, Fissurenver breachler and Dentinbondings, but also veterinary materials such as hoof material in question.
  • the encapsulation of the respective active substance can e.g. take place according to the following methods known per se:
  • DE 10 2004 013 637 A1 describes in paragraphs [0005-7] three known methods of microencapsulation.
  • DE 692 14 278 T2 describes dental cements with encapsulated in water-soluble material (m) redox initiator.
  • the jacket material used is cellulose acetyl butyrate.
  • bioavailable capsules are proposed whose sheath is to be produced by "electrostatic self-assembly.” An exemplary embodiment of this method is not included.
  • encapsulants are preferably for medical devices admissible polymers in question, such as polystyrene, its copolymers with other vinyl monomers, polymethyl methacrylate, its copolymers with other ethylenically unsaturated monomers, and other known per se materials that are familiar to those working in the field of encapsulation expert.
  • the encapsulation does not always produce spherical particles - it is sufficient if the active substance is completely enveloped.
  • the particle diameter is appropriate at up to 50 microns, preferably up to 10 microns, more preferably up to 0.1 microns. The lower limit is determined by the particle size of the smallest particles of the powder used and the thickness of the coating.
  • the active ingredient is present in the dental material preferably in amounts of up to 3% by weight, more preferably up to 1% by weight.
  • the lower limit depends on the strength of the antimicrobial effect.
  • the encapsulation can be produced in several steps ("layer by layer”), as in the cited documents DE 198 12 083 A1, DE 199 07 552 A1, EP 0 972 563, WO 99/47252 A2, US Pat. No. 6,479,146 B1 and WO 2007 / 031345.
  • the active ingredient may be embedded in dendritic polymer transport systems. This technology has become known as the "NT System”.
  • the capsules can also be produced with a double nozzle technique. This is offered by BRACE GmbH, Alzenau (DE 196 17 924 A1).
  • Inactivation of the active ingredient on the surface of the cured dental material is made more difficult, because active substance can diffuse from the inside constantly. Homogeneous distribution of the active ingredient in the bulk material is ensured by sufficient concentration of the microencapsulated active ingredients.
  • the encapsulation ensures that active ingredients can also be incorporated into dental materials which typically have only a low solubility in dental monomers.
  • octenidine 1.0 g of octenidine, 5.0 g of methyl methacrylate, 250 mg of hexadecane and 100 mg of 2,2'-azobis (2-methylbutyl-1-nitrile) are mixed in a 50 ml beaker and stirred until the octenidine is completely dissolved.
  • 72 mg of sodium dodecyl sulfate are dissolved in 24.0 g of demineralized water. Subsequently, the continuous phase is added to the disperse phase with continuous stirring and stirred for 1 h at 2000 U min-1.
  • the resulting macro-emulsion is miniemulgiert by means of an ultrasonic rod (1/2 "tip) for a period of 2 min at 90% amplitude in an ice bath.
  • the sample is transferred to a 50 ml flask and sealed overnight with continuous stirring at 1000 U min.
  • the suspension is filtered warm and freeze dried
  • the capsules are washed on a filter paper with 30 ml of ethanol and dried in vacuo capsules are prevented from swelling, 50 mg of the dried capsule material are removed and the particle size and octenidine content are determined
  • the particle size determined by dynamic light scattering (DLS) is 132 nm, the octenidine content in the capsules being 25% by weight of the original octenidine (corresponding to about 5% by weight of pure lucirin content of the capsules).

Abstract

In order to achieve an anti-plaque effect, dental material has at least one anti-microbial active substance enclosed in capsules made of encapsulating material providing solubility for dental monomers.

