EP4312945A1 - Matériau dentaire autoadhésif - Google Patents

Matériau dentaire autoadhésif

Info

Publication number
EP4312945A1
EP4312945A1 EP22720373.4A EP22720373A EP4312945A1 EP 4312945 A1 EP4312945 A1 EP 4312945A1 EP 22720373 A EP22720373 A EP 22720373A EP 4312945 A1 EP4312945 A1 EP 4312945A1
Authority
EP
European Patent Office
Prior art keywords
weight
meth
acrylate
dental material
dimethacrylate
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.)
Pending
Application number
EP22720373.4A
Other languages
German (de)
English (en)
Inventor
Maria Lechmann-Dorn
Michael Gerlach
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.)
Kulzer GmbH
Original Assignee
Kulzer GmbH
Kulzer and Co 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
Priority claimed from DE102021108477.6A external-priority patent/DE102021108477A1/de
Priority claimed from DE102021108476.8A external-priority patent/DE102021108476A1/de
Application filed by Kulzer GmbH, Kulzer and Co GmbH filed Critical Kulzer GmbH
Publication of EP4312945A1 publication Critical patent/EP4312945A1/fr
Pending 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
    • A61K6/80—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
    • 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
    • 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
    • A61K6/62—Photochemical radical initiators
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A61K6/76—Fillers comprising silicon-containing compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A61K6/77—Glass
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/78—Pigments

Definitions

  • Self-adhesive, radiation-curable, dental material comprising A) a monomer component with a difunctional urethane (meth)acrylate, hydrophilic alkylene oxide-based difunctional (meth)acrylate-based crosslinkers, at least one acidic monomer of an olefinic, acidic monoester of a phosphoric acid and / or an olefinic , acidic monoester of a thiophosphoric acid optionally in combination with an olefinic carboxylic acid and / or olefinic carboxylic anhydride and an initiator and / or an initiator system each having an absorption maximum of 420 to 550 nm and optionally with a co-initiator and optionally B) a filler component comprising at least one Dental glass, in particular A) the monomer component and B) the filler component in a mass ratio of a) 100: 0 to 60: 40 in fissure sealants or b) from 59: 41 to 20: 80
  • a high filler content is advantageous in order to achieve very good mechanical properties in the cured composite and at the same time to reduce the polymerization shrinkage that occurs during curing. These properties are also decisive for the long-term success of the tooth replacement material.
  • Fissure sealants are preventive products to minimize the risk of caries in deep fissures or in susceptible patients. Fissure sealants are polymerizable compositions that adhere to enamel.
  • the standard procedure for fissure sealing involves acid etching of the enamel followed by sealing with a low viscosity material, commonly referred to as flow, or a glass ionomer cement - without the prior use of a bonding agent.
  • suitable flow materials can be used in combination with an adhesive.
  • the object of the invention was to provide a dental, self-adhesive, polymerizable dental material which, depending on the filler content, can preferably be adjusted as a self-adhesive fissure sealant which bonds adhesively to enamel with high adhesive force, or as a self-adhesive composite.
  • the dental material to be developed should preferably be usable without prior chemical treatment of the dentine and/or the enamel, preferably without prior etching of the dentine and/or the enamel or the fissure surface.
  • that should Dental material can be applied to dentine and/or enamel without prior application of an adhesive.
  • the task of developing a self-adhesive dental material with reduced water absorption ⁇ g/mm 3 ) and/or reduced solubility ⁇ g/mm 3 was also expediently free from HEMA.
  • a self-adhesive composite offers the customer the advantage of using the restorative without prior use of an adhesive system and etchant on the tooth surface comprising enamel and dentine.
  • the composite according to the invention has a high adhesive strength due to the special coordination of the formulation of the composite, which generates very high adhesive strength both on enamel and on dentin in the self-etching mode.
  • the achieved adhesive values are significantly higher than the values achieved by the competitor on the market.
  • a dental material according to the invention shows a shear bond strength of greater than 15 MPa on dentin and greater than 20 MPa on enamel, while the following products are otherwise under the same conditions
  • Have shear bonds of 4.8 to 16.4 MPa (Vertise Flow (5.9 MPa SBS dentine, 16.4 ⁇ 4.2 MPa enamel, with TWL 2.1 ⁇ 2.9 MPa), Constic (4.8 MPa SBS -Dentine, 15 MPa enamel, with TWL 12.0 ⁇ 5.6 MPa)).
  • the invention relates to a self-adhesive, radiation-curable, polymerizable
  • A) a monomer component comprising a) at least one at least difunctional urethane (meth)acrylate, b) at least one hydrophilic alkylene oxide-based difunctional (meth)acrylate-based crosslinker which i) does not contain a urethane (meth)acrylate and/or ii) comprises no aromatic radicals, or a mixture of at least two of these crosslinkers, c) at least one olefinic, acidic ester of a phosphoric acid and/or at least one olefinic, acidic ester of a thiophosphoric acid, d) at least one initiator and/or an initiator system each having an absorption maximum of 420 to 550 nm and comprising i) diketone and at least one ii) co-initiator selected from a tert-amine and a 1,2-methylenedioxybenzene, where i) diketone and ii) co-initiator with a molar
  • each independently (meth)acrylate is selected from methacrylate and acrylate
  • each independently urethane (meth)acrylate is selected from urethane methacrylate and urethane acrylate
  • a filler component comprising at least one dental glass or mixtures of dental glasses, the total composition of the dental material being 100% by weight.
  • A) the monomer component and B) the filler component can be in a mass ratio of 100:0 to 30:70 and in equally preferred alternatives a) from 60:40 to 40:60 or b) from 59:41 to 20: 80 are present in the dental material, and the total composition of the dental material is 100% by weight.
  • the dental materials according to the invention can be used as fissure sealants with little or no filler content and as composites with a high filler content, in particular from about 41% by weight in the overall composition.
  • the invention also relates to a dental material comprising c) a mixture of acidic monomers comprising i) at least one olefinic, acidic ester of a phosphoric acid and/or at least one olefinic, acidic ester of a thiophosphoric acid, in combination with ii) at least one olefinic carboxylic acid and/or at least an olefinic carboxylic acid anhydride.
