Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C13/00—Dental prostheses; Making same
  • A61C13/08—Artificial teeth; Making same
  • A61C13/09—Composite teeth, e.g. front and back section; Multilayer teeth
• • 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
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C13/00—Dental prostheses; Making same
  • A61C13/08—Artificial teeth; Making same
  • A61C13/087—Artificial resin teeth
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C5/00—Filling or capping teeth
  • A61C5/70—Tooth crowns; Making thereof
  • A61C5/77—Methods or devices for making crowns
• • 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
  • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
  • A61K6/836—Glass
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
  • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

• the invention relates to a 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 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 task was a dental composite material to provide a homogeneous, monochrome staining 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. In addition, 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.
• 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 wide particle size distribution advantageous for a high packing density and excellent mechanical properties could not be maintained.
• a narrow particle size distribution has been developed.
• the mean value of the particle size distribution was set in a range of 0.7 to 1 ⁇ m.
• the lower packing density and reduced filler surface allows better flowability (lower structural viscosity).
• the shaping for the production of the blocks of material takes place by introducing the polymerizable dental composite material into a casting mold, hereinafter referred to as mold only, in particular 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.
• Preferred material blocks have at least one dimension of 1 cm in all spatial directions and are present as geometric shaped bodies.
• the low-shrinkage crosslinking of the relatively large composite quantity in one process step is advantageous in order to avoid stress cracks in the block / blank.
• High crosslinking densities, which are desirable for the material strength, can often lead to unusability of the polymerized molded parts due to the high shrinkage stresses.
• the invention relates to a polymerizable, dental composite material, in particular a thermally polymerizable composite material comprising
• Urethane (meth) acrylates preferably a mixture of at least three different urethane (meth) acrylates, especially of di- to deca-functional urethane (meth) acrylates,
• 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%.
• polymerizing the composite material according to the invention is a polymerized composite material having a flexural strength of greater than or equal to 200 MPa, more preferably equal to 210 MPa, preferably greater than or equal 230 MPa, and a modulus of elasticity of 15 to 20 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 having a dimension of at least 10 mm in all spatial directions.
• the inorganic filler component consists of a dental glass or a mixture of dental glasses having an average particle size of 0.7 to 1, 0 ⁇ and an amorphous metal oxide, in particular a non-agglomerated amorphous metal oxide.
• 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 50 of 0.7 to 1 ⁇ m, preferably with an average particle size of 0.8 to 0.95 ⁇ m, in particular with d 5 o of 0.90 ⁇ optional plus / minus 0.05 ⁇ , preferably plus / minus 0.05 ⁇ , and preferably with d 99 less than or equal to 10 ⁇ .
• a particularly preferred particle size distribution can be in the range from d with greater than or equal to 0.2 ⁇ to d 99 less than or equal to 5 ⁇ , preferably with d greater than or equal to 0.4 ⁇ to d 99 smaller 2.5 ⁇ and a mean diameter d 5 o of 0.8 to 1, 00 ⁇ .
• the dental composite material comprises
• the invention further provides a dental composite material comprising (i) from 70 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 silanized with silanes functionalized with methacryloxypropyl groups, and optionally at least one non-agglomerated amorphous metal oxide of a primary particle size of 2 to 45 nm, the amorphous metal oxide comprising 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 inorganic filler component are preferably 87 to 99 wt .-% of at least one dental glass or a mixture of dental glasses, preferably from 88 to 99 wt .-%, preferably 92 to 99 wt .-%, and optionally 1 to 13 wt .-% , in particular 1 to 12 wt .-%, preferably 1 to 8 wt .-% of amorphous metal oxide or mixture of metal oxides in the filler component before.
• the dental composite material comprises
• the di- to deca-functional urethane (meth) acrylates are used as monomers and do not include peroxy groups.
• the dental composite material (ii) comprises 10 to 30% by weight of a mixture of at least two different urethane (meth) acrylates comprising at least one difunctional urethane (meth) acrylate having a bivalent alicyclic group, in particular comprising bis ( 4 ', 7'-dioxa-3', 8'-dioxo-2'-azadecyl-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 trans isomers of the aforementioned compounds, and a difunctional urethane
• the dental composite material (ii) comprises 10 to 30% by weight of a mixture of at least two different urethane (meth) acrylates comprising at least one difunctional urethane (meth) acrylate having a bivalent alicyclic group which is selected from 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) tetrahydro-dicyclopentadiene and / or mixtures thereof and, optionally, mixtures of the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or the cis and trans isomers of the aforementioned compounds, and at least one further di
• the dental composite material (ii) comprises a mixture of at least two different urethane (meth) acrylates, preferably of three different urethane (meth) acrylates.
• (meth) acrylates or urethane (meth) acrylate with (meth) in parenthesis means that the term can include acrylates or urethane acrylates with and without methyl group.