Description

Patentanmeldung Heraeus Kulzer GmbH Patent application Heraeus Kulzer GmbH
Dentalmaterialien enthaltend antimikrobielle Wirkstoffe zur Verhinderung von Plaque-AnlagerungenDental materials containing antimicrobial agents for the prevention of plaque accumulation
Die Erfindung betrifft Dentalmaterialien enthaltend antimikrobielle Wirkstoffe zur Verhinderung von Plaque-Anlagerungen.The invention relates to dental materials containing antimicrobial agents for the prevention of plaque accumulation.
Hintergrund:Background:
Polymere Dentalmaterialien, insbesondere auf AcrylaWMethacrylat-Basis, welche zum dauerhaften Verbleib in die Mundhöhle eingebracht werden, neigen - insbesondere bei mangelnder Oralhygiene - zur Plaquebesiedelung an der Werkstoffoberfläche.Polymeric dental materials, in particular based on AcrylaWMethacrylat, which are introduced for permanent retention in the oral cavity, tend - especially in the absence of oral hygiene - plaque on the material surface.
Plaque setzt sich aus verschiedenen Bakterien und Hefen zusammen, welche sich durch Proteine und Kohlenhydrate fest auf Oberflächen, wie z.B. Zähnen, oder dentalen Werkstoffen verankern. Auf dieser ersten Bakterienschicht können sich dann weitere Bakterien festsetzen und damit eine dreidimensionale Kolonie bilden. Durch bestimmte Substanzen, welche von den Bakterien abgegeben werden, ist dieser „Biofilm" nahezu unangreifbar für Antibiotika. Neben dem hygienischen Aspekt führt Plaque im fortgeschrittenen Stadium auch zu einer starken Verfärbung, so dass es zu ästhetischen Beeinträchtigungen kommt.Plaque is composed of various bacteria and yeasts which are fixed by proteins and carbohydrates to surfaces such as e.g. Anchoring teeth or dental materials. On this first bacterial layer then more bacteria can settle and thus form a three-dimensional colony. Due to certain substances being released by the bacteria, this "biofilm" is almost invulnerable to antibiotics In addition to the hygienic aspect, plaque in the advanced stage also leads to a strong discoloration, resulting in aesthetic impairments.
Stand der Technik:State of the art:
Eine Verminderung der Plaque-Besiedlung kann entweder durch Mikrobizide, durch eine, z.B. auf Poly(ethylenglykolen) basierende, proteinabweisende Oberfläche oder durch eine hydrophobe Beschichtung der Dentalwerkstoffe, welche die Anhaftung der Bakterien auf dem Werkstoff erschwert, erfolgen.Reduction of plaque colonization can be achieved either by microbicides, by a, e.g. on poly (ethylene glycols) based, protein-repellent surface or by a hydrophobic coating of the dental materials, which makes the adhesion of the bacteria on the material difficult to take place.
Die Verwendung von quaternären Ammoniumsalzen als antimikrobielle Additive ist seit langem bekannt. So wird z.B. ein Silan mit quaternären Ammoniumgruppen als funktionelle Gruppe von der Firma Microbeshield hergestellt und zur antibakteriellen Ausrüstung von Filtern, Textilien und Wundauflagen vermarktet. Ferner sind Additive auf der Basis von kationischen Oligomeren bekannt (Akacid®), Poly-[2-(2-ethoxy)-ethoxyethyl)-guanidinium-chlorid (CAS No.: 374572-91- 5) , Fa. PoC POLYMER PRODUKTIONS GMBH1 Wien vgl. z.B. EP1280766B1) sowie silberhaltige Additive (silberhaltige Gläser, Salze, Zeolithe). Nachteile derartiger Beschichtungen im Nanometerbereich an der Oberfläche von Dentalwerkstoffen sind deren schlechte Abrasionsstabilitäten gegenüber den natürlichen Vorgängen bei der Nahrungsaufnahme durch das Kauen. Sie müssen daher wiederholt aufgetragen werden oder scheiden generell als proteinabweisende Schichten aus. Bei der Verwendung von mikro- oder nanoskaligem, metallischem Silber ist die Gewährleistung einer natürlichen Farbgebung von Zahnfleischimitat, Füllungen, Verblendungen bzw. künstlichem Zahnmaterial selbst nicht gegeben. Die silberhaltigen Materia- len erfahren eine gelb bis gräuliche Farbgebung, abhängig von der Korngröße des verwendeten Edelmetalls.The use of quaternary ammonium salts as antimicrobial additives has long been known. Thus, for example, a silane with quaternary ammonium groups is produced as a functional group by Microbeshield and marketed for the antibacterial treatment of filters, textiles and wound dressings. Further, additives based on cationic oligomers known (Akacid®), poly- [2- (2-ethoxy) -ethoxyethyl] guanidinium chloride (CAS No .: 374572-91-5), from PoC POLYMER PRODUKTIONS GMBH 1 Vienna cf. eg EP1280766B1) as well as silver-containing additives (silver-containing glasses, salts, zeolites). Disadvantages of such coatings in the nanometer range on the surface of dental materials are their poor abrasion stabilities compared to the natural processes in food intake by chewing. They must therefore be applied repeatedly or excrete as protein-repellent layers. When using micro- or nanoscale, metallic silver, the guarantee of a natural coloring of gingival imitation, fillings, veneers or artificial tooth material itself is not given. The silver-containing materials undergo a yellow to greyish color, depending on the grain size of the precious metal used.
In US 5,875,798 werden Zahnstocher mit eingekapselten Wirkstoffen beschrieben, die durch die mechanische Beanspruchung frei werden. Gemäß US 5,639,476 werden Formulierungen mit verzögerter Freisetzung für die Anwendung in Körperhöhlen ummantelt.In US 5,875,798 toothpicks are described with encapsulated agents that are released by the mechanical stress. According to US Pat. No. 5,639,476, sustained-release formulations are encased for application in body cavities.
Aufgabenstellung:Task:
Ziel der vorliegenden Erfindung ist es, ein Verfahren bereitzustellen, mit dem sich die Besiede- lung von Plaque auf dentalen Werkstoffen dauerhaft verhindern bzw. verzögern lässt, ohne die Produkteigenschaften des Dentalmaterials negativ zu beeinflussen.The aim of the present invention is to provide a method with which the colonization of plaque on dental materials can be permanently prevented or delayed without adversely affecting the product properties of the dental material.
In diesem Zusammenhang erwünschte Eigenschaften bzw. Teilaufgaben sind folgende:Desired characteristics or subtasks in this connection are the following:
A Homogene Verteilung des Wirkstoffes im Bulk-Material und auf der Materialoberfläche, keine punktuelle Verteilung.A Homogeneous distribution of the active substance in the bulk material and on the material surface, no punctiform distribution.
B Der Werkstoff sollte nach der Wirkstofffreisetzung keine Mikro- und Makroporen aufweisen, aus Gründen der Ästhetik sowie zur Vermeidung von Rissbildungen als Ausgangspunkte für Plaque-Neubesiedlung).B The material should have no micropores and macropores after drug release, for aesthetics and to avoid cracking as starting points for plaque resettlement).
C Eine Inaktivierung des Wirkstoffs auf der Oberfläche sollte erschwert sein.C Inactivation of the active ingredient on the surface should be difficult.
D Breites Wirkungsspektrum gegen typische Oralkeime (bakterizid sowohl gegen grampositive wie gram-negative Keime).D Wide range of activity against typical oral bacteria (bactericidal against both Gram-positive and Gram-negative bacteria).
E Gegebenenfalls viruzide und fungizide Eigenschaften.E If necessary, virucidal and fungicidal properties.
F Der Wirkstoff sollte retardierend freigesetzt werden.F The active substance should be released in a retarding manner.
G Der Wirkstoff sollte färb- und geruchlos sein. H Der Wirkstoff sollte eine so hohe Freisetzungsrate haben, dass eine antimikrobielle Wirksamkeit gegeben ist, jedoch keine toxischen oder irritierenden/sensibilisierenden Effekte auftreten.G The active substance should be colorless and odorless. H The active substance should have such a high release rate that antimicrobial efficacy is given, but no toxic or irritating / sensitizing effects occur.
I Der Wirkstoff darf die Polymerisation des Produktes nicht stören und die Werkstoffeigenschaften negativ beeinflussen, es darf keine Phasenseparation (Weichmachereffekt) auftreten.I The active substance must not interfere with the polymerization of the product and adversely affect the material properties; no phase separation (softening effect) must occur.
J Die Wahrscheinlichkeit, dass der Wirkstoff bei typischen Oralkeimen Resistenzbildung auslöst, sollte gering sein.J The likelihood of drug-induced resistance to typical oral bacteria should be low.
K Es sollten keine chemischen Reaktionen des Wirkstoffs mit den Monomeren, Füllstoffen, Initiatoren, Stabilisatoren und Farbstoffen während der Lagerung und Härtungsreaktion auftretenK There should be no chemical reactions of the active ingredient with the monomers, fillers, initiators, stabilizers and dyes during storage and curing reactions
Die Aufgaben werden dadurch gelöst, dass Dentalmaterial zur Verfügung gestellt wird, das in für Dentalmonomere löslichkeitsvermittelndes Verkapselungsmaterial eingehüllte antimikrobielle Wirkstoffe enthält. Derartige Kapseln enthalten vorzugsweise ein Dequalinium-Salz, ein Imino- pyridinium-Derivat, insbesondere ein Octenidin-Salz, Sanguinarin oder Akacid®) [Poly-[2-(2- ethoxy)-ethoxyethyl)-guanidinium-chlorid] (CAS No.: 374572-91-5). Die Kapseln sind im Dentalmaterial vor dem Aushärten homogen verteilt, so dass der daraus hergestellte jeweilige Formkörper (z.B. Inlay, Füllung oder Krone) ebenfalls eine homogene Verteilung des verkapselten Wirkstoffs aufweist.The objects are achieved by providing dental material containing antimicrobial agents encased in encapsulating material which solubilizes dental monomers. Such capsules preferably contain a dequalinium salt, an iminopyridinium derivative, in particular an octenidine salt, sanguinarine or Akacid®) [poly- [2- (2-ethoxy) ethoxyethyl) guanidinium chloride] (CAS no. : 374572-91-5). The capsules are homogeneously distributed in the dental material prior to curing, so that the respective shaped body produced therefrom (for example inlay, filling or crown) likewise has a homogeneous distribution of the encapsulated active substance.
Die Erfindung betrifft somit Dentalmaterial nach Anspruch 1. Vorteilhafte Ausgestaltungen sind den weiteren Ansprüchen zu entnehmen.The invention thus relates to dental material according to claim 1. Advantageous embodiments are given in the further claims.
Detaillierte BeschreibungDetailed description
Als mit den Merkmalen der Erfindung ausgestattete Materialien kommen solche für Füllungs- komposite, Verblendkomposite, Prothesenwerkstoffe, künstliche Zähne, Abformmassen, Schutzlacke, Fissurenversiegler und Dentinbondings, aber auch veterinärmedizinische Materialien wie Hufmaterial in Frage.As provided with the features of the invention, such materials for filling composites, Verblendkomposite, denture materials, artificial teeth, impression materials, protective coatings, Fissurenversiegler and Dentinbondings, but also veterinary materials such as hoof material in question.
Die Verkapselung des jeweiligen Wirkstoffs kann z.B. nach folgenden an sich bekannten Verfahren erfolgen:The encapsulation of the respective active substance can e.g. take place according to the following methods known per se:
DE 10 2006 050 153 A1 beschreibt Dentalmaterialien mit in Polymeren mikroverkapselten Photoinitiatoren. Dabei werden die Bedingungen so gewählt, dass ein konstanter Anteil an freiem Photoinitiator vorhanden ist. Insbesondere wird in_Absatz [0018] die Verkapselung von Photoinitiatoren nach der sogenannten Miniemulsionsmethode beschrieben. Dabei wird der zu verkapselnde Wirkstoff in einem durch einen geeigneten Emulgator [(z.B. Natriumdodecylsulfat, Polyoxyethylen-Sorbitanester (Tween)] stabilisierten Zweiphasensystem mit einem polymeri- sierbaren Anteil vorgelegt. Die durch Ultraschalleinwirkung erzeugte stabile Emulsion enthält zusätzlich einen thermischen Initiator, der die Polymerisation um die Wirkstoffpartikel herum einleitet.DE 10 2006 050 153 A1 describes dental materials with photoinitiators microencapsulated in polymers. The conditions are chosen so that a constant proportion of free Photoinitiator is present. In particular, the encapsulation of photoinitiators according to the so-called miniemulsion method is described in_example [0018]. The active substance to be encapsulated is initially charged in a two-phase system with a polymerizable fraction stabilized by a suitable emulsifier [(eg sodium dodecyl sulfate, polyoxyethylene sorbitan ester (Tween)].) The stable emulsion produced by the action of ultrasound additionally contains a thermal initiator which reverses the polymerization initiates the drug particles around.
In DE 10 2004 013 637 A1 werden in den Absätzen [0005-7] drei bekannte Methoden der Mik- roverkapselung beschrieben. DE 692 14 278 T2 beschreibt Dentalzemente mit in wasserlöslichem Material verkapselte(m) Redox-Initiator. Als Mantelmaterial wird Celluloseacetylbutyrat verwendet.DE 10 2004 013 637 A1 describes in paragraphs [0005-7] three known methods of microencapsulation. DE 692 14 278 T2 describes dental cements with encapsulated in water-soluble material (m) redox initiator. The jacket material used is cellulose acetyl butyrate.
DE 10 2005 007 374 A1 beschreibt mit medizinischen Markern versehene Nanopartikel, die durch Mikroemulsionspolymerisation (radikalisch oder anionisch) hergestellt werden sollen. Ein Ausführungsbeispiel für deren Herstellung gibt es nicht; es wird lediglich das fertige Produkt beschrieben (Fig. 1 und Absatz [0029]).DE 10 2005 007 374 A1 describes nanoparticles provided with medical markers which are to be produced by microemulsion polymerization (free-radical or anionic). An embodiment for their production does not exist; only the finished product is described (Figure 1 and paragraph [0029]).
In DE 102 44 503 A1 werden bioverfügbare Kapseln vorgeschlagen, deren Hülle durch „elektrostatische Selbstassemblierung" zustande kommen soll. Ein Ausführungsbeispiel für diese Methode ist nicht enthalten.In DE 102 44 503 A1, bioavailable capsules are proposed whose sheath is to be produced by "electrostatic self-assembly." An exemplary embodiment of this method is not included.
Ähnliche auf der Basis von Polyelektrolyten herstellbare Kapseln schlägt DE 10 2005 044 400 A1 vor. Danach sind derartige Kapseln aus DE 198 12 083 A1 , DE 199 07 552 A1 , EP 0 972 563 A1 , WO99/47252 A2 und US 6,479,146 B1 , bekannt, die sich besonders durch einstellbare Semipermeabilität auszeichnen. In den Absätzen [0004-5] werden Herstellmethoden dafür skizziert. Es handelt sich allerdings um Anforderungen, die im Inneren gehärteter Dentalwerkstoffe, die der Abrasion ausgesetzt sind, keine Rolle spielen.Similar capsules which can be produced on the basis of polyelectrolytes are proposed by DE 10 2005 044 400 A1. Thereafter, such capsules are known from DE 198 12 083 A1, DE 199 07 552 A1, EP 0 972 563 A1, WO99 / 47252 A2 and US Pat. No. 6,479,146 B1, which are particularly distinguished by adjustable semipermeability. In paragraphs [0004-5] manufacturing methods are outlined for it. However, these are requirements that are irrelevant in the interior of hardened dental materials that are exposed to abrasion.
Als Verkapselungsmittel kommen vorzugsweise für Medizinprodukte zulässige Polymere in Frage, wie z.B. Polystyrol, dessen Copolymere mit weiteren Vinylmonomeren, Polymethyl- methacrylat, dessen Copolymere mit weiteren ethylenisch ungesättigten Monomeren, sowie weitere an sich bekannte Materialien, die dem auf dem Verkapselungsgebiet tätigen Fachmann geläufig sind. Bei der Verkapselung ergeben sich nicht unbedingt stets sphärische Partikel - es genügt, wenn der Wirkstoff vollständig umhüllt ist. Der Partikeldurchmesser liegt zweckmäßig bei bis zu 50 μm, bevorzugt bis zu 10 μm, besonders bevorzugt bis zu 0,1 μm. Die untere Grenze wird durch die Partikelgröße der kleinsten Teilchen des eingesetzten Pulvers und die Dicke der Beschichtung bestimmt.As encapsulants are preferably for medical devices admissible polymers in question, such as polystyrene, its copolymers with other vinyl monomers, polymethyl methacrylate, its copolymers with other ethylenically unsaturated monomers, and other known per se materials that are familiar to those working in the field of encapsulation expert. The encapsulation does not always produce spherical particles - it is sufficient if the active substance is completely enveloped. The particle diameter is appropriate at up to 50 microns, preferably up to 10 microns, more preferably up to 0.1 microns. The lower limit is determined by the particle size of the smallest particles of the powder used and the thickness of the coating.
Der Wirkstoff liegt im Dentalmaterial bevorzugt in Mengen bis 3 Gew. %, besonders bevorzugt bis 1 Gew % vor. Die untere Grenze hängt von der Stärke der antimikrobiellen Wirkung ab.The active ingredient is present in the dental material preferably in amounts of up to 3% by weight, more preferably up to 1% by weight. The lower limit depends on the strength of the antimicrobial effect.