  • the invention also relates to a self-adhesive, radiation-curable, dental composite material, in particular composite material that can be cured or polymerized with visible light, comprising A) a monomer component comprising a) at least one at least difunctional urethane (meth)acrylate, b) at least one hydrophilic alkylene oxide-based di -functional (meth)acrylate-based crosslinking agent, which i) does not include any urethane (meth)acrylate and/or ii) does not contain any aromatic radicals, or a mixture of at least two of these crosslinking agents,
  • a mixture of acidic monomers comprising i) at least one olefinic, acidic ester of a phosphoric acid, in particular a monoester of a phosphoric acid, and/or at least one olefinic, acidic ester of a thiophosphoric acid, in particular a monoester of a thiophosphoric acid, preferably at least one monoester of a phosphoric acid with a mono-, di-, tri-, or tetra-(meth)acrylate, at least one monoester of a phosphoric acid with a mono-, di-, tri-, or tetra-urethane (meth)acrylate and/or monoester of a thiophosphoric acid with a mono -, di-
  • a filler component comprising at least one dental glass or mixtures of dental glasses, in particular dental glass with an average particle size dso of 0.2 to 2.0 mhi, with optionally at least one pigment, dye, UV and/or Vis stabilizer in A) and/or or B) can be present, and A) the monomer component and B) the filler component in a mass ratio of 100:0 to 20:80, in particular 100:0 to 30:70, in the dental material, in particular from 59:61 to 30: 70 in the composite material, and the overall composition of the dental material, preferably the composite material, is 100% by weight.
  • diketone and ii) co-initiator are present with a molar ratio of ii): i) of greater than or equal to 1.15, in particular greater than or equal to 1.2, with i) the diketone being greater than or equal to 0 50% by weight, in particular greater than or equal to 0.55% by weight, in particular greater than or equal to 0.6% by weight +/- 0.25% by weight, in the overall composition of the dental material.
  • the designation (meth)acrylate, (meth)acrylate-based or urethane (meth)acrylate consistently refers to both acrylate, acrylate-based or urethane acrylate and preferably methacrylate, methacrylate-based or urethane methacrylate and also mixtures of these disclosed.
  • the aforementioned urethane (meth)acrylates also include urethane methacrylate and/or urethane acrylate as the (meth)acrylate component.
  • carboxylic anhydride-functionalized (meth)acrylate monomers also include the respective carboxylic anhydride-functionalized methacrylate and/or carboxylic anhydride-functionalized acrylate monomers.
  • monoesters of phosphoric acids based on (meth)acrylates such as (meth)acryloyloxy derivatives; can be selected from the respective methacrylates and acrylates of the respective compound. This applies consistently to all (meth)acrylates, since they are selected from methacrylates and acrylates.
  • the dental material is described here as a dental material comprising a monomer component A) and a filler component B), these two components are present in the composite as a mixture.
  • This type of disclosure is known to the person skilled in the art in the dental field, since it only serves to characterize the two initially produced components A) and B) before they are mixed to produce the dental material.
  • the two components A) and B) are generally mixed beforehand in a disperser for the production of the dental material, such as a fissure sealant or composite.
  • the initiator system preferably comprises an initiator such as a diketone and a co-initiator. Particular preference is given to at least one initiator and/or one initiator system with an absorption maximum of 420 to 550 nm, each comprising at least one cycloaliphatic diketone and, as a co-initiator, an aromatic tert-amine.
  • the dental material in A) monomer component d) comprises from 0.3 to 2.5% by weight, in particular from 0.5 to 1.2% by weight, of at least one diketone, in particular 1.7 7-trimethylbicyclo[2.2.1]hepta-2,3-dione (champhorquinone), and 0.6 to 2.5% by weight, in particular from 1.0 to 2.0% by weight, preferably from 1.0 to 1.5% by weight of at least one tert-amine, in particular 2-n-butoxyethyl 4-(dimethylamino)benzoate, based on the total composition of 100% by weight of the A) monomer component.
  • the mass ratio of diketone to co-initiator is from 1:1 to 1:2.5, in particular from 1:1.5 to 1:2.5, preferably from 1:1.8 to 1:2.5.
  • the dental material comprises d) at least one initiator and/or an initiator system comprising i) diketone and ii) co-initiator selected from a tert-amine with a molar ratio of ii): i) greater than or equal to 1.15, in particular greater than or equal to 1.17, preferably greater than or equal to 1.2, and wherein i) the Diketone is greater than or equal to 0.4% by weight, in particular greater than or equal to 0.5% by weight, in the overall composition of the dental material of 100% by weight.
  • the diketone is present from 0.5 to 1.0% by weight and the co-initiator from 1.0 to 1.8% by weight in the total composition.
  • the diketone and the co-initiator are present from 0.5 to 1.0% by weight and the co-initiator from 1.0 to 1.8% by weight in the total composition, the co- Initiator is always present in excess of the dicton.
  • a dental material which comprises: i) at least one olefinic, acidic ester of a phosphoric acid and/or at least one olefinic, acidic ester of a thiophosphoric acid comprising at least one monoester of a phosphoric acid and a (meth)acrylate, monoester of a phosphoric acid and a urethane( meth)acrylate and/or at least one monoester of a thiophosphoric acid and a (meth)acrylate, each independently (meth)acrylate being selected from methacrylate and acrylate and urethane (meth)acrylate being independently selected from urethane methacrylate and urethane acrylate.
  • the esters of the following formulas I, Ia, Ib and II are particularly preferred, with the esters of the formulas I and II being more preferred.
  • Preferred i) olefinic, acidic monoesters of a phosphoric acid and/or an olefinic acidic monoester of a thiophosphoric acid comprise acidic monoesters of at least one phosphoric acid comprising at least two urethane (meth)acrylate groups, with at least two urethane (meth)acrylate groups being linked by at least one trivalent C atom and optional O atoms group are covalently bonded to an O atom of phosphoric acid and form the monoester of phosphoric acid, wherein the urethane (meth) acrylate groups are selected from urethane methyl acrylate and urethane acrylate groups, and each independently Urethane (meth)acrylate is selected from urethane methacrylate and urethane acrylate, 2-(meth)acryloyloxyethyl acid phosphate, 2- and 3-(meth)acryloyloxypropyl acid phosphate, 4-(meth)acrylo
  • a dental material that includes
  • A) a monomer component comprising a) 40 to 80% by weight of at least one at least difunctional urethane (meth)acrylate, b) 10 to 35% by weight of at least one hydrophilic alkylene oxide-based difunctional (meth)acrylate-based crosslinker, comprising i) no urethane (meth)acrylate and/or ii) no aromatic radicals, or a mixture of at least two of these crosslinkers, c) 5 to 30% by weight of a mixture of acidic monomers comprising i) at least one olefinic, acidic ester a phosphoric acid and/or at least one olefinic, acidic ester of a thiophosphoric acid, in combination with ii) at least one olefinic carboxylic acid and/or at least one olefinic carboxylic acid anhydride, d) 0.3 to 5% by weight of at least one initiator and/or an initiator system each with an absorption maximum of 420 to
  • a filler component comprising a) 90 to 100% by weight of at least one dental glass or mixtures of dental glasses, b) 0 to 10% by weight of inorganic fluorides, metal oxide, mixed oxides c) 0 to 5% by weight of at least one pigment, Dye, UV and/or Vis stabilizer, the total composition of filler component B) being 100% by weight, A) the monomer component and B) the filler component being present in the dental material in a mass ratio of 100:0 to 60:40, and the total composition of the dental material being 100% by weight.