• bifunctional alicyclic difunctional urethane (meth) acrylates include or are selected from bis (4 ', 7'-dioxa-3', 8'-dioxo-2'-aza-decyl-9'-ene) tetrahydrofuran.
• the bivalent alicyclic difunctional urethane acrylate is selected from 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) tetra-hydrodicyclopentadiene and / or mixtures this and optional mixtures of the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or the cis and trans isomers of the aforementioned compounds.
• the bivalent alkylene difunctional urethane (meth) acrylate is preferably selected from linear or branched bivalent alkylene group 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 with alternative designation 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,
• alkylene comprises linear or branched C3 to C20, preferably C3 to C6, more preferably a methyl group substituted alkylene, such as HEMA-TMDI.
• the bivalent alkylene preferably comprises 2,2,4-trimethylhexamethylene and / or 2,4,4-trimethylhexamethylene.
• the at least tetra-functional dendritic urethane methacrylate comprises tetra- to deca-functional dendritic urethane methacrylates.
• (ii) comprises 10 to 30% by weight of a mixture of at least two different urethane (meth) acrylates relative to the total composition, preferably 15 to 20% by weight, such as at least one difunctional urethane (meth ) bivalent alicyclic group-containing acrylate and at least one hexafunctional dendritic urethane (meth) acrylate and optionally at least one bivalent alkylene difunctional urethane (meth) acrylate.
• the composite material preferably comprises from 5 to 25% by weight, in particular from 15 to 19% by weight, of bis (4 ', 7'-dioxa-3', 8'-dioxo-2'-aza-decyl-9 ' en) 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 trans isomers of the abovementioned compounds, 1 to 15% by weight, in particular 5 to 6% by weight, of UDMA (1,6-bis (methacryloxy-2-ethoxycarbonylamino) -2,4,4-trimethylhexane), in particular HEMA
• the composite material comprises from 10 to 20% by weight of a mixture of at least three different urethane (meth) acrylates selected from 10 to 18% by weight comprising bis (4 ', 7'-dioxa-3', 8 ' -dioxo-2'-aza-decyl-9'-ene) tetrahydrodicyclopenta-diene, bis (4 ', 7'-dioxa-3', 8'-dioxo-2'-aza-9'-methyl-decyl- 9'-ene) -tetrahydrodicyclopentadiene and / or mixtures thereof and optionally mixtures of the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or the cis- and trans- Isomer of the aforementioned compounds, 3 to 8 wt .-% of a difunctional urethane (meth) acrylate with bivalent alkylene group
• 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 di-methacrylic esters of polyethers , tri-, tetra or multifunctional methacrylic esters of polyethers.
• the content of components (iii) is preferably from 0.15 to 5% by weight, particularly preferably from 0.1 to 2% by weight, of a di-methacrylic ester of a polyether, such as preferably a dimethacrylate-polyethylene glycol, dimethacrylate-polypropylene glycol.
• a di-methacrylic ester of a polyether such as preferably a dimethacrylate-polyethylene glycol, dimethacrylate-polypropylene glycol.
• TEGDMA dimethacrylate triethylene glycol
• DEGMA diethylene glycol dimethacrylate
• TEDMA dimethacrylate tetraethylene glycol
• 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. Furthermore, it is preferred if the composite material contains 0.01 to 2 wt .-% of water as a stabilizer, preferably 0, 1 to 1, 0 wt .-% water.
• the amount of viscosity of the dental polymerizable composite material is preferably 40 ° C in the range of 5 to 20 E + 03 (5 x 10 3 to 20 x 10 3 ), preferably in the range of 5 to 15 E + 03.
• the viscosity according to the invention is an important criterion for the later manufacturing process of the milling blocks, in order to accelerate an inflow of the composite material into the casting molds and at the same time to avoid the formation of air bubbles.
• 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 inorganic pigments, in particular comprising diethyl 2,5-dihydroxy terephthalate, N, N'-bis (3,5-xylyl) perylene-3,4: 9, 10-bis (dicarbimide), copper
• Phthalocyanine titanate pigment, in particular chromium titanate titanate (rutile structure), spinel black, in particular pigments based on iron oxide black (Fe 3 O 4 ), iron (Fe) being 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 0.01 to 1 wt .-%.
• 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 dental composite material comprises component (i) which forms the filler component, wherein the filler component comprises (i.1) 85 to 95% by weight of at least one dental glass, in particular from 90 to 94.5% by weight. %, preferably from 92 to 94.5 wt .-% and optionally (i.2) from 5 to 15 wt .-% of amorphous metal oxide, in particular 5 to 10 wt .-%, preferably 5.5 to 8 wt .-% in which filler components, wherein (i.1) and (i.2) are 100% by weight of the filler component.
