EP1572096A1 - Materiau de restauration dentaire - Google Patents

Materiau de restauration dentaire

Info

Publication number
EP1572096A1
EP1572096A1 EP03772326A EP03772326A EP1572096A1 EP 1572096 A1 EP1572096 A1 EP 1572096A1 EP 03772326 A EP03772326 A EP 03772326A EP 03772326 A EP03772326 A EP 03772326A EP 1572096 A1 EP1572096 A1 EP 1572096A1
Authority
EP
European Patent Office
Prior art keywords
kit according
weight
primer
phosphoric acid
groups
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Withdrawn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
EP03772326A
Other languages
German (de)
English (en)
Inventor
Peter Dziuron
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.)
Merz Pharma GmbH and Co KGaA
Original Assignee
Merz Pharma GmbH and Co KGaA
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 Merz Pharma GmbH and Co KGaA filed Critical Merz Pharma GmbH and Co KGaA
Publication of EP1572096A1 publication Critical patent/EP1572096A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/40—Primers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
    • 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
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the invention relates to a kit for producing a dental restoration material for restoring teeth and dentures and for fastening dental material, and a restoration material that can be produced from the kit.
  • a so-called dental material is often attached to a tooth surface or in a tooth cavity.
  • This dental material can in particular be metallic, ceramic or plastic materials, for example inlays, crowns, fillings or the like. It is important to establish a good bond between the tooth and the dental material (filling or inlay), since marginal gap formation can occur if there is insufficient adhesion. Bacteria can penetrate into the marginal gap and cause secondary caries and / or damage the pulp.
  • crowns or other prefabricated fillings are usually attached to the tooth surface or in the tooth cavity using a dental restoration material or cement. This cement must in turn bond well with the material of the tooth.
  • a primer is known from EP-A-1 121 924 with which tooth surfaces can be prepared for connection to a dental composite material.
  • the invention has for its object to a kit and a dental restoration material of the type mentioned create, which enables good adhesion values when attaching different dental materials to teeth.
  • the invention thus relates to a kit for producing a dental restoration material which contains:
  • an electron donor active in an acidic environment selected from the group consisting of sulfinic acid and its salts,
  • At least one filler is a compound releasing Zn2 + and / or Mg 2+ ions.
  • the invention further relates to the use of this kit for producing a dental restoration material for restoring teeth and / or dentures and / or for fastening dental material.
  • Another object of the invention is a dental restoration material that can be obtained from a kit according to the invention.
  • a dental restoration material in the sense of the invention is a cement, polymerizable material or the like (in particular a dental cement) with the aid of which so-called dental materials can be attached to teeth.
  • dental materials to be attached can be, for example, composites (for example Arabes®, VOCO, Cuxhaven; Tetri-Ceram®, for Vivadent, Liechtenstein), and gold-containing alloys (for example, Degulor M and Stabilor G, for Degussa, Hanau), palladium alloys or non-precious metal alloys (e.g. Wironiu, BEGO, Bremen) as well as ceramic materials such as zirconium oxide or e.g. Empress 1 (3M Espe, Seefeld).
  • composites for example Arabes®, VOCO, Cuxhaven; Tetri-Ceram®, for Vivadent, Liechtenstein
  • gold-containing alloys for example, Degulor M and Stabilor G, for Degussa, Hanau
  • the primer used as part of the kit according to the invention can be a one-component system or preferably a multi-component system and is already known per se from EP-A-1 121 924.
  • the primer used according to the invention is preferably free of amine.
  • amine-free means that the amines usually used together with a peroxide as polymerization initiators are not present in the agent according to the invention, or at most in a very small proportion (preferably less than 0.5% by weight) caused by any impurities.
  • amine-free does not exclude that amines are contained in the bonds or composite materials which may be used in addition to the agent according to the invention or are added as separate polymerization initiators when the primer according to the invention is processed together with such bonds or composite materials.
  • the corresponding tooth surface or tooth cavity is first prepared with the primer for connection to the second main component of the kit, the polymerizable material.
  • preparation of tooth surface or cavity encompasses both the etching and the priming of the tooth surface, as is known from EP-A-1 121 924.
  • Priming involves establishing a good connection between the primer and the tooth surface, for example by penetrating the phosphoric acid ends arranged on the spacer sections of the molecules into the dentin tubules of the tooth substance.
  • the primer ensures good mechanical adhesion to the tooth or denture surface.
  • the steps of etching and priming can be carried out in one step.
  • the primer contains phosphoric acid and / or phosphoric acid esters and / or diphosphates.
  • phosphoric acid ester encompasses both mono-, di- and triesters of phosphoric acid and its salts.
  • HPMA hydroxypropyl methacrylate
  • Other suitable alcohol groups are particularly preferably water-soluble vinyl compounds with a hydroxyl group. According to the invention, however, it is preferred if the agent contains no hydroxyethyl methacrylate (HEMA) or HEMA ester. According to the invention, it is therefore possible to dispense with the use of this substance which has a high risk of allergy.
