EP3654923A1 - Matériau composite dentaire et ébauches à fraiser de ce matériau composite - Google Patents

Matériau composite dentaire et ébauches à fraiser de ce matériau composite

Info

Publication number
EP3654923A1
EP3654923A1 EP18783400.7A EP18783400A EP3654923A1 EP 3654923 A1 EP3654923 A1 EP 3654923A1 EP 18783400 A EP18783400 A EP 18783400A EP 3654923 A1 EP3654923 A1 EP 3654923A1
Authority
EP
European Patent Office
Prior art keywords
composite material
equal
dental
meth
urethane
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
EP18783400.7A
Other languages
German (de)
English (en)
Inventor
Andreas Utterodt
Kurt Reischl
Nelli Schönhof
Michael Eck
Raif KOCOGLU
Jutta Schneider
Caroline Kempka
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
Application filed by Kulzer GmbH, Kulzer and Co GmbH filed Critical Kulzer GmbH
Publication of EP3654923A1 publication Critical patent/EP3654923A1/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
    • A61K6/891—Compounds obtained otherwise than 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
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/79—Initiators
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/15—Compositions characterised by their physical properties
    • A61K6/17—Particle size
    • 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
    • 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
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
    • 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
    • A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
    • 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
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A61K6/893—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Definitions

  • the invention relates to a polymerizable, dental composite material comprising
  • dental composites which are universally applicable for a direct adhesive restoration as well as for the extraoral production of indirect dentures. From the material class of the dental composite are suitable in principle only the inorganic-organic hybrid materials with larger amounts of inorganic filler such. Dental glass and / or mineral nano-agglomerates.
  • the micro-fiber composites with pre-polymer fillers introduced in the 1980s are not suitable for use in the posterior region (classes I and II) due to the limited wear resistance (abrasion resistance).
  • a high filler content is advantageous in order to achieve very good mechanical properties of 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 denture material.
  • the excellent material properties of dental composites with polyalicyclic structural elements for the direct adhesive restoration, in particular the low shrinkage force with high flexural strength, are known.
  • the object of the invention was to provide a dental composite material which is suitable for the production of larger blocks of material, in particular of geometric shaped bodies, such as milling blocks. Furthermore, the object was to provide a dental composite material which has a homogeneous, monochrome coloration before and after the polymerization. In this case, the homogeneous, monochrome dyeing should be feasible even with larger blocks of material. Furthermore, polychrome, ie multi-colored blocks of material with defined color should be produced.
  • a dental composite material should be provided which is easily flowable in the unpolymerized state and yet has excellent mechanical properties in the polymerized state and in the polymerization has a low shrinkage even in the production of larger blocks of material. Furthermore, the composite material during curing, even in large-volume material blocks, neither cracks or pores develop.
  • the filler system the monomer mixture, and the pigment system had to be modified.
  • the monomer system should be adjusted in accordance with the filler system to obtain a tuned high flexural strength in combination with a modulus of elasticity in the range of 12 to 23 GPa for polymerized dental material blocks of the composites.
  • Bulky moldings for producing larger blocks of material can not be photopolymerized because of the limited penetration of the light into the composite material.
  • the initiator system had to be adapted and further developed by using at least one thermally initiated peroxide.
  • the usual blue light photoinitiators such as the Champherquinone initiator system have been excluded to avoid color changes due to the composite layer thickness.
  • the initiator system care must be taken that, on the one hand, no tensions are built up in the large blocks of material due to the reaction kinetics, for example, of a peroxide in order to prevent crack formation in the interior of the blocks, since the thermal conductivity of the materials is low.
  • the shaping for the production of the blocks of material takes place by introducing the polymerizable, dental composite material into a casting mold, hereinafter only in shape called, under pressure.
  • the applied pressure is preferably 500 to 300 MPa. or [N / mm 2 ].
  • the polymerization is carried out at elevated temperature, which is preferably in the range of about 90 to 150 ° C. It is polymerized in a closed mold to minimize, preferably avoid, the formation of air bubbles. Preference is given to polymerizing under a pressure of from 120 to 320 MPa, preferably to less than or equal to 300 MPa, at a temperature of from 100 to 180 ° C., preferably by 140 ° C., for at least 10 minutes to 10 hours.
  • the material blocks preferably have at least one dimension of 1 cm in all spatial directions and are present as geometric shaped bodies.
