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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/50—Preparations specially adapted for dental root treatment
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/50—Preparations specially adapted for dental root treatment
  • A61K6/54—Filling; Sealing

Definitions

• the invention relates to a dental filling material mixture, in particular a material mixture for filling root canals, containing (a) an epoxide and (b) an amino acid and / or an amino acid derivative. Furthermore, the invention relates to a method for producing a dental filling material by providing a dental filling material mixture and then curing the mixture as well as the dental filling material obtainable by this method. Furthermore, the invention comprises a kit for providing a dental filling material mixture in which components (a) and (b) are present separately from one another. Background of the invention
• Root canal filling materials are used to fill a prepared root canal. Treatments for these fillings are usually "blind.” This means that the result of the preparatory measures and the filling itself can not be visually assessed directly.
• a root canal treatment the pulp tissue is first removed. Subsequently, the root canal lumen is treated with standardized instruments, rinsed and dried. Often, the root canal is not immediately filled, but filled with antimicrobial calcium hydroxide paste for a few days to weeks.
• several methods are suitable. As a standard technique, the lateral condensation has been proven in the multiple gutta-percha with Root canal filling material coated and introduced into the channel. Usually, a standardized gutta-percha pencil (conforming to the last instrument size of the reprocessing) is fitted into the prepared root canal. The seat of this pen (main pen / masterpoint) is often checked by X-ray.
• the pin and / or the channel wall are coated with a Bentin, and the pin is re-introduced into the root canal.
• any remaining gaps can be reduced by the subsequent insertion of needle-like condensation instruments.
• These condensing instruments adjust the deformed pin and the filling material of the channel wall. Additional pins can be added to fill the often irregular channel wall. However, this procedure is very cumbersome and often leads to an unsatisfactory seal.
• Plastic fillings can be made of different materials: amalgam, plastic cement and composites are common materials. There are differences, among other things, in terms of durability, resistance to chewing pressure, cost and aesthetics.
• Special filling materials are used in the field of root canal treatments.
• a prerequisite of such filling materials is to permanently hermetically and biocompatible seal the entire root canal system to prevent the ingress of To prevent liquids and microorganisms in the root canal.
• Fillers available on the dental market consist essentially of zinc oxide or calcium hydroxide together with an organic salt former or a combination of epoxides and amines.
• materials based on eugenol (a phenylpropanoid) and calcium hydroxide do not meet the high standards of modern materials in terms of adhesion and processability.
• the edge sealing of the filling to the tooth edge is one of the main aspects.
• the material used must seal the canal in order to prevent the infiltration of infectious germs, otherwise there is a risk of infection.
• the prerequisite for obtaining the tightness is a very low solubility of the filler.
• the material must be tissue-compatible, since it can come into contact with living tissue when introduced into the root canal.
• the filler material of the glass ionomer cements is known for its tight edge seal, as it has chemical-physical adhesion to the dentin. In addition, it shows a very low solubility and is also classified as tissue-compatible. Glass ionomer cements available today are relatively inexpensive. However, they are severely limited in durability and compressive strength. Furthermore, they lack sufficient processing time for introduction into the root canal. The dentist usually needs 1 hour to fill the root canal, including X-ray, but GICs cure much faster.
• urotropin is used in these epoxy resins in addition to the epoxide as a further ingredient.
• the urotropin releases during the hardening of the filling, however, the toxic formaldehyde, which can lead to health effects such as allergic reactions.
• WHO World Health Organization
• CMRs carcinogenic to humans'
• BfR Federal Institute for Risk Assessment
• dental filler mixtures such as root canal filling materials
• dental filler mixtures which do not have the aforementioned disadvantages of the materials known from the prior art. Consequently, there is a need for dental filling material mixtures, in particular for filling root canals, which are based on the most natural substances possible, are tissue-compatible, have a long shelf life and are resistant to biodegradation in the oral flora are, have optimal curing properties and can also be easily processed.
• a dental filling material mixture for filling root canals containing (a) an epoxide and (b) an amino acid or an amino acid derivative.