  • the invention also relates to a dental material which comprises A) comprising a monomer component a) 40 to 80% by weight of at least one at least difunctional urethane (meth)acrylate, b) 10 to 35% by weight of at least one hydrophilic alkylene oxide-based difunctional (meth)acrylate-based crosslinker, i) no urethane (meth)acrylate and/or ii) no aromatic radicals, or a mixture of at least two of these crosslinkers, c) 5 to 30% by weight of a mixture of acidic monomers comprising i) at least one olefinic, acidic ester of a phosphoric acid and/or at least one olefinic, acidic ester of a thiophosphoric acid, in combination with ii) at least one olefinic carboxylic acid and/or at least one olefinic carboxylic acid anhydride, d) 0.3 to 5% by weight of at least one initiator and/or an initiator system
  • a filler component comprising a) 90 to 100% by weight of at least one dental glass or mixtures of dental glasses, b) 0 to 10% by weight of inorganic fluorides, metal oxide, mixed oxides c) 0 to 5% by weight of at least one pigment, Dye, UV and/or Vis stabilizer, the total composition of the filler component B) being 100% by weight, A) the monomer component and B) the filler component being present in the dental material in a mass ratio of 100:0 to 20:80, and the total composition of the dental material being 100% by weight.
  • the monoesters comprise the monoesters of the formulas I, Ia, Ib, II and/or mixtures comprising at least two of these monoesters.
  • n is independently 1 to 100, in particular n is 1 to 20, and
  • R 1 , R 2 and R 3 correspond to a group of the formula III, IIIb and/or IIIa and the or the remaining radicals of R 1 , R 2 and R 3 are selected from at least one group of formulas IV, V, VIa, VIb, VIIa, VIIb, Villa and/or VI Mb, where R 4 and R 5 are each independently in the groups of formulas IV, V, Via , Vlb, Vlla, Vllb, Villa and
  • VI Mb are selected from H, methyl and ethyl, in particular the remaining groups are selected from at least two formulas from IV, V, Via, VIIb, VIIa, VIIb, Villa and/or VII Ib, and
  • R 6 is selected independently in the groups of the formulas Ia, Ib, IIIa, IIIb, Villa and VII Ib from H and methyl,
  • m 0 or 1 to 100 in formulas Villa and / or VI Nb, in particular 1 to 20, with R 6 is selected from H and methyl.
  • R 10A and R 10B / R 10C are selected from H and methyl, with preferably R 10A , R 10B and R 10C each being H or methyl.
  • n is preferably 1 to 10, particularly preferably 1
  • Particularly preferred acidic monomers comprise a c) mixture of acidic monomers comprising i) at least one acidic monoester of at least one phosphoric acid of the general formulas I and/or II, 2-(meth)acryloyloxyethylphenyl acid phosphate and/or 10-(meth)acryloyloxydecyl acid phosphate, and ii) 4-methacryloyloxyethyl trimellitic acid (4-MET) and/or its anhydride (4-META).
  • the dental material preferably comprises in A) the monomer component as c) i) 4 to 20 wt general formulas I, Ia, Ib and/or II, 2-(meth)acryloyloxyethylphenyl acid phosphate and/or 10-(meth)acryloyloxydecyl acid phosphate, or mixtures of at least two of the acidic esters, and ii) 2 to 10% by weight of at least one olefinic carboxylic acid and/or at least one olefinic carboxylic acid anhydride, in particular
  • the dental material preferably comprises as c) i) 2 to 10 wt II, 2-(meth)acryloyloxyethylphenyl acid phosphate and/or 10-(meth)acryloyloxydecyl acid phosphate, or mixtures of at least two of the acidic esters, and ii) 1 to 5% by weight of at least one olefinic carboxylic acid and/or at least one olefinic carboxylic acid anhydride, in particular 4-methacryloyloxyethyl trimellitic acid (4- MET) and/or its anhydride (4-META), in relation to the total composition of 100% by weight of the dental material.
  • Another preferred dental material comprises A) the monomer component, optionally mixed with B) the filler component, the dental material comprising a) 20 to 80% by weight of at least one at least difunctional urethane (meth)acrylate, b) at least two hydrophilic alkylene oxide based difunctional (meth)acrylate-based crosslinkers each selected from the combinations i) and ii) or i) and iii) or i), ii) and iii), with i) 10 to 20% by weight of 1,2 -Ethandiol dimethacrylate, diethylene glycol dimethacrylate (DEGMA), triethylene glycol dimethacrylate (TEGDMA), tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol
  • the filler component comprises a) 90 to 100% by weight of at least one dental glass or a mixture of dental glasses, b) 0 to 10% by weight of inorganic fluorides, metal oxide, mixed oxides, crystalline metal oxide and/or silicate, in particular 2 to 10 % by weight, preferably 5 to 10% by weight, c) 0 to 5% by weight, in particular 0.1 to 0.5% by weight, of at least one pigment, dye,
  • UV and/or Vis stabilizer and/or a mixture of at least two of the fillers the total composition of filler component B) being 100% by weight
  • A) the monomer component and B) the filler component in a mass ratio of 100 : 0 to 20 : 80 are present in the dental material and the total composition of the dental material is 100% by weight.
  • a dental material which comprises:
  • the dental material comprising a) 20 to 40% by weight of at least one at least difunctional urethane (meth)acrylate, b) at least two hydrophilic alkylene oxide-based difunctional (meth) acrylate-based crosslinkers each selected from the combinations i) and ii) or i) and iii) or i), ii) and iii), with i) 10 to 20% by weight of 1,2-ethanediol dimethacrylate, diethylene glycol dimethacrylate (DEGMA) , Triethylene glycol dimethacrylate (TEGDMA), tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate dipropylene glycol diacrylate, tripropylene glycol diacrylate, t
  • At least one co-initiator selected from 2-n-butoxyethyl 4-(dimethylamino)benzoate and/or piperonyl alcohol, the mass ratio of diketone to co-initiator being from 1:1.5 to 1:3, preferably 1:2 with +/- 0.15, e) 0 to 10% by weight of at least one tri-, tetra-, penta- and/or hexa-functional (meth)acrylate-based crosslinker which is not a urethane (meth)acrylate, f) 0 to 5% by weight, in particular 0.1 to 0.5% by weight, of at least one pigment, dye,
  • UV and/or Vis stabilizer the total composition of the monomer component A) being 100% by weight, and optional
  • the filler component comprises a) 90 to 100% by weight of at least one dental glass or a mixture of dental glasses, b) 0 to 10% by weight of inorganic fluorides, metal oxide, mixed oxides, crystalline metal oxide and/or silicate, in particular 2 to 10 wt .-%, preferably 5 to 10 wt .-%, c) 0 to 5 wt .-% at least one pigment, dye, UV and / or Vis
  • the total composition of the filler component B) being 100% by weight
  • A) the monomer component and B) the filler component in a mass ratio of 59:41 to 20:80 in Dental material are present, and wherein the total composition of the dental material is 100% by weight.