  • the invention relates to a polymerizable, dental composite material, in particular a thermally polymerizable composite material comprising
  • Dental glasses and optionally at least one amorphous metal oxide,
  • R 1 , R 2 and R 3 , R 4 are each independently H or C1-C4 alkyl unsubstituted or substituted, in particular with R 1 , R 4 is H and R 2 and R 3 is C1 to C4 alkyl.
  • the thermally polymerizable composite material is additionally polymerizable photochemically.
  • a thermally polymerizable composite material is understood as meaning a composite material that can be polymerized at greater than or equal to 60 to 150 ° C., preferably at greater than or equal to 70 to 150 ° C., particularly preferably from 90 to 150 ° C. It is further preferred according to the invention if the volume shrinkage is less than or equal to 1, 5%.
  • a polymerized composite material with a flexural strength of greater than or equal to 190 MPa, in particular greater than or equal to 230 MPa, and a modulus of elasticity of 12 to 21 GPa, in particular both dry and after water storage with thermocycling available.
  • the polymerized composite material is preferably present as a material block, in particular in the form of a milling blank with a dimension of at least 10 cm in all spatial directions.
  • Preferred dental glasses are: aluminosilicate glasses or fluoroaluminosilicate glasses, barium aluminum silicate, strontium silicate, strontium borosilicate, lithium silicate and / or lithium aluminum silicate and mixtures of at least two of the aforementioned dental glasses.
  • amorphous metal oxide or as a mixture of amorphous metal oxides it is possible to use amorphous spherical fillers based on oxide or mixed oxide, such as amorphous SiO 2 , ZrO 2 or mixed oxides of SiO 2 and ZrO 2 .
  • the dental composite material comprises at least one dental glass, in particular a radiopaque dental glass, an average particle size d 5 o of 0.1 to 1, 0 ⁇ , in particular in an alternative of 0.7 to 1, 0 ⁇ , 0.7 ⁇ to 0.9 ⁇ , preferably with an average particle size of 0.8 to 0.95 ⁇ , in particular with d 50 of 0.90 ⁇ optionally plus / minus 0.05 ⁇ , preferably plus / minus 0.05 ⁇ , and preferably with d 99 less than or equal to 10 ⁇ .
  • d 99 is less than or equal to 10 ⁇ .
  • Particularly preferred is an average particle size of d 50 of about 0.40 ⁇ optional plus / minus 0.1 ⁇ , in particular plus / minus 0.05 ⁇ , preferably in particular plus / minus 0.03 ⁇ , and preferably less than or equal to d 99 10 ⁇ .
  • a particularly preferred particle size distribution may be in the range from d with greater than or equal to 0.05 ⁇ to d 99 less than or equal to 5 ⁇ , preferably with d greater than or equal to 0.2 ⁇ to d 99 smaller 2.5 ⁇ and a mean diameter d 5 o of 0.4 to 0.9 ⁇ .
  • the dental composite material (i) comprises 70 to 85 wt .-% of at least one inorganic filler component comprising at least one dental glass or a mixture of dental glass with different average particle sizes, wherein the average particle size d 50 in the range of 0.1 to 0 , 7 ⁇ of greater than or equal to 70 to 80 wt .-% with respect to the composite material, in particular greater than or equal to 71 to 76 wt .-%.
  • the invention further provides a dental composite material comprising (i) 60 to 85% by weight of at least one inorganic 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 one amorphous metal oxide having a primary particle size of 2 to 45 nm, wherein the amorphous metal oxide comprises precipitated silica, zirconium oxide, mixed oxides or mixtures thereof, in particular the metal oxides are silanized.
  • the dental composite material preferably comprises as inorganic filler component (i.1) 70 to 84 wt .-% of at least one dental glass, in particular 70 to 80 wt .-%, preferably 71 to 76 wt .-% and optionally (i .2) 1 to 15% by weight of amorphous metal oxide, in particular 3 to 10% by weight, preferably 4 to 8% by weight, in the overall composition.
  • the ratio of dental glass to amorphous metal oxide is preferably from 20: 1 to 5: 1, preferably from 15: 1 to 10: 1.
  • the dental composite material comprises
  • the dental composite material may comprise a mixture of at least two different urethane (meth) acrylates, preferably three different urethane (meth) acrylates selected from at least one difunctional urethane (meth) acrylate having a bivalent alicyclic group, a difunctional urethane (meth ) Acrylate with bivalent alkylene group and optionally at least one at least tetrafunctional dentrist urethane (meth) acrylate, preferably at least one hexafunctional dendritic urethane (meth) acrylate.