• the present invention further provides a process for producing a dental filling material for filling root canals by curing the dental filling material mixture comprising (a) an epoxide and (b) an amino acid and / or an amino acid derivative, in particular by curing at body temperature (ca. 37 ° C).
• the present invention also relates to a dental filling material, in particular for filling root canals, which is obtainable by the described method.
• the present invention further relates to a kit for providing a dental filling material mixture in which the components (a) and (b) are present separately from one another.
• a polyaminoalcohol is formed from a primary or a disecondary amine and an epoxide, in particular a di-, tri- or oligoepoxide as shown in the following reaction scheme.
• R 'and R "independently of one another are any organic radical such as Alky 1, Ary 1 or cycloalkyl, optionally substituted and may also contain heteroatoms, and n is a positive integer.
• the inventive dental filler mixtures for filling root canals comprise as the first component (component (a)) an epoxide.
• the epoxides according to the invention are particularly suitable for the production of root canal filling material in the form of high molecular weight, thermoplastic polymers by polyaddition reactions with an amine component.
• the epoxides used according to the invention include monomeric and polymeric epoxides and combinations thereof.
• the epoxy monomers preferably used may be aliphatic, cycloaliphatic, aromatic or heterocyclic, optionally substituted and may also contain heteroatoms.
• Suitable polymeric epoxies include linear polymers having terminal epoxide groups such as diglycidyl ethers of polyoxyalkylene glycol, polymers having oxirane moieties such as polybutadiene polyepoxide, and polymers having pendant epoxide groups such as glycidyl methacrylate polymers or copolymers.
• the epoxides according to the invention can be present as pure substance as well as mixtures.
• the epoxide units preferably contain 1, 2, 3 or more epoxide groups per molecule, more preferably 2 or 3 epoxide groups per molecule.
• epoxides for the purposes of the present invention are epoxide-group-containing di- and triglycidyl ethers connected via an aliphatic, cyclic, aromatic or branched radical R.
• heteroatoms may also be present in the radical R.
• Particularly preferred is bisphenol A diglycidyl ether (BADGE).
• the dental filler mixture according to the invention also contains as component (b) an amine component in the form of an amino acid and / or an amino acid derivative, wherein the amine component may also be present as mixtures of amino acids and / or amino acid derivatives.
• amino acid is a natural amino acid.
• natural amino acid here includes in particular the known proteinogenic amino acids, preferably in L-form, in particular selected from lysine, histidine, tryptophan, arginine or mixtures thereof, particularly preferred is lysine, in particular L-lysine.
• the dental filling material mixture contains an amino acid derivative.
• the amino acid derivative may also be present as a mixture with one or more underivatized amino acids.
• the amino acid may be derivatized at the carboxy terminus (C-terminus), at the ajm terminus (N-terminus) or at the ⁇ -C-atom.
• the amino acid is C- and / or N-terminally modified.
• Particularly preferred of the amino acid derivatives are esters of the aforementioned natural amino acids. Preferred examples include L-lysine tert-butyl ester or L-lysine methyl ester.
• the amine component in the form of the airiino acid or amino acid derivative is particularly preferably a cyclic amine component which is prepared by reaction of L-lysine methyl ester according to the method as described in WO 2005/123669, but with the difference that no lysine salts but the lysine methyl ester mentioned is used.
• the L-Lysinmethylester reacts to ⁇ -aminocaprolactam according to the following reaction, the reaction conditions are given only by way of example, although other, the skilled person apparent conditions may be suitable.
• the epoxide component and the amine component that is, the amino acid or the amino acid derivative, in a molar ratio of 10: 1 to 1: 10 mol / mol, preferably in a molar ratio of 2: 1 to 1: 2, more preferably in a molar ratio of about 1: 1.
• a particularly preferred combination of epoxide and amino component is the use of a mixture of bisphenol A diglycidyl ether (BADGE) with a-aminocaprolactam, wherein the optimum molar mixing ratio of the amine with B ADGE is 1: 1 mol / mol, but even a mixing ratio of up to 1: 2 mol / mol still leads to a product with good properties in terms of curing, durability and processing properties.