  • a dental material in particular a composite material, is comprised, with an A) monomer component comprising a) 40 to 80% by weight, in particular 50 to 80% by weight, at least one at least difunctional urethane (meth)acrylate, b ) 10 to 35% by weight, in particular 15 to 35% by weight, preferably 20% by weight with +/- 5% by weight, in particular with +/- 3% by weight, of at least one hydrophilic alkylene oxide based di-functional (meth) acrylate-based crosslinker, the i) no urethane (meth) acrylate and / or ii) no aromatic radicals, or a mixture of at least two of these crosslinkers, c) 5 to 30% by weight, in particular 10 to 20% by weight, of a mixture of acidic monomers, as disclosed, d) 0.3 to 5 Wt Is monomer component, and optionally with at least one tert-amine as a co-initiator or a
  • the subject matter of the invention also includes a dental material
  • Dental material comprises a) 20 to 80% by weight of at least one at least difunctional urethane (meth)acrylate, b) 8 to 20% by weight of at least one hydrophilic alkylene oxide-based difunctional (meth)acrylate-based crosslinking agent which i) no urethane (meth)acrylate and/or ii) no aromatic radicals, or a mixture of at least two of these crosslinkers, c) i) 4 to 20% by weight of at least one acidic monoester of at least one phosphoric acid of the general formulas I and/or II, 2-(meth)acryloyloxyethylphenyl acid phosphate and/or
  • 10-(meth)acryloyloxydecyl acid phosphate and ii) 1 to 10% by weight, in particular 1.5 to 5% by weight, of at least one olefinic carboxylic acid and/or at least one olefinic carboxylic anhydride, in particular at least one carboxylic acid-functionalized and/or carboxylic anhydride-functionalized (meth)acrylate
  • co-initiator selected from tert-amine and 1,2-methylenedioxybenzene in particular selected from 2-n-butoxyethyl -4-(dimethylamino)benzoate and/or piperonyl alcohol
  • % in particular a) 0 to 40% by weight or b) 50 to 76% by weight of at least one dental glass or a mixture of dental glasses, in particular 50 to 76% by weight, g) 0 to 10% by weight inorganic fluoride such as ytterbium fluoride, metal oxide,
  • Another preferred dental material comprises A) the monomer component optionally mixed with B) the filler component, the dental material comprising a) 20 to 30% by weight of at least one at least difunctional urethane (meth)acrylate, b) at least two hydrophilic alkylene oxides -based difunctional (meth)acrylate-based crosslinkers each selected from the combinations i) and ii) or i) and iii) or i), ii) and iii), with i) 5 to 10% by weight 1, 2-ethanediol dimethacrylate, diethylene glycol dimethacrylate (DEGMA), triethylene glycol dimethacrylate (TEGDMA), tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacryl
  • 2-(Meth)acryloyloxyethylphenyl acid phosphate and/or 10-(meth)acryloyloxydecyl acid phosphate ii) 0.5 to 5% by weight, in particular 3.75 to 10% by weight, of 4-(methacryloyloxyethyl)-trimellitic anhydride (4- META) and/or 4-methacryloyloxyethyl trimellitic acid (4-MET), and d) 0.3 to 1.5% by weight of at least one diketone selected from 1,7,7-trimethylbicyclo[2.2.1]hepta -2,3-dione (champhorquinone), phenylpropanedione, and
  • At least one co-initiator selected from 2-n-butoxyethyl 4-(dimethylamino)benzoate and/or piperonyl alcohol, the mass ratio of diketone to co-initiator being from 1:1.7 to 1:3, preferably 1:2 with +/-0.15, e) 0 to 10% by weight of at least one tri-, tetra-, penta- and/or hexa-functional (meth)acrylate-based crosslinker which is not a urethane (meth)acrylate, f) 0 to 5% by weight, in particular 0.1 to 0.5% by weight, of at least one pigment, dye,
  • UV and/or Vis stabilizer g) 10 to 80% by weight of at least one dental glass or a mixture of dental glasses, in particular 50 to 80% by weight, h) 0 to 10% by weight of inorganic fluorides, metal oxide, Mixed oxides, crystalline metal oxide and/or silicate, the aforementioned components a) to h) resulting in the overall composition of 100% by weight of the dental material.
  • UDMA urethane dimethacrylate
  • TEGDMA TEGDMA
  • PPGDA polypropylene glycol diacrylate
  • a) at least one at least difunctional urethane (meth)acrylate is preferably selected from difunctional urethane (meth)acrylate with a divalent alkylene group, including difunctional urethane (meth)acrylates with a linear or branched divalent alkylene group with 3 up to 20 carbon atoms, urethane dimethacrylate functionalized ethers with a linear or branched bivalent alkylene group with 3 to 20 carbon atoms, urethane dimethacrylate functionalized polyethers with a linear or branched bivalent alkylene group with 3 to 20 carbon atoms, urethane diacrylate Oligomer, bis(methacryloxy-2-ethoxycarbonylamino)alkylene and/or bis(methacryloxy-2-ethoxycarbonylamino)-substituted alkylene ethers are preferred, 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4
  • the difunctional urethane (meth)acrylate with a divalent alkylene group is preferably selected from linear or branched urethane dimethacrylates functionalized with a divalent alkylene group, ethers functionalized with urethane dimethacrylate or polyethers with alkylene group(s), such as bis(methacryloxy-2-ethoxycarbonylamino)-alkylene, bis(ethacryloxy-2-ethoxycarbonylamino)-substituted polyalkylene ethers, preferably
  • 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane UDMA.
  • a bis(methacryloxy-2-ethoxycarbonylamino)alkylene is preferred, where alkylene comprises linear or branched C3 to C20, preferably C3 to C6, such as particularly preferably an alkylene substituted with methyl groups.
  • the divalent alkylene preferably includes 2,2,4-trimethylhexamethylene and/or 2,4,4-trimethylhexamethylene.