  • difunctional urethane (meth) acrylates having a bivalent alicyclic group comprising bis (4 ', 7'-dioxa-3', 8'-dioxo-2'-aza-decyl-9'-ene) tetrahydrodicyclopentadiene, bis (4 ', 7'-dioxa-3', 8'-dioxo-2'-aza-9'-methyl-decyl-9'-ene) tetrahydrodicyclopentadiene and / or mixtures thereof and optionally mixtures of 3.8- / 3.9 - / 4,8- / 3,10- / 4,10-isomers and / or the cis and transisomers of the aforementioned compounds.
  • the bivalent alkylene difunctional urethane (meth) acrylate is preferably selected from linear or branched bivalent alkylene functionalized urethane dimethacrylates, urethane dimethacrylate functionalized polyethers having alkylene group (s) such as bis (methacryloxy-2-ethoxycarbonylamino) alkylene , Bis (methacryloxy-2-ethoxycarbonylamino) substituted polyalkylene ethers, preferably 1, 6-bis (methacryloxy-2-ethoxycarbonylamino) -2,4,4-trimethylhexane, UDMA or HEMA-TDMI.
  • alkylene group (s) such as bis (methacryloxy-2-ethoxycarbonylamino) alkylene , Bis (methacryloxy-2-ethoxycarbonylamino) substituted polyalkylene ethers, preferably 1, 6-bis (methacryloxy-2-ethoxycarbonylamino) -2,4,4-trimethylhex
  • the bivalent alkylene preferably comprises 2,2,4-trimethylhexamethylene and / or 2,4,4-trimethylhexamethylene.
  • the at least tetra-functional dendritic urethane methacrlylate comprises tetra- to deca-functional dendritic urethane methacrylates.
  • the dental composite material as component (iii) comprises 0.01 to 5% by weight of at least one di-, tri-, tetra- or multifunctional monomer which is not urethane acrylate and is selected from (meth) acrylate esters of tetrahydrodicyclopentadiene, preferably bis (methacryloyloxymethyl) -tetrahydrodicyclopentadiene, bis (acryloyloxymethyl) tetrahydro-dicyclopentadiene, di (meth) -acrylic esters and optionally mixtures comprising at least one 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomer and / or cis and trans isomer of the aforementioned compounds and optionally di-methacrylic esters of Polyethers, tri-, tetra- or multi-functional (meth) acrylic esters of polyethers.
  • the content of components (iii) is preferably from 0.15 to 5% by weight, particularly preferably from 1.0 to 2% by weight, of a di-methacrylic ester, di-methacrylic ester of a polyether, such as, preferably, a dimethacrylate-polyethylene glycol, dimethacrylate -Polypropylenglycol.
  • a di-methacrylic ester, di-methacrylic ester of a polyether such as, preferably, a dimethacrylate-polyethylene glycol, dimethacrylate -Polypropylenglycol.
  • Particularly preferred are dimethacrylate triethylene glycol (TEGDMA), diethylene glycol dimethacrylate (DEGMA) and dimethacrylate tetraethylene glycol (TEDMA).
  • the composite material in component (iv) comprises at least one stabilizer selected from water, at least one benzophenone derivative, preferably alkoxy-substituted benzophenone and / or phenol derivative such as 2-hydroxy-4-methoxybenzophenone, 2,6-bis (1, 1-dimethyl) -4-methylphenol, or a mixture of the three stabilizers.
  • the stabilizers are preferably present in the total composition at from 0.01 to 14% by weight, more preferably from 0.7 to 10% by weight, in particular from 0.5 to 2% by weight.
  • the composite material contains 0.01 to 2% by weight of water as stabilizer, preferably 0.1 to 1.0% by weight of water.
  • at least one pigment comprising at least one fluorescent pigment and optionally at least one organic color pigment and / or at least one inorganic color pigment, in particular non-fluorescent color pigments, are added to the composite material.
  • the at least one fluorescent pigment is preferably an organic fluorescent pigment, in particular a non-polymerizable, organic fluorescent pigment optionally comprising arylcarboxylic acid esters, arylcarboxylic acids, coumarin, rhodamine, naphthanimide or a derivative of the respective substance.
  • Inorganic fluorescent pigments may include CaAl 4 O 7 : Mn 2+ , (Ba 0 .98 Eu 0 .2) MgAl 10 Oi 7 , BaMgF 4 : Eu 2+ , Y (1,995) Ce (0.005) SiO 5 .