• BADGE bisphenol A diglycidyl ether
• the polyaddition reaction that occurs upon curing of this combination can be represented by the following reaction scheme, where n is a positive integer.
• the dental filler mixture contains at least one antimicrobial substance (component (c)).
• component (c) Commonly used starting materials, which emanate an antibacterial effect, are in particular colloidal silver, iodides and / or paraformaldehyde, which are to be regarded as critical due to health risks. Fillers and auxiliaries
• the dental filler mixture according to the invention may further contain one or more fillers and / or auxiliaries (component (d)), which may be organic or inorganic.
• Fillers and auxiliaries used in the material mixtures according to the invention are in particular those described in EP 0 673 637 Bl.
• the dental filler mixture may contain a further amine component, in particular a non-natural-based amine, more preferably selected from polyetheramine, imidazoline, imidazole and / or adamantylamine.
• a further amine component in particular a non-natural-based amine, more preferably selected from polyetheramine, imidazoline, imidazole and / or adamantylamine.
• the dental filler mixture may include an inorganic filler.
• the inorganic adjuvant is a radiopaque excipient.
• this should be at least 200% radiopaque (based on a 1 mm thick aluminum layer (100%)).
• Dentin has an X-ray opacity of about 118%.
• Inorganic fillers include, in particular, silicate, silicate glass, quartz, zinc oxide, barium sulfate, barium silicate, strontium silicate, barium borosilicate, strontium borosilicate, borosilicate, lithium silicate, amorphous silicate, bismuth compounds such as bismuth oxochloride, calcium phosphate, zinc oxide, apathite, calcium silicate, hydroxyapathite, barium sulfate, bismuth subcarbonate, bismuth (III ) oxide, calcium tungstate, calcium hydroxide, titanium (IV) oxide, ferrous oxide or mixtures thereof.
• Preferred radiopaque fillers are in particular selected from bismuth (III) oxide, calcium tungstate, calcium hydroxide, zinc oxide, titanium (IV) oxide and / or iron (II) oxide.
• the radiopacity can be controlled by the above-described admixed radiopaque fillers, such as bismuth oxide (Bi 2 0 3 ) or calcium tungstate (CaW0 4 ) and give, among other things, the dentist the opportunity to check the quality of the treatment performed by a subsequent control recording.
• the filler content of the invention is preferably between 20 and 90 wt .-%, more preferably between 40 and 85 wt .-% based on the total dental filler material mixture.
• the radiopacity is generally at least 3 mm / mm Al.
• Organic auxiliaries or fillers comprise in particular polymer granules, silicones and optionally dyes.
• the material mixtures according to the invention are preferably provided as a two-component or multicomponent system, particularly preferably in the form of a kit.
• the material mixture is provided as a two-component system, wherein the two components (I) and (II) are mixed only shortly before use to fill a root canal.
• Component (I) generally consists of an epoxide or an epoxide mixture, optionally mixed with an antibacterial component and auxiliaries and fillers, while the component (II) in particular an amine or an amine mixture, optionally mixed with an antibacterial component and auxiliaries and fillers.
• the present invention further relates to a method for producing a dental filling material such as a root canal filling material by curing the filler mixture described above.
• the filler material can be produced in particular by curing the filler mixture described above.
• the filler material mixture is prepared shortly before carrying out the process by mixing the components (a) and (b) provided separately from one another, and then curing the mixture.
• the separate provision of the components is preferably carried out by using the kit described above.
• Curing usually takes place by thermal action. This leads to a polyaddition reaction between the epoxide and the amine component, ie the amino acid or the amino acid derivative. Curing is preferably carried out at body temperature, ie at about 37 ° C.
• the hardening of the filler mixture for However, preservation of the dental filling material can also be initiated and / or accelerated by non-body-own, ie external heat sources.