  • UDMA (1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane) is particularly preferred.
  • the invention also relates to a dental material, in particular a composite material, which preferably comprises as b) at least two different hydrophilic alkylene oxide-based difunctional (meth)acrylate-based crosslinkers, one crosslinker being selected from i) and one crosslinker from ii) is selected or the crosslinker is selected separately from i) and iii) or at least one crosslinker is selected separately from i), ii) and iii), particularly preferably b) at least two different at least di-, tri-, tetra-, polyfunctional alkylene oxide-based difunctional (meth)acrylate-based crosslinkers selected from: i) 1,2-ethanediol dimethacrylate, diethylene glycol glycol dimethacrylate (DEGMA), triethylene glycol glycol dimethacrylate (TEGDMA), tetraethylene glycol glycol dimethacrylate, propylene glycol glycol dimethacrylate, dipropylene glycol glycol dimeth
  • the composite material can comprise as: e) at least one tri-, tetra-, penta- and/or hexa-functional (meth)acrylate-based crosslinker which is not a urethane (meth)acrylate and is selected from (i) having three ( Meth-)acrylate groups from trimethylolpropane trimethacrylate, ethoxylated (15)-trimethylolpropane triacrylate, ethoxylated-5-pentaerythritol triacrylate, propoxylated (5.5)-glyceryl triacrylate,
  • trimethylolpropane triacrylate tris(2-hydroxyethyl)isocyanurate triacrylate, and/or (ii) with four (meth)acrylate groups from di-trimethylolpropane tetraacrylate, ethoxylated-(4)-pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, di-trimethylolpropane tetramethacrylate, ethoxylated -(4)-pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate and/or (iii) with five (meth)acrylate groups from dipentaerythritol pentaacrylate, i-pentaerythritol pentamethacrylate, dipentaerythritol pentaacrylate, di(tetramethylolmethane)pentamethacrylate and
  • the c) mixture of the acidic monomers preferably comprises i) at least one olefinic acidic monoester of a phosphoric acid and/or at least one olefinic acidic monoester of a thiophosphoric acid, in particular at least one phosphoric acid-based (meth)acrylate, phosphoric acid-based urethane (meth)acrylate and/or or at least one thiophosphoric acid-based (meth)acrylate
  • biphenyltetracarboxylic dianhydride and 2-(3,4-dicarboxybenzoyloxy)1,3-di(meth)acryloyloxypropane.
  • the respective (meth)acrylates are each independently selected from methacrylates and acrylates, this also applies in particular to urethane (meth)acrylates which are independently selected from urethane methacrylates and urethane acrylates and in monoesters of phosphoric acid and all other olefinic compounds mentioned.
  • MAC-10 11-(meth)acryloyloxy-1,1-undecanedioic acid
  • 2-(meth)acryloyloxyethylphenyl acid phosphate and/or 10-(meth)acryloyloxydecylic acid phosphate are particularly preferred.
  • the content of the acidic monomers MDP and 4-META and/or 4-MET in the monomer component can be very low and very good adhesion values can be achieved with the composite according to the invention.
  • the MDP content can be about 4 to 5% by weight in the monomer component and the 4-META and/or 4-MET content can be about 2% by weight in the monomer component, with adhesion to dentin ( bovine tooth) in the range of 16 to 21 MPa and on enamel (bovine tooth) in the range of 4 to 21 Mpa.
  • the composite material in the A) monomer component can comprise i) at least one monofunctional (meth)acrylate-based monomer, in particular comprising 2-hydroxyethyl methyl acrylate (HEMA).
  • HEMA 2-hydroxyethyl methyl acrylate
  • Suitable monofunctional (meth)acrylate-based monomers include aromatic vinyl compounds such as styrene and divinylbenzene, vinyl esters such as vinyl acetate, aliphatic esters of (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth )acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate.
  • a dental material has an A) monomer component comprising a) 40 to 80% by weight of at least one at least difunctional urethane (meth)acrylate, b) 10 to 35% by weight of at least one hydrophilic alkylene oxide-based di- functional (meth)acrylate-based crosslinker which i) does not include urethane (meth)acrylate and/or ii) does not contain any aromatic radicals, or a mixture of at least two of these crosslinkers, c) 5 to 30% by weight of a mixture of acidic monomers comprising i) at least one olefinic, acidic ester of a phosphoric acid, in particular of the formula I, Ia, Ib and/or II, and/or at least one olefinic, acidic ester of a thiophosphoric acid, in combination with ii) at least one olefinic carboxylic acid and/or at least one olefinic carboxylic anhydride, d
  • filler component in the dental material selected from fissure sealants or composite material preferably at least one a) dental glass or a mixture of dental glasses, and b) optionally comprising at least one inorganic fluoride and/or amorphous metal oxide, mixed oxide, crystalline metal oxide, silicate, are used, where a ) the at least one dental glass comprises aluminosilicate glasses or fluoroaluminosilicate glasses, barium aluminum silicate, barium aluminum borofluorosilicate, strontium silicate, strontium borosilicate, lithium silicate and/or lithium aluminum silicate, dental glasses containing ytterbium fluoride and mixtures of at least two of the aforementioned dental glasses, and optionally b) comprises ytterbium fluoride, amorphous spherical fillers on oxide or Mixed oxide base, such as amorphous S1O2, ZrÜ2 or mixed oxides of S1O2 and ZrÜ2, pyrogenic or precipitated silica
  • the fillers can all be preferably silanized.
  • Common silanizing agents include (meth)acryloyloxypropyltrimethoxysilane and (meth)acryloyloxypropyltriethoxysilane or (meth)acryloyloxymethyltrimethoxysilane and (meth)acryloyloxymethyltriethoxysilane.
  • the dental material in particular the dental composite material, comprises at least one dental glass and/or mixtures of these, in particular a radiopaque dental glass or mixtures of these, with an average particle size dso of 0.2 to 5.0 mhi, in particular with dso of 0, 2 to 2.0 mhi, preferably with an average particle size of 0.2 to 1.75 mhi, in particular with dso of 1.0 mhi, optionally plus/minus 0.6 mhi, preferably plus/minus 0.05 mhi, and preferably with dgg less than or equal to 10 mGP.
  • an average particle size dso of 0.2 to 5.0 mhi in particular with dso of 0, 2 to 2.0 mhi, preferably with an average particle size of 0.2 to 1.75 mhi, in particular with dso of 1.0 mhi, optionally plus/minus 0.6 mhi, preferably plus/minus 0.05 mhi, and preferably with dgg less than
  • a particularly preferred particle size distribution can be in the range from dio greater than or equal to 0.1 mhi to dgg less than or equal to 5 mhi, preferably with dio greater than or equal to 0.4 mhi to dgg less than 2.5 mhi and an average diameter dso of 0.8 to 1.00 mhi.