  • the composite may comprise organic pigments and also inorganic pigments, in particular comprising diethyl 2,5-dihydroxyterephthalate, N, N'-bis (3,5-xylyl) perylene-3,4: 9, 10-bis ( dicarbimide), copper phthalocyanine, titanate pigment, in particular chromium antimony titanate (rutile structure), spinel black, in particular pigments based on iron oxide black (Fe 3 O 4 ), wherein iron (Fe) is partially substituted by chromium and copper or nickel and chromium or manganese, zinc iron chromium spinel, brown spinel; ((Zn, Fe) (Fe, Cr) 2 0 4 ) Cobalt zinc aluminate blue spinel and / or titanium oxide.
  • the pigments comprising fluorescent and color pigments are preferably present at 0.01 to 10 wt .-% in the total composition, particularly preferably from 0.01 to 5 wt .-%, preferably from
  • the choice of pigments must be specifically tailored to the dental composite composition in order to be able to set a homogeneous color both in the polymerizable composite and in the polymerized composite. Also, the production of the large blocks of material requires a vote on the selection as well as the concentration of the pigments to avoid unwanted discoloration due to the dimensioning of the polymerized material blocks.
  • Suitable initiators are peroxides, hydroxyperoxides or mixtures comprising these.
  • Suitable thermal initiators can be used as free-radical initiators in the temperature range from 70 to 150.degree. C., preferably from 90 to 150.degree.
  • Preferred thermal initiators comprise at least one initiator selected from: tert-butyl-peroxy-2-ethylhexanoate, dibenzoyl peroxide, dicumyl peroxide, dicumyl hydroperoxide, azobisisobutyronitrile, benzylbarbituric acid derivative.
  • the polymerization preferably takes place in a casting mold, which preferably has a geometric shape.
  • the polymerization under elevated pressure minimizes or avoids the formation of air bubbles in the polymerized composite material.
  • the shrinkage of the polymerizable composite material is preferably less than 2.0%, in particular less than 1, 5%, particularly preferably less than or equal to 1.4%.
  • the polymerized composite material preferably has no voids or cracks of a size greater than or equal to 200 nm; in particular, a block of material has no voids or cracks.
  • the polymerized composite material has a density greater than or equal to 2.0 g / cm 3 , in particular a density greater than or equal to 2.1 g / cm 3 .
  • the polymerized dental composite material which is obtainable in particular by thermal polymerization of the composite material has a flexural strength of greater than or equal to 200 MPa, in particular a flexural strength of greater than or equal to 210 MPa, preferably greater than or equal to 220 MPa, preferably greater than or equal to 230 MPa. greater than or equal to 240 MPa, greater than or equal to 250 MPa in accordance with EN ISO 6872: 2008.
  • the flexural strength of the composite material is preferably greater than or equal to 230 MPa, preferably greater than or equal to 240 MPa, greater than or equal to 250 MPa, in particular smaller equal to 300 MPa.
  • the flexural strength is preferably greater than or equal to 200 MPa, in particular greater than or equal to 210 MPa, preferably greater than or equal to 220 MPa, in particular greater than or equal to 230 MPa (7 days, 37 ° CH 2 0) according to EN ISO 6872: 2008.
  • the flexural strength after storage for 7 days in water with thermocycling is preferably greater than or equal to 200 MPa, preferably greater than or equal to 210 MPa, preferably greater than or equal to 220 MPa, particularly preferably greater than or equal to 230 MPa to less than or equal to 300 MPa according to EN ISO 6872: 2008 where the storage in water is analogous to Dent. Mater. J. 2014; 33 (5) 705-710 with 5000 cycles.
  • the flexural strength and the modulus of elasticity were determined analogously to Dent. Materials J 2014; 33 (4/5), 705 to 710 prepared and measured (dry and after a 7-day storage in water with and without thermocycling), ie according to EN ISO 6872: 2008 or with additional water storage.
  • the ISO 6872 standard was created to test ceramic materials that were available as CAD / CAM blocks. Now that the composite materials are also produced and processed in the same dimensioning, a comparable analogous test with water storage should be carried out.
  • the preparation of test specimens according to the composite standard (ISO4049) can not be made from such blocks due to the dimension of the specimens.
  • flexural strength of a dental composite is not limited to large values (> 100 MPa), balanced / optimal elasticity is advantageous for the application.
  • the modulus of elasticity should ideally correspond to that of dentin of hard tooth substance, so that in the dedicated application a failure is avoided as possible.
  • Brittle (high modulus) materials are prone to chipping or fracture.
  • To elastic materials (low modulus of elasticity) deform under the chewing load and the cementation dissolves (debonding). From the literature (Dwayne D. Arola et al., Biomaterials 27 (2006) 2131-2140), the material properties (flexural strength and modulus of elasticity) of human hard tooth substance as a function of the orientation (anisotropic material properties due to crystallite orientation) are known.