  • An electron donor which is effective in an acidic environment is to be understood as any substance which, at pH values below 7, preferably also in the acidic range (pH 3 and less), can react with a polymerization initiator of an autopolymerizing material in such a way that the first , to
  • the Electron donor used according to the invention ensures that this first step can also function in the strongly acidic environment created by phosphoric acid.
  • the sulfinate content of the primer is preferably between 1 and 10% by weight, more preferably 2 and 5% by weight, particularly preferably about 3% by weight. This content is calculated as sodium sulfonate.
  • the primer component of the kit according to the invention is commercially available from Merz Dental GmbH, Lütjenburg, under the name Resulcin® AquaPrime.
  • the second essential component of the kit according to the invention is a polymerizable material. It contains polymerizable, unsaturated monomers and / or oligomers and / or prepolymers, preferably compounds containing acrylic, methacrylic, vinyl and / or styryl groups. Suitable polymerisable compounds are familiar to the person skilled in the art and are used in the prior art for the production of composites or compomers. Examples include bis-GMA, UDMA, TEDMA, polymerizable acids such as MSA or the like.
  • the curing agent is preferably a polymerization catalyst or system, particularly preferably a peroxide such as, for example, benzoyl peroxide.
  • Fillers in the sense of the invention can be organic or preferably inorganic fillers, for example quartz, (pyrogenic) silicic acid, aluminum oxides, glasses such as barium glasses, aluminum fluorosilicate glasses or the like. Suitable fillers are known to the person skilled in the art.
  • the fillers or the filler contain a compound releasing Zn 2+ or Mg 2+ ions.
  • Ion-releasing means that the fillers or filler constituents release Zn2 + and / or Mg 2+ ions under the conditions of the use of the kit in an aqueous environment or in the oral cavity.
  • the dental restoration material can harden by two different reaction mechanisms. The primary curing takes place through the rapid free radical polymerization of the polymerizable compounds. Secondary curing takes place in the polymer matrix through a cement reaction between the zinc or magnesium ions on the one hand and excess phosphate groups of the primer on the other. This cement reaction has two benefits.
  • the dental restoration material according to the invention produced from the kit according to the invention is equally suitable for fastening dental materials of all kinds (metals, ceramics, plastics) to teeth.
  • the proportion of the compounds releasing zinc and / or magnesium ions in the total amount of the polymerizable material is preferably 2 to 15% by weight, more preferably 6 to 10% by weight (calculated in each case as ZnO or MgO).
  • the phosphoric acid esters and / or diphosphates of the primer of the kit according to the invention particularly preferably contain at least partially polymerizable double bonds.
  • the primer particularly preferably contains:
  • R 2 is H or
  • R 3 is selected from the group consisting of alkylene groups, alkyleneoxy groups with one or more alkyleneoxy units, alkylene or alkyleneoxy groups substituted with one or more hydroxy groups;
  • the primer also contains a mixture of phosphoric acid, a major proportion of phosphoric acid mono- and / or diesters
  • Phosphoric acid triesters and diphosphates.
  • the low proportion of phosphoric acid is used for the preliminary etching of the tooth surface.
  • the phosphoric acid esters used according to the invention are molecules whose acidic hydroxyl groups can chemically combine with the calcium on the tooth surface.
  • the partially esterified phosphoric acid group is connected to a methacrylate group via an alkylene or alkyleneoxy group (which may carry hydroxyl groups) which serves as a spacer.
  • the methacrylate groups can partially polymerize and thus form a film on the tooth surface into which the dental material can polymerize. Due to their good mobility, the phosphoric acid ends of the molecules can penetrate dentinal tubules and thus improve the mechanical adhesion to the tooth surface.
  • the percentages in claim 2 relate to the so-called resin content of the primer, which is 100% for a solvent-free mixture. It decreases according to the amount of water added.
  • the primer of phosphoric acid, mono-, di- and triesters and diphosphates according to the invention has both good storage stability and a very high adhesive force. This primer can be used for etching and priming in a single process step.
  • the spacer group in the phosphoric acid derivatives is preferably selected from the group consisting of alkylene groups with 2-4 C atoms, ethyleneoxy or propyleneoxy groups, which can consist of up to 4 glycol units (ethylene or propylene glycol units), and alkylene groups with 2-4 C atoms which are substituted with one or two hydroxyl groups.
  • Preferred spacers are ethylene or propylene groups, and also a group of the formula
  • the main part of the primer preferably consists of phosphoric acid mono- and diesters, it is preferably 30-90% by weight, more preferably 40-80% by weight, based on the resin content. A ratio of 20-50% by weight of phosphoric acid monoester and 25-45% by weight of phosphoric acid diester is further preferred.
  • the phosphoric acid content of the primer is preferably 1-3% by weight.
  • the water content in the ready-to-use primer used is preferably 20-95% by weight, more preferably 20-50% by weight, particularly preferably 25-30% by weight.