Die Verkapselung kann in mehreren Schritten („layer by layer") hergestellt werden, wie in den zitierten Schriften DE 198 12 083 A1 , DE 199 07 552 A1 , EP 0 972 563, WO 99/47252 A2, US 6,479,146 B1 und WO 2007/031345 beschrieben.The encapsulation can be produced in several steps ("layer by layer"), as in the cited documents DE 198 12 083 A1, DE 199 07 552 A1, EP 0 972 563, WO 99/47252 A2, US Pat. No. 6,479,146 B1 and WO 2007 / 031345.
Der Wirkstoff kann in dendritischen Polymertransportsystemen eingebettet sein. Diese Technologie ist als „NT System" bekannt geworden.The active ingredient may be embedded in dendritic polymer transport systems. This technology has become known as the "NT System".
Die Kapseln können auch mit einer Doppeldüsentechnik erzeugt werden. Diese wird von der Firma BRACE GmbH, Alzenau, angeboten (DE 196 17 924 A1).The capsules can also be produced with a double nozzle technique. This is offered by BRACE GmbH, Alzenau (DE 196 17 924 A1).
Vorteile der ErfindungAdvantages of the invention
Eine Inaktivierung des Wirkstoffs auf der Oberfläche des ausgehärteten Dentalmaterials wird erschwert, weil ständig Wirkstoff aus dem Inneren nachdiffundieren kann. Eine homogene Verteilung des Wirkstoffes im Bulk-Material wird dabei durch ausreichende Konzentration der mik- roverkapselten Wirkstoffe sichergestellt. Die Verkapselung sorgt dafür, dass auch Wirkstoffe in Dentalmaterialien eingearbeitet werden können, welche typischerweise nur eine geringe Löslichkeit in Dentalmonomeren aufweisen.Inactivation of the active ingredient on the surface of the cured dental material is made more difficult, because active substance can diffuse from the inside constantly. Homogeneous distribution of the active ingredient in the bulk material is ensured by sufficient concentration of the microencapsulated active ingredients. The encapsulation ensures that active ingredients can also be incorporated into dental materials which typically have only a low solubility in dental monomers.
Es ist unter Umständen auch möglich, farbige Wirkstoffe einzuarbeiten, sofern das Verkapse- lungsmaterial der Compositfarbe entspricht.It may also be possible to incorporate colored active substances if the encapsulation material corresponds to the composite color.
Das folgende Beispiel erläutert die Erfindung näher. Teile und Prozentangaben beziehen sich, wie in der übrigen Beschreibung, auf das Gewicht, sofern nicht anders angegeben.The following example explains the invention in more detail. Parts and percentages are by weight unless otherwise indicated, as in the rest of the description.
AusführunαsbeispielAusführunαsbeispiel
PMMA-VerkapselungPMMA encapsulation
Die Herstellung erfolgt in Analogie zu DE 10 2006 050 503 A1 , Beispiel 1.The preparation is carried out analogously to DE 10 2006 050 503 A1, Example 1.
Zur Herstellung der dispersen Phase werden 1.0 g Octenidin, 5.0 g Methylmethacrylat, 250 mg Hexadekan und 100 mg 2,2'-Azobis-(2-methylbutyl-1-nitril) im 50 ml Becherglas vermischt und gerührt, bis das Octenidin vollständig gelöst ist. Für die kontinuierliche Phase werden 72 mg Natriumdodecylsulfat in 24.0 g demineralisiertem Wasser gelöst. Anschließend wird die kontinuierliche Phase unter kontinuierlichem Rühren zur dispersen Phase gegeben und 1 h bei 2000 U min-1 gerührt. Die entstandene Makro-Emulsion wird mittels eines Ultraschallstabes (1/2" Spitze) für eine Schalldauer von 2 min bei 90% Amplitude im Eisbad miniemulgiert. Die Probe wird in einen 50 ml Kolben überführt und über Nacht verschlossen unter kontinuierlichem Rühren bei 1000 U min<-1> und 70° C polymerisiert. Die Suspension wird warm filtriert und gefriergetrocknet. Zur Aufreinigung und Entfernung von unverkapseltem Octenidin werden die Kapseln auf einem Filterpapier mit 30 ml Ethanol gewaschen und im Vakuum getrocknet. Durch erneute Gefriertrocknung wird restliches Ethanol entfernt, hierdurch wird eine Quellung der Kapseln verhindert. 50 mg des getrockneten Kapselmaterials werden entnommen und Partikelgröße und Octenidingehalt bestimmt. Die mit der dynamischen Lichtstreuung (DLS) bestimmte Teilchengröße beträgt 132 nm, der Octenidinanteil in den Kapseln beträgt 25 Gew.% des ursprünglich eingesetzten Octenidins (entspricht ca. 5 Gew.% reinem Lucirinanteil der Kapseln). To prepare the disperse phase, 1.0 g of octenidine, 5.0 g of methyl methacrylate, 250 mg of hexadecane and 100 mg of 2,2'-azobis (2-methylbutyl-1-nitrile) are mixed in a 50 ml beaker and stirred until the octenidine is completely dissolved. For the continuous phase, 72 mg of sodium dodecyl sulfate are dissolved in 24.0 g of demineralized water. Subsequently, the continuous phase is added to the disperse phase with continuous stirring and stirred for 1 h at 2000 U min-1. The resulting macro-emulsion is miniemulgiert by means of an ultrasonic rod (1/2 "tip) for a period of 2 min at 90% amplitude in an ice bath.The sample is transferred to a 50 ml flask and sealed overnight with continuous stirring at 1000 U min The suspension is filtered warm and freeze dried For purification and removal of unencapsulated octenidine, the capsules are washed on a filter paper with 30 ml of ethanol and dried in vacuo capsules are prevented from swelling, 50 mg of the dried capsule material are removed and the particle size and octenidine content are determined The particle size determined by dynamic light scattering (DLS) is 132 nm, the octenidine content in the capsules being 25% by weight of the original octenidine (corresponding to about 5% by weight of pure lucirin content of the capsules).