  • the modulus of elasticity of human hard tooth substance is between 15 and 19 GPa. It was therefore desirable to provide a composite with an modulus of elasticity which lies in the range of the human tooth hard substance, that is to say preferably in the range of 15-20 GPa, in order to imitate tooth-like properties.
  • the invention therefore also relates to a polymerized, dental composite material having a modulus of elasticity greater than or equal to 12 to 21 GPa, preferably 15 to 20 GPa (dry and after a 7-day storage, dry) according to EN ISO 6872: 2008, in particular analogous to the method as in Dent. Mater. J. 2014; 33 (5) 705-710.
  • the publication also compares in Table 3 further results of the three-point bending test for CAD / CAM blocks of different dental materials measured by this method.
  • the modulus of elasticity according to the invention is preferably from 12 to 20 GPa, preferably from 14 to 20 GPa, more preferably from 15 to 20 GPa (measured after a 7-day storage in water with thermocycling) and / or the modulus of elasticity is preferably greater than or equal to 12 to 20 GPa (7 Days, 37 ° CH 2 0), preferably greater than or equal to 14 to 20 GPa, particularly preferably greater than or equal to 15 to 20 GPa.
  • the method in the exemplary embodiments is based on the method as described in Dent. Mater. J. 2014; 33 (5) 705-710. It is clear that the setting of an elastic modulus similar to that of the tooth hard substance in the range of 15 to 20 GPa both in dry storage as well as storage at 37 ° C plus thermocycling was previously not possible.
  • Table 1 Flexural strength in MPa and modulus of elasticity in GPa of Table 3 in Dent. Mater. J. 2014; 33 (5) 705-710
  • the invention relates to a polymerized, dental composite material comprising 60 to 85 wt .-% of at least one inorganic filler component comprising at least one dental glass having a mean particle size d 50 from 0.1 to 1, 0 ⁇ and optionally at least one amorphous, silanized metal oxide of a primary particle size of 2 to 45 nm, 10 to 30 wt.% of at least one polymer based on at least one monomer, preferably based on a mixture of the following monomers, comprising at least one bis-urethane derivative selected from 1, 3-bis ( 5'-alkyl-3 ', 8'-dioxo-2'-aza-4', 7'-dioxa-decyl-9'-ene) phenyl and / or 1, 3-bis (5 ', 9'-dialkyl -3 ', 8'-dioxo-2'-aza-4', 7'-dioxa-decyl-9'-ene) phenyl and
  • the polymerized, dental composite material may preferably be in the form of a material block, in particular as a three-dimensional block of material in the form of a geometric shaped body, in particular in the form of a milling blank with adapter for fixing in an automated material-removing device, particularly preferably in the form of a cylinder, a cuboid, preferably in Shape of a cube. Furthermore, it is preferred if the edges and / or corners of the shaped bodies are rounded.
  • the dimensions of the cylinder are preferably: height greater than or equal to 10 mm to less than or equal to 15 mm and radius greater than or equal to 3 to less than or equal to 7 mm, alternatively with a height greater than or equal to 10 mm to less than or equal to 20 mm and a radius greater than or equal to 5 to less than or equal to 7 mm.
  • the dimensions of the cuboid are preferably a, b, and c are greater than or equal to 4 mm, in particular greater than or equal to 10 mm, and a smaller than or equal to 20 mm, in particular less than or equal to 18 mm, b less than or equal to 14 mm and c smaller than or equal to 20 mm, in particular smaller equal to 18 mm.
  • a three-dimensional block of material has at least one edge length of at least 10 mm, preferably 14 mm.
  • Material blocks used as milling blocks preferably have the shape of cuboids, the cuboids preferably having a volume of 12 mm x 14 mm x 17 or 18 mm, alternatively 14 x 14 mm, or 15 x 15 mm and a height of 17 to 18 mm.
  • One to all edges and corners can be straight or rounded.
  • the invention further relates to the use of a dental composite material for the production of dental prosthetic restorations, in particular for the production of indirect dentures, in a material-removing method, in particular in a method in which the polymerized composite material by means of milling, cutting, polishing, breaking, chipping and or boring, particularly preferred in a process in which the polymerized composite material is removed by means of laser energy.
  • a particularly preferred use for the material is the use in a method of making dental prosthetic restorations in a material ablation process in which the material is ablated by laser energy.
  • the particle size, and preferably the particle size distribution has been specially adapted to a process in which the polymerized composite material is removed by means of laser energy and the prosthetic restorations can be produced.