  • the subject of the invention is a dental material comprising a filler component comprising at least one dental glass comprising barium aluminum borosilicate glass, barium aluminum borofluorosilicate glass, in particular silanized, preferably functionalized with methacryloxypropyl groups and optionally at least one non-agglomerated amorphous metal oxide with a primary particle size of 2 to 45 nm, the amorphous metal oxide being precipitated Silicon dioxide, zirconium oxide, mixed oxides or mixtures of these, in particular the metal oxides are silanized.
  • a filler component comprising at least one dental glass comprising barium aluminum borosilicate glass, barium aluminum borofluorosilicate glass, in particular silanized, preferably functionalized with methacryloxypropyl groups and optionally at least one non-agglomerated amorphous metal oxide with a primary particle size of 2 to 45 nm, the amorphous metal oxide being precipitated Silicon dioxide, zirconium oxide, mixed oxides or mixtures of these
  • the diketone is preferably a 1,7,7-trimethylbicyclo[2.2.1]hepta-2,3-dione (champhorquinone), phenylpropanedione, benzoyltrimethylgermane (BTMGe) and/or dibenzoyldiethylgermane (DBDEGe ), and the at least one co-initiator preferably comprises 2-n-butoxyethyl-4-(dimethylamino)benzoate and/or as 1,2-methylenedioxybenzene piperonyl alcohol (1,2-methylenedioxybenzene-4-methanol).
  • champhorquinone champhorquinone
  • BTMGe benzoyltrimethylgermane
  • DBDEGe dibenzoyldiethylgermane
  • the at least one co-initiator preferably comprises 2-n-butoxyethyl-4-(dimethylamino)benzoate and/or as 1,2-methylenedioxybenzen
  • tertiary amines may include 2-(ethylhexyl)-4-(N,N-dimethylamino)benzoate, dimethylaminobenzoic acid ester, triethanolamine, N,N-3,5-,N,N-3,5-tetramethylaniline, 4-(dimethylamino)phenylethyl alcohol, dimethylaminobenzoic acid ester, 4-(N,N-dimethylamino)benzoic acid.
  • At least one pigment such as titanium dioxide, a dye, and in particular at least one UV and/or Vis stabilizer comprising 2-hydroxy4-methoxybenzoic acid can be present both in the monomer component and/or in the filler component.
  • the c) mixture of acidic monomers preferably comprises i) ii) at least one olefinic, acidic ester of phosphoric acid, preferably a monoester of phosphoric acid, and/or at least one olefinic, acidic ester of thiophosphoric acid, preferably a monoester of thiophosphoric acid, more preferably at least one monoester of a Phosphoric acid and a (meth)acrylate, a monoester of a phosphoric acid and a urethane (meth)acrylate and/or at least one monoester of a thiophosphoric acid and a (meth)acrylate, esters of the formula I, Ia, Ib and/or II as well as being particularly preferred Mixtures
  • the dental material in A) comprises monomer component in c) as i) 4 to 20% by weight, in particular 9.5 to 20% by weight, of at least one olefinic, acidic ester of a phosphoric acid and/or at least one olefinic, acidic ester of a thiophosphoric acid, preferably at least one monoester of a phosphoric acid and a (meth)acrylate, monoester of a phosphoric acid and a urethane (meth)acrylate, at least one monoester of a thiophosphoric acid and a (meth)acrylate and/or at least one monoester of a thiophosphoric acid and of a urethane (meth)acrylate, esters of the formula I, Ia, Ib and/or II and mixtures containing these being particularly preferred, and as ii) 2 to 10% by weight, in particular 3.75 to 10% by weight, at least one olefinic carboxylic acid and/or
  • (Meth)acrylate is used consistently as a synonym for methyl acrylate or acrylate, i.e. any (meth)acrylates are disclosed as methyl acrylates or acrylates, regardless of whether these were disclosed as crosslinkers, urethane or monoesters of a phosphoric acid.
  • a dental material is preferred with A) monomer component comprising a) 50 to 80% by weight of at least one at least difunctional urethane (meth)acrylate, b) 10 to 35% by weight, in particular 15 to 35% by weight, preferably 20 % by weight with +/- 5% by weight, in particular 20% by weight +/- 3% by weight, of at least one hydrophilic alkylene oxide based di-functional (meth) acrylate-based crosslinker, which i) no urethane (meth) acrylate and / or ii) comprises no aromatic radicals, or a mixture of at least two of these crosslinkers, c) i) 4 to 20% by weight , in particular 9.5 to 20% by weight, at least one olefinic, acidic ester of a phosphoric acid and/or at least one olefinic, acidic ester of a thiophosphoric acid, in particular at least one monoester of a phosphoric acid and a (meth)
  • -% at least one dental glass or similar which is a mixture of dental glasses b) 0 to 10% by weight, in particular 5 to 10% by weight, of inorganic fluoride, such as ytterbium fluoride, metal oxide, such as S1O2, mixed oxides, silicates, quartz, feldspar and/or mixtures thereof, c) 0 to 5% by weight, in particular 0.1 to 0.6% by weight, of at least one pigment, such as T1O2, dye, UV and/or Vis stabilizer, and/or
  • inorganic fluoride such as ytterbium fluoride
  • metal oxide such as S1O2
  • mixed oxides such as silicates, quartz, feldspar and/or mixtures thereof
  • at least one pigment such as T1O2, dye, UV and/or Vis stabilizer, and/or
  • A) the monomer component and B) the filler component are present in the dental material in a mass ratio of 55:45 to 35:65 and the overall composition of the dental material is 100% by weight.
  • Another particularly preferred dental material comprises as A) a monomer component which comprises a) 50 to 80% by weight of at least one at least difunctional urethane (meth)acrylate, b) at least two hydrophilic alkylene oxide-based difunctional (meth) acrylate-based crosslinkers each selected from the combinations i) and ii) or i) and iii) or i), ii) and iii), with i) 10 to 20% by weight of 1,2-ethanediol dimethacrylate, diethylene glycol dimethacrylate (DEGMA) , triethylene glycol dimethacrylate (TEGDMA), tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate wt% polyethylene glycol di(meth)acryla t and/or polyprop
  • a filler component comprising a) 90 to 100% by weight of at least one dental glass, b) 0 to 10% by weight, in particular 5 to 10% by weight inorganic fluorides such as ytterbium fluoride, metal oxide such as S1O2, mixed oxides, crystalline metal oxide, silicate, c) 0 to 5% by weight, in particular 0.1 to 0.6% by weight, at least a pigment such as PO2, dye, UV and/or Vis stabilizer, the total composition of the monomer component A) being 100% by weight, and B) a filler component comprising a) 90 to 100% by weight of at least one dental glass, b) 0 to 10% by weight, in particular 5 to 10% by weight inorganic fluorides such as ytterbium fluoride, metal oxide such as S1O2, mixed oxides, crystalline metal oxide, silicate, c) 0 to 5% by weight, in particular 0.1 to 0.6% by weight, at least a pigment such as PO2, dye, UV and
  • compositions in which the contents of the components are mentioned, the contents that are mentioned behind in particular are to be understood as belonging together; the same applies in subgroups for the contents mentioned there as preferred.