• Calorimetric determination of the glass transition temperature was carried out on DSC-822 from Mettler-Toledo. The samples were measured in an aluminum crucible at a heating and cooling rate of 15 K / min. The temperaure program went through a heating and cooling cycle between -20 ° C and 100 ° C three times. For the determination of the glass transition temperature, the center of the glass transition was averaged over all temperature program cycles.
• the processing viscosity can be influenced by the proportion of fillers and is between 1 and 10 Pa * s.
• the curing time at about 37 ° C is at mixing in the molar ratio 1: 1 (epoxy to amine) about 1.5 hours after a viscosity of> 100 Pa * s is reached.
• the processing viscosity is the average of the measured viscosity values ([Pa * s]) in the range of 5 to 25 minutes after mixing. To compare the curing rate, the duration after mixing was determined until a viscosity of 100 Pa * s was reached.
• the dental filler material mixture according to the invention is suitable due to optimal material properties, in particular as Brakanalfullmaterialmischung.
• optimal material properties in particular as Brakanalfullmaterialmischung.
• the root canal fillings according to the invention which are obtained by the filling material mixtures according to the invention, a sustained bactericidal effect, with long shelf life of the filling, good tissue compatibility and optimal curing properties.
• the mixtures according to the invention can be easily processed.
• ⁇ -amino-s-caprolactam used in the following examples was synthesized by the method described above. All other starting materials were obtained from common chemical suppliers.
• a filler is prepared by homogeneously mixing 2.59 g (7.60 mmol) of diglycidyl ether of bisphenol-A (BADGE, also referred to as 2,2-bis [4- (2,3-epoxypropoxy) -phenyl] propane), 1.00 g (7.60 mmol) of ⁇ -amino-s-caprolactam and 1.80 g of fillers consisting of bismuth (III) oxide, zinc oxide and titanium (IV) oxide in a ratio of 3: 3.5: 1.
• the glass transition temperature is about 55 ° C.
• Example 2 Example 2:
• Component one consisting of 1.00 g (7.60 mmol) of ⁇ -amino-s-caprolactam is added with component two consisting of 2.30 g (7.60 mmol) of trimethylolpropane triglycidyl ether (MW: 302.37 g / mol) a homogeneous paste mixed.
• 1.65 g of fillers bismuth (III) oxide, zinc oxide and titanium (IV) oxide in a ratio of 3: 3.5: 1 are added to the dental filling compound produced in this way.
• AH Plus® like the material mixture in Example 2, is based on a two-component system.
• Component one is composed of the following ingredients: bisphenol A epoxy resin, bisphenol F epoxy resin, calcium tungstate, zirconium oxide, iron oxide and highly dispersed silicone oil.
• component two the following ingredients are found: dibenzyl-diamine, aminoadamantane, tricyclodecane-diamine, calcium tungstate, zirconium oxide, silicone oil, fumed silica.
• the two components are mixed manually in the ratio 1: 1.
• the glass transition temperature is about 35 ° C.
• Comparative Example 2 Component one consisting of 2 g (14.27 mmol) of diglycidyl ether of bisphenol A (also referred to as 2,2-bis [4- (2,3-epoxypropoxy) phenyl] propane) and component two consisting of 1, 22 g (7, 13 mmol) of urotropin are mixed.
• the paste produced is mixed with 1.61 g of bismuth (III) oxide, zinc oxide and titanium (IV) oxide in a ratio of 3: 3.5: 1.
• the glass transition temperature is about 45 ° C.
• the filler material mixtures according to the invention are at least equivalent in their material properties to the compositions known from the prior art, and in some cases have even better curing properties.
• the compositions according to the invention are more tissue-compatible and do not require the use of harmful amines such as urotropin or aminoadamantane.

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• Health & Medical Sciences (AREA)
• Oral & Maxillofacial Surgery (AREA)
• Epidemiology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Veterinary Medicine (AREA)
• Dental Preparations (AREA)

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• 2011
  • 2011-09-01 DE DE102011112249A patent/DE102011112249A1/de not_active Withdrawn
• 2012
  • 2012-08-30 WO PCT/EP2012/003646 patent/WO2013029790A2/de active Application Filing

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