  • a particular advantage of the dental material according to the invention is that it offers the possibility of a clear Process simplification in the manufacture of indirect dentures allowed by the dentist or the dental technician making at least one intraoral scan in the oral cavity of the patient and then directly using the thus obtained digital dental information a prosthetic dental restoration, such as a crown or inlay, taking into account other Device parameters etc. can produce.
  • the prepared dental prosthetic restoration can then be used on the patient, fixed and, if necessary, slightly reworked. For example, an intra-oral scan is taken before grinding a tooth to make a tooth stump for a crown and another intra-oral scan of the tooth stump.
  • the polymerized composite material may be used for the manufacture of dental prosthetic restorations including crowns, inlays, onlays, superstructures, artificial teeth, denture teeth, dental bridges, dental ridges, spacers, abutments or veneers.
  • the polymerizable composite material may also be used as a composite material Production of direct adhesive dental restorations.
  • urethane (meth) acrylates are the following: (ii) at least one urethane (meth) acrylate, in particular a urethane dimethacrylate, preferably a bis (methacryloxy-2-ethoxycarbonylamino) alkylene, diurethane acrylate oligomer, alkyl-functional Urethane dimethacrylate oligomers, aromatically functionalized urethane dimethacrylate oligomers, aliphatic unsaturated urethane acrylates, bis (methacryloxy-2-ethoxycarbonylamino) substituted polyethers, aromatic urethane diacrylate oligomers, aliphatic urethane diacrylate oligomers, aliphatic urethane diacrylates, hexafunctional aliphatic urethane resins, aliphatic urethane triacrylate, aliphatic urethane acrylate oligomer, unsaturated
  • difunctional and polyfunctional urethane (meth) acrylates in particular urethane di (meth) acrylates, particularly preferably the at least one (iii) urethane dimethacrylate selected from linear or branched alkyl-functionalized urethane dimethacrylates, urethane dimethacrylate functionalized polyethers, especially bis (methacryloxy-2-) ethoxycarbonylamino) alkylene, bis (methacryloxy-2-ethoxycarbonylamino) substituted polyether, preferably 1,6-bis (methacryloxy-2-ethoxycarbonylamino) -2,4,4-trimethylhexane.
  • Suitable urethane (meth) acrylates are available under the following trade names: Ebecryl 230 (aliphatic urethane diacrylate), Actilane 9290, Craynor 9200 (di-urethane acrylate oligomer), Ebecryl 210 (urethane diacrylate oligomeric oligomers), Ebecryl 270 (aliphatic urethane diacrylate oligomer), Actilane 165 , Actilane 250, Genome 1 122 (monofunctional urethane acrylate), Photomer 6210 (Cas no.
  • the urethane (meth) acrylates may preferably be selected from the abovementioned urethane (meth) acrylates or from a mixture of at least two different, preferably at least three, different urethane (meth) acrylates mentioned above.
  • the at least one further di-, tri-, tetra- or multi-functional monomer which is not a urethane (meth) acrylate may preferably be selected from at least one of the following monomers, in particular a mixture of monomers comprising 1, 4-butanediol dimethacrylate (1,4-BDMA) or pentaerythritol tetraacrylate, bis-GMA monomer (bisphenyl-A-glycidyl methacrylate), triethylene glycol dimethacrylate (TEGDMA) and diethylene glycol dimethacrylate (DEGMA), tetraethylene glycol di (meth) acrylate, Decanediol di (meth) acrylate, dodecanediol di (meth) acrylate, hexyldecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (
  • Typical other difunctional monomers are tri- or tetraethylene glycol di (meth) acrylate, BDMA, 1,4-butanediol dimethacrylate (1,4-BDMA), bis-GMA monomer (bisphenyl-A) Glycidyl methacrylate, an addition product of methacrylic acid and bisphenol A diglycidyl ether), diethylene glycol di (meth) acrylate, bisphenol A di (meth) acrylate, decanediol di (meth) acrylate, dodecanediol di (meth) acrylate, hexyl decane diol (meth ) acrylate, as well as butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylates, ethoxylated / propoxylated bisphenol A di (meth)
  • Tri- and tetrafunctional monomers or multicrosslinkers include trimethylolpropane tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate.
  • At least one of the following monomers may be present in the composite material comprising at least one monomer, in particular a mixture of monomers of methyl methacrylate, Ethyl methacrylate, propyl methacrylate, butyl methacrylate, n-hexyl methacrylate, 2-phenoxyethyl methacrylate, isobornyl methacrylate, isodecyl methacrylate, polypropylene glycol mono-methacrylate, tetrahydrofuryl methacrylate, polypropylene glycol mono-methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, n-hexyl methacrylate.