  • the disclosure is also to be understood in connection with the non-exhaustive examples listed and is aimed at the chemist or materials scientist.
  • a polymerized dental material obtainable by polymerization, in particular by polymerization using visible light
  • the polymerized dental material has a shear bond strength to bovine tooth dentin of greater than or equal to 10 MPa, preferably greater than or equal to 15 MPa, preferably greater than or equal to 17 MPa, particularly preferably greater than or equal to 20 MPa, and/or a shear bond strength on bovine tooth melt of greater than or equal to 12 MPa, preferably greater than or equal to 19 MPa, preferably greater than or equal to 22 MPa, particularly preferably greater than or equal to 23 MPa.
  • the subject matter of the invention is also the use of a hardenable or polymerizable dental material for radiation-hardening, self-adhesive bonding to dentine and/or enamel of teeth, in particular human or veterinary teeth.
  • Radiation curing preferably takes place by means of visible light (Vis radiation), preferably in the wavelength range from 420 to 500 nm, preferably at 485 nm.
  • Suitable light sources are LED lamps.
  • the invention also relates to a self-adhesive, radiation-curable dental material, in particular a fissure sealant or a dental composite material or self-adhesive, polymerized, in particular radiation-cured composite material for use in sealing fissures in enamel and/or dentin, and/or for use in radiation-curing, self-adhesive adhesion on substrates, including metallic substrates, ceramic substrates and/or hybrid materials including polymers, in particular non-precious metals, zirconium, composites, precious metals, on dentin and/or enamel of teeth, in particular human or veterinary teeth.
  • the invention also relates to a dental material for use as a self-adhesive fissure sealant or for use as a self-adhesive dental composite.
  • the shear bond strength is measured according to DIN EN:ISO 29022 (2013).
  • Bovine tooth Enamel and/or dentine surfaces were prepared on 120 to 320 grit SiC paper. In the case of the "uncut" surfaces, mechanically cleaned bovine tooth enamel surfaces are used as the adhesive surface (Sof-Lex discs from 3M).
  • the fissure sealant is massaged onto the tooth substrate and exposed to light for 10 s with a Tranzlux Wave (Kulzer GmbH, spectrum: 440 to 480 nm, power density 1200 milliwatts/cm 2 ). The material is then filled into cylindrical plastic molds (Ultradent equipment) and cured for 20 s.
  • TWC thermal cycle, thermal cycling bath/thermal cycling load for artificial aging
  • the shear bond strength is determined using a universal testing device (crosshead speed 1 mm/min). 24 h measurements 37 °C in H2O. Measurement universal test device (room temperature). Unless otherwise stated, RZS / RZD are the 24-hour measurements.
  • the flexural strength and the flexural modulus of elasticity are measured according to the DIN-ISO 4049 standard (polymer-based filling, restoration and fixing materials, measurements at room temperature, 2019).
  • the water absorption/solubility is determined according to DIN-ISO 4049 Section 7.12 to 4-8. Test specimens with a diameter of 15 mm and a width of 1 mm are cured, dried, stored in H2O at 37° C. for 7 days and dried again.
  • the film thickness of the fissure sealant is determined according to ISO 4049 7.5.
  • the material is loaded between 2 glass plates with 150 N for 180 s, hardened and the difference is measured with an outside micrometer.
  • the hardness is determined as follows: Harden the 10 mm Delrin form/Teflon form test specimen for 20 s on the upper side (OS). Mark underside (US). Store in H2O for 24 h at 37 °C, grind flat and determine the penetration force (N/mm 2 )/penetration depth of the top/bottom with Zwick universal hardness using a diamond.
  • alkylene oxide-based difunctional methacrylates used in the following examples such as TEGDMA, PEGDMA or DDDMA (dodecanediol dimethacrylate), especially in preferred alternatives due to the combination of these and/or due to the content in the non-polymerized state of the fissure sealant, cause good flow to the Enamel as well as penetration into fissures and thus the high adhesive strength after radiation curing. Adhesion to the enamel occurs without prior etching of the enamel.
  • the concentration of the initiator and the ratio of diketone to co-initiator in the dental material are decisive, since a high crosslinking conversion during polymerisation also causes good adhesion to the substrate, in this case dentin and/or enamel.
  • the content of the combination of camphorquinone (CQ)/tertiary amine (2-n-butoxyethyl)-4-(dimethylamino)benzoate, BEDB) should be greater than 0.2% by weight, in particular greater than 0.3% by weight for the diketone and greater than 0.4% by weight, in particular 0.6% by weight, of the co-initiator in the initiator system in the monomer component, preferably in the overall composition of the dental material.
  • Table 1 shows the shear bond strength values achieved on ground cattle tooth enamel (RZS), unpolished enamel (RZS-unpolished/RZS-uncut) after a thermal change bath (TWL) in dental material that is otherwise qualitatively and quantitatively identical in composition (measurement according to ISO 29022 in MPa).
  • RZS ground cattle tooth enamel
  • RZS-unpolished/RZS-uncut unpolished enamel
  • TWL thermal change bath
  • Particle sizes of the fillers The particle sizes are determined using laser diffraction.
  • the particle size is usually determined by means of laser diffraction with the Cilas device or alternatively Horiba LA-950 (Retsch) or DT1200 (Dispersion Technology). be there Unsilanized fillers are measured in (destilled) water and silanized fillers are measured in isopropanol.
  • the accuracy for particle sizes of 1.5 microns or D50 1.5 microns is also at least in this range.
  • alkylene oxide-based difunctional methacrylates used in the following examples such as TEGDMA, PEGDMA or DDDMA (dodecanediol dimethacrylate), in particular due to the combination of these and/or due to the content in the non-polymerized state of the composite, cause good flow to the polar substrate of the dentin and the enamel and thus the high adhesion after radiation curing.
  • the initiator concentration in the composite is also very important, since a high degree of crosslinking conversion during polymerisation with visible light also results in good adhesion to the substrate, in this case dentin and enamel.