Claims

Patentansprüche claims
1. Dentalmaterial enthaltend mindestens einen antimikrobiellen Wirkstoff, der in Kapseln aus für Dentalmonomere löslichkeitsvermittelndem Verkapselungsmaterial eingehüllt ist.A dental material containing at least one antimicrobial agent encased in capsules of encapsulating material that solubilizes dental monomers.
2. Dentalmaterial nach Anspruch 1 , dadurch gekennzeichnet, dass der Wirkstoff ein Iminopyridinium-Derivat ist.2. Dental material according to claim 1, characterized in that the active ingredient is an iminopyridinium derivative.
3. Dentalmaterial nach Anspruch 1 , dadurch gekennzeichnet, dass der Wirkstoff ein Octenidin-Salz ist.3. Dental material according to claim 1, characterized in that the active ingredient is an octenidine salt.
4. Dentalmaterial nach Anspruch 1 , dadurch gekennzeichnet, dass der Wirkstoff Poly-[2-(2-ethoxy)-ethoxyethyl)-guanidinium-chlorid (Akacid®) ist.4. Dental material according to claim 1, characterized in that the active ingredient is poly- [2- (2-ethoxy) -ethoxyethyl] guanidinium chloride (Akacid®).
5. Dentalmaterial nach Anspruch 1 , dadurch gekennzeichnet, dass der Wirkstoff ein Dequalinium-Salz ist.5. Dental material according to claim 1, characterized in that the active ingredient is a dequalinium salt.
6. Dentalmaterial nach Anspruch 1 , dadurch gekennzeichnet, dass der Wirkstoff Sanguinarin ist.6. Dental material according to claim 1, characterized in that the active substance is sanguinarine.
7. Dentalmaterial nach mindestens einem der Ansprüche 1 - 6, dadurch gekennzeichnet, dass die Kapseln einen Durchmesser bis 50 μm aufweisen.7. dental material according to at least one of claims 1-6, characterized in that the capsules have a diameter of up to 50 microns.
8. Dentalmaterial nach mindestens einem der Ansprüche 1 - 6, dadurch gekennzeichnet, dass die Kapseln einen Durchmesser bis 10 μm aufweisen.8. Dental material according to at least one of claims 1-6, characterized in that the capsules have a diameter of up to 10 microns.
9. Dentalmaterial nach mindestens einem der Ansprüche 1 - 6, dadurch gekennzeichnet, dass die Kapseln einen Durchmesser bis 0,1 μm aufweisen.9. dental material according to at least one of claims 1-6, characterized in that the capsules have a diameter of 0.1 microns.
10. Dentalmaterial nach mindestens einem der Ansprüche 1 - 9, dadurch gekennzeichnet, dass die Kapseln mit einer layer-by-layer-Technologie (LBL) hergestellt werden10. Dental material according to at least one of claims 1-9, characterized in that the capsules are produced with a layer-by-layer technology (LBL)
11. Dentalmaterial nach mindestens einem der Ansprüche 1 - 9, dadurch gekennzeichnet, dass der Wirkstoff in einem dendritischen Polymer-Transportsystem eingebettet ist.11. Dental material according to any one of claims 1-9, characterized in that the active ingredient is embedded in a dendritic polymer transport system.
12. Dentalmaterial nach mindestens einem der Ansprüche 1 - 9 dadurch gekennzeichnet, dass die Kapseln mit einer Doppeldüsentechnik hergestellt werden. 12. Dental material according to at least one of claims 1-9, characterized in that the capsules are manufactured with a double nozzle technique.
13. Dentalmaterial nach mindestens einem der Ansprüche 1 - 9, dadurch gekennzeichnet, dass die Kapseln so ausgestattet sind, dass der Wirkstoff durch Druck (beim Kauen), enzymatischen Abbau durch Speichelproteine, Körperwärme, Diffusion durch Poren oder Abrasion freigesetzt wird.13. Dental material according to any one of claims 1-9, characterized in that the capsules are equipped so that the active ingredient is released by pressure (when chewing), enzymatic degradation by salivary proteins, body heat, diffusion through pores or abrasion.
14. Dentalmaterial nach mindestens einem der Ansprüche 1 - 9, dadurch gekennzeichnet, dass die Kapseln aus mindestens zwei Mitgliedern der Gruppe der natürlichen und s ynthetischen Polymere und der natürlichen und synthetischen Wachse bestehen.Dental material according to at least one of claims 1-9, characterized in that the capsules consist of at least two members of the group of natural and synthetic polymers and of natural and synthetic waxes.
15. Dentalmaterial nach mindestens Ansprüche 1 - 9, dadurch gekennzeichnet, dass die Kapseln aus einem natürlichen oder synthetischen Polymer oder einem natürlichen oder synthetischen Wachs bestehen.15. Dental material according to at least claims 1-9, characterized in that the capsules consist of a natural or synthetic polymer or a natural or synthetic wax.
16. Dentalmaterial nach mindestens einem der Ansprüche 1 - 12, dadurch gekennzeichnet, dass die Kapseln eine zur Löslichkeitsvermittlung funktionalisierte Oberfläche aufweisen.16. Dental material according to at least one of claims 1-12, characterized in that the capsules have a functionalized for solubilization surface.
17. Dentalmaterial nach mindestens einem der Ansprüche 1 - 12, dadurch gekennzeichnet, dass die Kapseln mechanisch so stabil sind, dass sie den während des Produktionsprozesses dentaler Materialien üblicherweise auftretenden hohen Scherkräfte unzerstört widerstehen.17. Dental material according to any one of claims 1-12, characterized in that the capsules are mechanically stable so that they withstand the high shear forces usually occurring during the production process of dental materials undestroyed.
18. Dentalmaterial nach mindestens einem der Ansprüche 1 - 17, dadurch gekennzeichnet, dass der oder die Wirkstoff(e) in Mengen bis zu 3 Gew. % im Dentalmaterial vorliegen.18. Dental material according to any one of claims 1-17, characterized in that the or the active ingredient (s) in amounts up to 3 wt.% Are present in the dental material.
19. Dentalmaterial nach Anspruch 18, dadurch gekennzeichnet, dass der oder die Wirkstoffe) in Mengen bis zu 1 Gew. % im Dentalmaterial vorliegen.19. Dental material according to claim 18, characterized in that the active substance (s) are present in amounts of up to 1% by weight in the dental material.
20. Dentalmaterial nach mindestens einem der Ansprüche 1 - 19, dadurch gekennzeichnet, dass eine weitere, unverkapselte antimikrobielle Komponente enthalten ist.20. Dental material according to any one of claims 1-19, characterized in that a further, unencapsulated antimicrobial component is included.
21. Dentalmaterial nach Anspruch 20, wobei die weitere Komponente den Gruppen der monokationischen Antiseptika, dikationischen Antiseptika, oligo- oder polymeren kationischen Antiseptika und antiseptischen Schwermetall-Verbindungen angehört. 21. Dental material according to claim 20, wherein the further component belongs to the groups of monocationic antiseptics, dicationic antiseptics, oligomeric or polymeric cationic antiseptics and antiseptic heavy metal compounds.
PCT/EP2009/009125 2009-01-08 2009-12-17 Dental materials comprising anti-microbial active substances for preventing plaque deposits WO2010078936A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009004368.3 2009-01-08
DE102009004368A DE102009004368A1 (en) 2009-01-08 2009-01-08 Dental materials containing antimicrobial agents for the prevention of plaque accumulation

Publications (1)

Publication Number Publication Date
WO2010078936A1 true WO2010078936A1 (en) 2010-07-15

Family

ID=41650418

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/009125 WO2010078936A1 (en) 2009-01-08 2009-12-17 Dental materials comprising anti-microbial active substances for preventing plaque deposits

Country Status (2)

Country Link
DE (1) DE102009004368A1 (en)
WO (1) WO2010078936A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107847643A (en) * 2016-01-17 2018-03-27 孙国明 Biocompatibility polysaccharide hydrogel and application method

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008021473A1 (en) * 2008-04-29 2009-11-12 Heraeus Kulzer Gmbh Dental materials equipped with antiplaque agent (s)
DE102010035856A1 (en) 2010-08-30 2012-03-01 Heraeus Kulzer Gmbh Dental material comprises molecularly dispersed octenidine dihydrochloride, which is dissolved in solubilizing hydroxy functionalized dental monomers
KR102315893B1 (en) * 2014-10-16 2021-10-22 삼성전자주식회사 Cooperation sensing method of terminal and terminal of performing cooperation sensing

Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4206215A (en) * 1976-02-25 1980-06-03 Sterling Drug Inc. Antimicrobial bis-[4-(substituted-amino)-1-pyridinium]alkanes
DE69214278T2 (en) 1991-03-19 1997-04-24 Agrevo Uk Ltd FUNGICIDE COMPOSITIONS
US5639476A (en) 1992-01-27 1997-06-17 Euro-Celtique, S.A. Controlled release formulations coated with aqueous dispersions of acrylic polymers
DE19617924A1 (en) 1996-05-05 1997-11-13 Brace Gmbh Chemie Plastics Dat Piezoelectric excitation of sprayed fluid close to nozzle exits
JPH1025218A (en) * 1996-07-12 1998-01-27 Kuraray Co Ltd Antimicrobial filler
DE19641775A1 (en) * 1996-08-22 1998-02-26 Merck Patent Gmbh Process for the production of active ingredient-containing bone cements
US5875798A (en) 1997-09-23 1999-03-02 Advanced Medical Instruments, Inc. Therapeutic toothpick for treating oral and systemic diseases
WO1999047252A2 (en) 1998-03-19 1999-09-23 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Production of nanocapsules and microcapsules by layer-wise polyelectrolyte self-assembly
DE19812083A1 (en) 1998-03-19 1999-09-30 Max Planck Gesellschaft Simple preparation of coated particles, used to prepare systems for slow and/or targeted release of actives including pharmaceuticals, contrast agents, herbicides, pesticides, catalysts and pigments
EP0972563A1 (en) 1998-07-15 2000-01-19 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Fabrication of multilayer-coated particles and hollow shells via electrostatic self-assembly of nanocomposite multilayers on decomposable colloidal templates
DE19907552A1 (en) 1999-02-22 2000-08-31 Max Planck Gesellschaft New stable polyelectrolyte capsules of controllable permeability, prepared by coating template particles, useful e.g. for controlled drug release
US6479146B1 (en) 1998-03-19 2002-11-12 Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften, E.V. Fabrication of multilayer-coated particles and hollow shells via electrostatic self-assembly of nanocomposite multilayers on decomposable colloidal templates
DE10244503A1 (en) 2002-09-25 2004-04-08 Capsulution Nanoscience Ag Method for the preparation and stabilization of micro and nano suspensions with amphiphiles and polyelectrolytes
EP1280766B1 (en) 2000-05-11 2004-12-22 POC Polymer Produktions GmbH Biocidal polymers based on guanidine salts
WO2005009495A1 (en) * 2003-07-18 2005-02-03 Biomet Deutschland Gmbh Use of antiseptic active principles in pmma bone cements
US20050048005A1 (en) * 2003-08-26 2005-03-03 Stockel Richard F. Antimicrobial compositions for dental applications
DE102004013637A1 (en) 2004-03-19 2005-10-13 Capsulution Nanoscience Ag Process for the preparation of CS particles and microcapsules using porous templates as well as CS particles and microcapsules
EP1649874A2 (en) * 2004-10-07 2006-04-26 Heraeus Kulzer GmbH PMMA bone cement containing antibiotics
DE102005007374A1 (en) 2005-02-17 2006-08-24 Universität Ulm Nano-particle, useful e.g. as carriers for transport of active substances, comprises hydrophobic and biocompatible functionalized polymer, active material and/or marker
DE102005044400A1 (en) 2005-09-16 2007-03-22 Capsulution Nanoscience Ag Process for the encapsulation and controlled release of poorly water soluble (hydrophobic) liquid and solid drugs
US20070172434A1 (en) * 2006-01-24 2007-07-26 Jernberg Gary R Antimicrobial dental materials, restorations, and prostheses
DE102006050503A1 (en) 2006-10-26 2008-04-30 GM Global Technology Operations, Inc., Detroit Shifting clutch for switching device or synchronizing device, particularly control gear of vehicle, has ratchet wheel provided with selector teeth and pivoted on shaft around axis
DE102006050153A1 (en) 2006-10-25 2008-05-08 Ivoclar Vivadent Ag Microencapsulated photoinitiators and their use for dental materials
WO2009030413A2 (en) * 2007-08-28 2009-03-12 Schulz Hans H Method for the prophylaxis of caries and parodontopathy
EP2113237A1 (en) * 2008-04-29 2009-11-04 Heraeus Kulzer GmbH Dental materials with anti-plaque agents

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6553996B2 (en) * 2000-09-08 2003-04-29 Jon D. Kittelsen Dental appliance with antimicrobial additive
DE102005045146A1 (en) * 2005-09-15 2007-03-29 Schülke & Mayr GmbH Antimicrobial preparation useful for treating e.g. wound, eczema and vaginal infections comprises octenidine dihydrochloride encapsulated in liposomes
US7544377B2 (en) * 2005-12-02 2009-06-09 Gic Innovations Company Chewable compositions with fast release magnolia bark extract