  • the invention further provides a composite material which preferably additionally contains at least one or more substances from the groups of fillers, pigments, stabilizers, regulators, antimicrobial additives, UV absorbers, thixotropic agents, catalysts and crosslinkers.
  • Such additives are - as well as pigments, stabilizers and regulators - used in rather small amounts, eg. B. in total from 0.01 to 3.0 wt .-%, particularly 0.01 to 1, 0 wt.% Based on the total mass of the material.
  • Suitable stabilizers are, for. As hydroquinone monomethyl ether or 2,6-di-tert-butyl-4-methylphenol (BHT).
  • the following initiators and / or initiator systems for auto or cold polymerization comprise a) at least one initiator, in particular at least one peroxide and / or an azo compound, in particular LPO: dilauroyl peroxide, BPO: dibenzoyl peroxide, t-BPEH: tert-butyl per-2-ethylhexanoate, AIBN: 2,2'-azobis (isobutyronitrile), DTBP: di-tert-butyl peroxide, and optionally b) at least one activator, in particular at least one aromatic amine, such as N, N-dimethyl-p-toluidine, N, N Dihydroxyethyl-p-toluidine and / or p-
  • an azo compound in particular LPO: dilauroyl peroxide
  • BPO dibenzoyl peroxide
  • t-BPEH tert-butyl per-2-ethylhexanoate
  • redox systems in particular a combination selected from dibenzoyl peroxide, dilauroyl peroxide and camphorquinone with amines selected from N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine and diethyl p-dimethylaminobenzoate.
  • the initiator system may be a redox system comprising a peroxide and a reducing agent selected from ascorbic acid, ascorbic acid derivative, barbituric acid or a barbituric acid derivative, sulfinic acid, sulfinic acid derivative, particularly preferred is a redox system comprising (i) barbituric acid or thiobarbituric acid or a barbituric acid or thiobarbituric acid derivative and (ii) at least one copper salt or copper complex and (iii) at least one compound having an ionic halogen atom, particularly preferred is a redox system comprising 1-benzyl-5-phenylbarbituric acid, copper acetylacetonate and Benzyldibutylammoniumchlorid.
  • the polymerization in the 2-component prosthesis base material is particularly preferably started via a barbituric acid derivative.
  • Suitable initiators for the polymerization reaction of cold-curing or autopolymerizing starting mixtures are, in principle, those with which free-radical polymerization reactions can be started.
  • Preferred initiators are peroxides and azo compounds, such as the following: LPO: dilauroyl peroxide, BPO: dibenzoyl peroxide, t-BPEH: tert-butyl per-2-ethylhexanoate, AIBN: 2,2'-azobis (isobutyronitrile), DTBP: di tert-butyl peroxide.
  • suitable activators for.
  • aromatic amines are added.
  • suitable amines are N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine and diethyl p-dibenzylaminobenzoate.
  • the amines regularly act as co-initiators and are usually present in an amount of up to 0.5 wt .-%. The following embodiments are intended to illustrate the invention without limiting the invention to these examples.
  • Bending properties were determined using a three-point bending test according to ISO 6872: 2008 (ISO 6872: 2008, Dentistry - Ceramic Materials, 3rd ed, International Organization for Standardization, Geneva, 2008).
  • the rod-shaped specimens, 4.0 mm wide, 14.0 mm long and 1.2 mm thick, were made with a low-speed diamond saw (Isomet, Buehler, Lake Bluff, IL, USA).
  • Samples from the first group were stored under dry conditions at room temperature (23 ⁇ 2 ° C).
  • the second group was stored in 37 ° C deionized water for 7 days, while the third group in 37 ° C deionized water for 7 days followed by 5,000 thermal cycles (thermocycling 5 ° C to 55 ° C, residence time 30 s) using a thermocyclic Device (HA-K178, Tokyo Giken Inc., Tokyo, Japan).
  • the width and thickness of each sample were measured by a digital micrometer (MDC-25M, Mitsutoyo Co., Tokyo, Japan, minimum value: 0.001 mm).
  • E FL 3 / 4b 3 d
  • F the load at a suitable location in the rectilinear part of the spring characteristic
  • L the span (12,0 mm)
  • b the width of the sample
  • h the thickness of the sample
  • d the bend at the Last F is.
  • the hardness test is carried out with the Zwick universal device:
  • the measured values of samples according to the invention are in the range from 800 to 850.