  • the level of the combination of camphorquinone (CQ)/tertiary amine should preferably be greater than 0.3%/greater than 0.6% by weight in the total composition.
  • Table 1 shows the shear bond strength values (SBS, Shear Bond Strength) achieved on bovine tooth dentine (RZD) and bovine tooth enamel (RZS).
  • Table 1 SBS bovine tooth dentine in MPa with various acidic monomers (MDP, MMD404, MMD406) these are pure monomer mixtures without fillers (a) 74.1% by weight, UDMA, 15% by weight TEGDMA, 10% by weight % acidic monomer, b) 74.1% by weight UDMA, 14.1% TEGDMA, 10% by weight acidic monomer:
  • 4-META (4-methacryloyloxyethytrimellitic anhydride) in combination with a phosphoric acid-containing monomer such as MDP (10-methacryloyloxydecyl dihydrogen phosphate) significantly increases dentin adhesion.
  • MDP 10-methacryloyloxydecyl dihydrogen phosphate
  • DDDMA dodecanediol-di-methacrylate
  • the highest shear bond strengths can be achieved with composites with the combination of acidic monomers of carboxylic acids or carboxylic acid anhydrides with acidic esters and two different alkylene oxide-based difunctional methacrylates comprising TEGDMA and PEGDMA or TEGDMA and DDDA, see Table 2a/2b.
  • 4-META (4-methacryloyloxyethytrimellitic acid anhydride) in combination with a phosphoric acid-containing monomer such as MDP (10-methacryloyloxydecyl dihydrogen phosphate) again significantly increases adhesion.
  • High shear bond strengths can be achieved with dental materials in the combination of acidic monomers of carboxylic acids or carboxylic acid anhydrides with acidic esters of phosphoric acid and two different alkylene oxide-based difunctional methacrylates including TEGDMA and PEGDMA (polyethylene glycol dimethyl acrylate), TEGDMA and polyethylene glycol diacrylate or TEGDMA and DDDA can be achieved.
  • TEGDMA and PEGDMA polyethylene glycol dimethyl acrylate
  • TEGDMA and TEGDMA and DDDA can be achieved.
  • the propylene glycol diacrylate-based fissure sealants also show reduced water absorption with increased shear bond strength with and without TWC.
  • Examples 15, 16 and 17 were created with a proportion of the filler component of 60% by weight in the dental material for the production of a composite, and their adhesion performance clearly distinguishes them from the competitor Constic and Vertise Flow.
  • Table 3b Examples 15, 16 and 17 with a filler content of 60% by weight
  • Table 3c Shear bond strength according to ISO 29022 on cattle tooth enamel (RZS), especially visible after aging in thermal cycling (TWL):
  • Table 7a With 60% by weight of filler for the composite formulation with various acidic monomer combinations, or EBADMA and HEMA
  • Table 7b With 60% by weight of filler for the composite formulation with various acidic monomer combinations, or EBADMA and HEMA Table 8a: With 60% by weight of filler as a composite formulation with various acidic monomer combinations, or TEGDMA and other crosslinkers, hydrophilic crosslinkers or crosslinkers of the formula IX, such as EBADMA Table 8b: With 60% by weight of filler as a composite formulation with various acidic monomer combinations, or TEGDMA and other hydrophilic crosslinkers and crosslinkers of the formula IX, such as EBADMA
  • Table 8c Comparative examples Table 9: Dental material comprising monomers a), b) and c) with variation in the filler system

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  • Health & Medical Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
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  • Veterinary Medicine (AREA)
  • Inorganic Chemistry (AREA)
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  • Biophysics (AREA)
  • Plastic & Reconstructive Surgery (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

Matériau dentaire autoadhésif radiodurcissable comprenant A) un composant monomère comprenant un (méth)acrylate d'uréthane difonctionnel, des agents de réticulation à base de (méth)acrylate difonctionnel à base d'oxyde d'alkylène hydrophiles, au moins un monomère acide d'un monoester acide oléfinique d'un acide phosphorique et/ou un monoester acide oléfinique d'un acide thiophosphorique, éventuellement en combinaison avec un acide carboxylique oléfinique et/ou un anhydride d'acide carboxylique oléfinique, et un initiateur et/ou un système initiateur présentant respectivement un maximum d'absorption compris entre 420 et 550 nm et éventuellement avec un co-initiateur et éventuellement B) un composant de charge comprenant au moins un verre dentaire, en particulier A) le composant monomère et B) le composant de charge étant présents avec un rapport massique a) compris entre 100 : 0 et 60 : 40 dans les matériaux de scellement de sillons ou b) compris entre 59 : 41 et 20 : 80 dans les matériaux composites et la composition totale du matériau de scellement de sillons ou du matériau composite étant égale à 100 % en poids.
EP22720373.4A 2021-04-02 2022-03-31 Matériau dentaire autoadhésif Pending EP4312945A1 (fr)

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DE102021108477.6A DE102021108477A1 (de) 2021-04-02 2021-04-02 Selbstadhäsiver Fissurenversiegler
DE102021108476.8A DE102021108476A1 (de) 2021-04-02 2021-04-02 Selbstadhäsives Dentalmaterial
PCT/EP2022/058709 WO2022207877A1 (fr) 2021-04-02 2022-03-31 Matériau dentaire autoadhésif

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US4871786A (en) 1988-10-03 1989-10-03 Minnesota Mining And Manufacturing Company Organic fluoride sources
GB2257433A (en) 1991-07-12 1993-01-13 Bipin Chandra Muljibhai Patel Dental material usable as e.g. fissure sealant
EP1124529B1 (fr) 1998-11-03 2008-01-09 New Age Biomaterials, Inc. Charge amelioree destinee aux materiaux composites dentaires
JP5933156B2 (ja) * 2004-07-27 2016-06-08 デンツプライ デトレイ ゲー．エム．ベー．ハー． 歯科用接着剤組成物
JP2010184997A (ja) * 2009-02-12 2010-08-26 Gc Corp 二成分系開始剤及びそれを利用した重合性組成物
DE102010003881A1 (de) * 2010-04-12 2011-10-13 Voco Gmbh Dentale Abdeckmasse
EP3603606B1 (fr) * 2017-03-31 2024-11-13 Mitsui Chemicals, Inc. Monomère adhésif pour matériau dentaire
DE102018123330A1 (de) * 2018-09-21 2020-03-26 Kulzer Gmbh Strahlenhärtbare Zusammensetzung zur Verwendung in Rapid-Prototyping oder Rapid-Manufacturing Verfahren
JP7121809B2 (ja) * 2018-12-28 2022-08-18 三井化学株式会社 歯科材料用モノマー組成物、歯科材料用組成物及び歯科材料

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