  • Low water contents of at most 50, preferably at most 40, more preferably at most 30,% by weight are preferred, which considerably simplifies application in the mouth area due to the higher viscosity of the primer at a lower water content.
  • the invention further relates to the use of a kit described above for producing a dental restorative material for filling, sealing, restoring teeth and dentures, and in particular for preparing teeth for the attachment of a dental material.
  • Another object of the invention is a dental restoration material that can be obtained from a kit according to the invention.
  • the tooth surface is treated with the primer according to the invention
  • the polymerizable material is applied.
  • Dental materials to be fastened such as, for example, inlays, crowns or the like, can then be inserted or put on.
  • the kit according to the invention is at least a two-component system with the components primer and polymerizable material. As a rule, however, these two components in turn consist of two or more components themselves; preferred constellations can be found in subclaims 17 to 21.
  • the kit is particularly preferably a four-component system in which primers on the one hand and polymerizable material on the other hand each consist of two components.
  • the term component denotes the components or elements of the kit to be handled by the user (dentist) and is not to be confused with the chemical components or ingredients of the kit.
  • the primer of the kit according to the invention is preferably a two-component system in which one component contains phosphoric acid and / or phosphoric acid esters and / or diphosphates and the other component in aqueous solution is a salt of a sulfinic acid.
  • sulfinates Compared to free sulfinic acid, sulfinates have the advantage of being stable in aqueous solution, but in the case of the salts the free electron pair of the sulfur is more strongly bound to this atom and is therefore only available to a limited extent for the initialization of the peroxide (hardening agent).
  • a primer is produced from this two-component system shortly before use.
  • the phosphoric acid milieu of the first component then forms free sulfinic acid, which is an effective electron donor.
  • the disadvantage of free sulfinic acid namely its easy oxidizability or disproportionation, is negligible when this free acid is released shortly before use.
  • the tooth surface is primed with this primer.
  • the polymerizable material is then applied, which in turn is preferably mixed from two components.
  • One component can, for example, the polymerizable Compounds and fillers contain, the other component of the curing agent.
  • a certain amount of mixing of the primer and the polymerizable material then takes place directly on the tooth surface, which then leads to the fact that, after polymerizing, the described additional cement reaction can take place with the participation of excess phosphoric acid of the primer and zinc or magnesium ions.
  • Primer component A 29 g of HPMA (hydroxypropyl methacrylate) are taken up in 50 ml of chloroform. The solution is under
  • the reaction mixture is analyzed by 31 P-NMR spectroscopy. It has the following composition: 1% phosphoric acid, 39.5% phosphoric acid monoester, 29.1% phosphoric acid diester, 0.5% phosphoric acid triester, 28.5% diphosphate. All percentages are percentages by weight.
  • Primer component B is a 3% aqueous sodium sulfinate solution.
  • the polymerizable material contains the following polymerizable monomers: Bis-GMA (isopropylidene-bis [2 (3) -hydroxy-
  • TEDMA (3,6-dioxaoctamethylene dimethacrylate 13.3 g barium alumoborosilicate glass 48.0 g
  • An amine such as, for example, N, N-dimethyl-p-toluidine, whose free electron pair on
  • a nitrogen interacts with the peroxide and can thus initiate the radical formation reaction. According to the invention, this is not absolutely necessary, since sulfinic acid as an electron donor can also initiate autopolymerization.
  • the components of the polymerizable material mentioned are homogenized before use.
  • the crowns were extracted from extracted human teeth, the exposed dentin surfaces were ground on wet grinding wheels (corundum, 600 grit) and checked for enamel freedom by light microscopy. With these surfaces fixed on a glass plate, the teeth were embedded in Technovit (from Kulzer, Wehrheim) and, after devestment, ground again briefly and checked by light microscopy to ensure that the dentin surfaces are free of embedding plastic and lie in one plane with it.
  • the 1: 1 mixed primer was then Components A and B were rubbed on the ground dentin surfaces over a period of 30 s and then dried until the layer on the dentin surface no longer moved noticeably in the air flow.
  • a self-adhesive plastic film with a circular opening with a diameter of 5.5 mm was glued to each of the primed dentin surfaces to prevent the adhesive material from creeping up on the test stamp during the further process.
  • the mixed polymerizable material from example 1 was then applied on the one hand as a thin film to the composite surfaces of the respective test stamps from example 2 and on the other hand a sufficient proportion (as a small drop) with the circular opening of the plastic film on the primed dentine surface of the exposed primer with scrubbing movements with a short-haired, solid brush for 5 s.
  • the test stamp with its pretreated composite surface was then placed concentrically on the pretreated exposed area of the dentin surface under light pressure.
  • test specimens were produced in accordance with the methods described in Examples 2 and 3 and the shear bond strengths were determined.
  • Comparative Example 1 13.4 Mpa Comparative Example 2: not measurable Comparative Example 3: 2 MPa