Patent Citations (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4206215A (en) * 1976-02-25 1980-06-03 Sterling Drug Inc. Antimicrobial bis-[4-(substituted-amino)-1-pyridinium]alkanes
DE69214278T2 (en) 1991-03-19 1997-04-24 Agrevo Uk Ltd FUNGICIDE COMPOSITIONS
US5639476A (en) 1992-01-27 1997-06-17 Euro-Celtique, S.A. Controlled release formulations coated with aqueous dispersions of acrylic polymers
DE19617924A1 (en) 1996-05-05 1997-11-13 Brace Gmbh Chemie Plastics Dat Piezoelectric excitation of sprayed fluid close to nozzle exits
JPH1025218A (en) * 1996-07-12 1998-01-27 Kuraray Co Ltd Antimicrobial filler
DE19641775A1 (en) * 1996-08-22 1998-02-26 Merck Patent Gmbh Process for the production of active ingredient-containing bone cements
US5875798A (en) 1997-09-23 1999-03-02 Advanced Medical Instruments, Inc. Therapeutic toothpick for treating oral and systemic diseases
WO1999047252A2 (en) 1998-03-19 1999-09-23 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Production of nanocapsules and microcapsules by layer-wise polyelectrolyte self-assembly
DE19812083A1 (en) 1998-03-19 1999-09-30 Max Planck Gesellschaft Simple preparation of coated particles, used to prepare systems for slow and/or targeted release of actives including pharmaceuticals, contrast agents, herbicides, pesticides, catalysts and pigments
US6479146B1 (en) 1998-03-19 2002-11-12 Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften, E.V. Fabrication of multilayer-coated particles and hollow shells via electrostatic self-assembly of nanocomposite multilayers on decomposable colloidal templates
EP0972563A1 (en) 1998-07-15 2000-01-19 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Fabrication of multilayer-coated particles and hollow shells via electrostatic self-assembly of nanocomposite multilayers on decomposable colloidal templates
DE19907552A1 (en) 1999-02-22 2000-08-31 Max Planck Gesellschaft New stable polyelectrolyte capsules of controllable permeability, prepared by coating template particles, useful e.g. for controlled drug release
EP1280766B1 (en) 2000-05-11 2004-12-22 POC Polymer Produktions GmbH Biocidal polymers based on guanidine salts
DE10244503A1 (en) 2002-09-25 2004-04-08 Capsulution Nanoscience Ag Method for the preparation and stabilization of micro and nano suspensions with amphiphiles and polyelectrolytes
WO2005009495A1 (en) * 2003-07-18 2005-02-03 Biomet Deutschland Gmbh Use of antiseptic active principles in pmma bone cements
US20050048005A1 (en) * 2003-08-26 2005-03-03 Stockel Richard F. Antimicrobial compositions for dental applications
DE102004013637A1 (en) 2004-03-19 2005-10-13 Capsulution Nanoscience Ag Process for the preparation of CS particles and microcapsules using porous templates as well as CS particles and microcapsules
EP1649874A2 (en) * 2004-10-07 2006-04-26 Heraeus Kulzer GmbH PMMA bone cement containing antibiotics
DE102005007374A1 (en) 2005-02-17 2006-08-24 Universität Ulm Nano-particle, useful e.g. as carriers for transport of active substances, comprises hydrophobic and biocompatible functionalized polymer, active material and/or marker
DE102005044400A1 (en) 2005-09-16 2007-03-22 Capsulution Nanoscience Ag Process for the encapsulation and controlled release of poorly water soluble (hydrophobic) liquid and solid drugs
WO2007031345A2 (en) 2005-09-16 2007-03-22 Capsulution Nanoscience Ag Method for the encapsulation and controlled-release of poorly water-soluble (hydrophobic) liquid and solid active ingredients
US20070172434A1 (en) * 2006-01-24 2007-07-26 Jernberg Gary R Antimicrobial dental materials, restorations, and prostheses
DE102006050153A1 (en) 2006-10-25 2008-05-08 Ivoclar Vivadent Ag Microencapsulated photoinitiators and their use for dental materials
DE102006050503A1 (en) 2006-10-26 2008-04-30 GM Global Technology Operations, Inc., Detroit Shifting clutch for switching device or synchronizing device, particularly control gear of vehicle, has ratchet wheel provided with selector teeth and pivoted on shaft around axis
WO2009030413A2 (en) * 2007-08-28 2009-03-12 Schulz Hans H Method for the prophylaxis of caries and parodontopathy
EP2113237A1 (en) * 2008-04-29 2009-11-04 Heraeus Kulzer GmbH Dental materials with anti-plaque agents

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107847643A (en) * 2016-01-17 2018-03-27 孙国明 Biocompatibility polysaccharide hydrogel and application method

Also Published As

Publication number Publication date
DE102009004368A1 (en) 2010-07-15

Similar Documents

Publication Publication Date Title
DE60116142T2 (en) DENTAL MASSES
EP0731692B1 (en) Device for effecting the controlled release of active substances
DE60007650T2 (en) Encapsulated active material, immobilized in hydrogel microbeads
DE3834634C2 (en) Antiseptic-containing alginate impression material
DE10340277B4 (en) Personal care products containing silver agglomerates
KR20090121291A (en) Method for preparing particles comprising metal oxide coating and particles with metal oxide coating
DE2121480A1 (en) X-ray opaque methacrylate particles soluble in monomer
WO1981001366A1 (en) Use of silicic acid pellets as exipients for dental mass material
EP2698142B1 (en) Dental filling materials and dental varnish for the inhibition of biofilm formation of streptococcus mutans, and their preparation
EP2103296B1 (en) Polymer-coated glass filler for use in dental material
DE69818287T2 (en) DENTINSCHUTZLACK
Wang et al. Rapid antibiofilm effect of Ag/ZnO nanocomposites assisted by dental LED curing light against facultative anaerobic oral pathogen Streptococcus mutans
EP2550863A1 (en) Particles on a polyacrylate basis containing active materials
EP0832636A2 (en) Polymerisable dental material and use of apatite fillers in the dental material
WO2010078936A1 (en) Dental materials comprising anti-microbial active substances for preventing plaque deposits
DE10340800A1 (en) Production of acrylic bone cement, e.g. for anchoring prostheses in bone, involves using X-ray contrast medium which has been functionalised with (meth)acrylate after coating with melamine-formaldehyde resin
DE102008021473A1 (en) Dental materials equipped with antiplaque agent (s)
EP2461785B1 (en) Dental materials containing antimicrobial agents, particularly for the prevention of plaque deposits
EP1919436B1 (en) Material primarily for medical, long-term in vivo use, and method for the production thereof
WO2017149474A1 (en) Process for the production of antimicrobial dental adhesives including graphene and relative product thereof
WO2019243187A1 (en) Method for producing an antibacterial chitosan-containing polymer for medical purposes, in particular for wound treatment
DE19713048A1 (en) Plaque inhibiting composite
EP2346539B1 (en) Polymerizable multi-component prosthesis starting material, particularly for dental prostheses
EP2384733B1 (en) Antimicrobial dental materials
DE2408640A1 (en) ACRYLIC POLYMER BLEND

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09799540

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 09799540

Country of ref document: EP

Kind code of ref document: A1