  • Table 4b Bending strengths and Young's modulus (according to EN ISO 6872) 7 days RT dry
  • Example 3 244 MPa 14.8 GPa 7 days, 37 ° CH 2 0
  • Example 3 216 MPa 13.6 GPa 7 days, 37 ° CH 2 0,
  • Example 4 232 MPa 15.9 GPa 7 days, 37 ° CH 2 0
  • Example 4 219 MPa 15.3 GPa 7 days, 37 ° CH 2 0,

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Chemical & Material Sciences (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Dental Preparations (AREA)
  • Dental Prosthetics (AREA)

Abstract

L'invention concerne un matériau composite dentaire polymérisable, comprenant : (i) 70 à 85 % en poids d'au moins un composant de charge inorganique comportant au moins un verre dentaire et éventuellement au moins un oxyde métallique amorphe ; (ii) 10 à 30 % en poids d'au moins un monomère contenant 1,3-bis (5 '-alkyl-3 ', 8 '-dioxo-2 '-aza -4 ', 7 '-dioxa-décya-décyl -9 '-énapine)phényle et/ou 1,3-Bis(5',9'-dialkyl-3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-ène)phényle, les groupes alkyle étant choisis respectivement indépendamment parmi des groupes alkyle en C1 à C4 linéaires ou ramifiés, éventuellement dans un mélange d'au moins deux (méth)acrylates d'uréthane différents ; (iii) 0,01 à 5 % en poids d'au moins un monomère di -, tri -, tétra-ou multifonctionnel qui n'est pas un (méth)acrylate d'uréthane, notamment comportant Bis(méthacryloyloxyméthyl)-tétrahydrodicyclopentadiène, Bis(acryloyloxyméthyl)tétrahydrodicyclopentadiène ou un mélange comportant au moins un monomère di -, tri -, tétra-ou multi-fonctionnel qui n'est pas un (méth)acrylate d'uréthane ; (iv) 0,01 à 10 % en poids au moins d'un amorceur, d'un système amorceur et éventuellement au moins d'un stabilisant et éventuellement au moins d'un pigment, la composition totale du matériau composite s'établissant à 100 % en poids ; ainsi qu'un matériau composite polymérisé offrant une résistance à la flexion supérieure ou égale à 190 MPa et un module d'élasticité de 12 à 21 GPA aux fins de fabrication d'une prothèse dentaire indirecte.
EP18783400.7A 2017-10-04 2018-10-01 Matériau composite dentaire et ébauches à fraiser de ce matériau composite Pending EP3654923A1 (fr)

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DE102017123016.5A DE102017123016A1 (de) 2017-10-04 2017-10-04 Dentales Kompositmaterial sowie Fräsrohlinge dieses Kompositmaterials
PCT/EP2018/076594 WO2019068614A1 (fr) 2017-10-04 2018-10-01 Matériau composite dentaire et ébauches à fraiser de ce matériau composite

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US6653375B2 (en) * 1998-01-28 2003-11-25 Ivoclar Ag Urethane di(meth)acrylate derivatives of 1,3-bis(1-isocyanato-1-methylethyl)benzene
DE102005002845A1 (de) 2004-02-18 2005-09-15 Heraeus Kulzer Gmbh Dispersionen nanoskaliger, nicht-agglomerierter Teilchen zum Einsatz in Dentalmaterialien
DE102007034457A1 (de) 2007-07-20 2009-01-22 Heraeus Kulzer Gmbh Dentalkomposite mit niedriger Schrumpfspannung und hoher Biegefestigkeit
EP2436365B1 (fr) * 2010-09-30 2017-03-08 VOCO GmbH Matériau composite comprenant un monomère doté d'un élément structurel polyalicyclique
US10130563B2 (en) * 2014-03-31 2018-11-20 Mitsui Chemicals, Inc. Dental polymerizable monomer compositions
JP2016130300A (ja) 2015-01-13 2016-07-21 株式会社トクヤマデンタル ポリアリールエーテルケトン樹脂材料用プライマー、接着キット、及び接着方法
US10470980B2 (en) 2015-03-31 2019-11-12 Mitsui Chemicals, Inc. Dental polymerizable monomers, compositions, adhesive dental materials and kits

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DE102017123016A9 (de) 2019-06-13
WO2019068614A1 (fr) 2019-04-11
US11234904B2 (en) 2022-02-01
CN111163743A (zh) 2020-05-15
US20200315925A1 (en) 2020-10-08
DE102017123016A1 (de) 2019-04-04
JP7203836B2 (ja) 2023-01-13

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