Landscapes

  • 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)
  • Plastic & Reconstructive Surgery (AREA)
  • Dental Preparations (AREA)

Abstract

L'invention concerne un nécessaire pour produire un matériau de restauration dentaire, comprenant : a) une amorce qui contient : aa) de l'acide phosphorique et/ou un ester de l'acide phosphorique et/ou un diphosphate ; ab) un donneur d'électrons actif en milieu acide, sélectionné dans le groupe comprenant l'acide sulfinique et ses sels ; b) un matériau polymérisable qui contient : ba) des monomères et/ou oligomères et/ou prépolymères insaturés polymérisables ; bb) un durcisseur ; bc) des substances de remplissage. Le nécessaire selon l'invention est caractérisé en ce qu'au moins une substance de remplissage se présente sous la forme d'un composé qui libère des ions Zn<2+> et/ou Mg<2+>. La présente invention se rapporte en outre à un matériau de restauration dentaire produit au moyen dudit nécessaire. Cette invention permet de fixer de manière efficace et stable une pluralité de matériaux dentaires (métaux, céramiques, plastiques) sur les dents.
EP03772326A 2002-12-04 2003-11-11 Materiau de restauration dentaire Withdrawn EP1572096A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10256690A DE10256690A1 (de) 2002-12-04 2002-12-04 Dentales Restaurationsmaterial
DE10256690 2002-12-04
PCT/EP2003/012589 WO2004050042A1 (fr) 2002-12-04 2003-11-11 Materiau de restauration dentaire

Publications (1)

Publication Number Publication Date
EP1572096A1 true EP1572096A1 (fr) 2005-09-14

Family

ID=32318949

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03772326A Withdrawn EP1572096A1 (fr) 2002-12-04 2003-11-11 Materiau de restauration dentaire

Country Status (4)

Country Link
EP (1) EP1572096A1 (fr)
AU (1) AU2003279378A1 (fr)
DE (1) DE10256690A1 (fr)
WO (1) WO2004050042A1 (fr)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4540722A (en) * 1982-01-15 1985-09-10 Minnesota Mining And Manufacturing Company Dentin and enamel adhesive
DE3536076A1 (de) * 1985-10-09 1987-04-09 Muehlbauer Ernst Kg Polymerisierbare zementmischungen
US5639239A (en) * 1995-01-12 1997-06-17 Earle; Jeffrey O. Dental dentin bonding system
US5866631A (en) * 1995-12-22 1999-02-02 Tokuyama Corporation Dental primer composition and polymerization catalyst
TWI262795B (en) * 1999-05-31 2006-10-01 Kuraray Co Adhesive composition and method for producing it
EP1121924A3 (fr) * 2000-02-07 2003-12-10 Merz Pharmaceuticals GmbH Apprêt pour préparer des surfaces dentaires avant l'application d'une obturation en matériau composite et matériau pour la fixation de prothèses dentaires
DE10124028B4 (de) * 2001-05-16 2010-02-18 3M Espe Ag Selbstadhäsive Dentalmaterialien

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004050042A1 *

Also Published As

Publication number Publication date
AU2003279378A1 (en) 2004-06-23
DE10256690A1 (de) 2004-06-17
WO2004050042A1 (fr) 2004-06-17

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