• the dental composite material comprises the components (ii) and (iii) which form the monomer component, the monomer component comprising (ii.1) 55 to 75% by weight of at least one 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 the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or the cis and trans isomer of the abovementioned compounds and (ii.2) from 21 to 38% by weight of at least one difunctional urethane (meth
• % in particular 0.2 to 9 wt .-% of at least one tetra to deca functional dendritic urethane methacrylate, in particular a dendritic six-fold urethane methacrylate, wherein the urethane (meth) acrylates and (iii) 1 to 10% by weight of at least one di-, tri-, tetra- or multi-functional monomer which is not a urethane (meth) acrylate, where the monomers (ii.1), (ü-2), (ii.3) and (iii) 100 wt .-% in the monomer component.
• 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 230 MPa, preferably greater than or equal to 240 MPa, preferably greater than or equal to 250 MPa according to EN ISO 6872: 2008.
• the bending strength of the composite material is preferably greater than or equal to 200 MPa, greater than or equal to 240 MPa, greater than or equal to 250 MPa, preferably greater than or equal to 255 MPa, preferably greater than or equal to 260 MPa, especially to less than or equal to 300 MPa.
• 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 elastic modulus were measured according to Dent. Materials J 2014; 33 (4/5), 705 to 710 prepared and measured (dry and after a 7-day storage in water with thermocycling up to 10,000 cycles, usually with 5000 cycles), 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 a block due to the dimension of the specimens.
• the 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 the dentine of the tooth hard substance, so that in the intended application a failure is avoided as far 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).
• the invention therefore also relates to a polymerized dental composite material having a modulus of elasticity greater than or equal to 15 to 20 GPa, preferably from 16 to 21 GPa after 7 days of dry storage and optionally greater than or equal to 15 GPa after storage for 7 days in water with thermocycling of 5000 Cycles measured according to EN ISO 6872: 2008, in particular according to the method as described in Dent. Mater. J. 2014; 33 (5) 705-710.
• the publication also compares further results of the three-point bending test for CAD / CAM blocks of various dental materials in Table 3 measured by this method.
• the modulus of elasticity is preferably 15 to 20 GPa, preferably from 16 to 20 GPa (measured after a 7-day storage in water with thermocycling 5000 cycles) and / or the modulus of elasticity is preferably 17 to 21 GPa, preferably from 18 to 21 GPa (dry for 7 days).
• Table 1 Extract from Table 3 of the Dent. Mater. J. 2014; 33 (5) 705-710
• the invention provides a polymerized, dental composite material comprising 70 to 85% by weight of at least one inorganic filler component comprising at least one dental glass having an average particle size d 50 of 0.7 to 1.0 ⁇ m 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 of tetrahydrodicyclopentadiene, in particular a difunctional urethane ( meth) acrylate of tetrahydrodicyclopentadiene and at least one di-urethane (meth) acrylate having a bivalent alkylene group at least one tetra- to deca-functional dendritic urethane methacrylate, and at least one di-, tri-, tetra or multi
• 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 of greater than or equal to 10 mm to less than or equal to 15 mm with a radius of 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 greater radius equal to 5 to less than 7 mm.
• the dimensions of the cuboid are preferably for a, b, and c are greater than or equal to 4 mm, in particular greater than or equal to 10 mm and a less 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 less than or equal to 20 mm, in particular less than or 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 that are used as milling blocks preferably have the shape of cuboids, wherein the cuboid preferably has a volume of 12 mm x 14 mm x 17 or 18 mm, alternatively 14 x 14 mm, or 15x15 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 allows the possibility of a significant simplification of the process in the production of indirect dentures by the dentist or the dental technician at least one Intraoralscan in the mouth of the patient and then using the thus obtained digital dental information directly a prosthetic dental supply, such as a crown or an inlay, taking into account other device parameters, etc. can produce.
• the prepared dental prosthetic restoration can then be inserted into the patient, attached and, if necessary, slightly reworked. For example, an intraoral scan is taken before grinding a tooth to make a tooth stump for a crown, and another intraoral scan of the tooth stump.
• the polymerized composite material can be used to make dental prosthetic restorations including crowns, inlays, onlays, superstructures, artificial teeth, denture teeth, dental bridges, dental bars, spacers, abutments, veneers.
• the polymerizable composite material can also be used as a composite material for the production of direct adhesive dental restorations.
• the urethane (meth) acrylates according to the invention are likewise preferably 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, Aromatic-Functionalized Urethane Dimethacrylate Oligomers, aliphatic unsaturated urethane acrylates, bis (methacryloxy-2-ethoxycarbonylamino) substituted polyethers, urethane diacrylate oligomers, aliphatic urethane diacrylate oligomers, aliphatic urethane diacrylates, hexafunctional aliphatic urethane resins, aliphatic urethane triacrylate, aliphatic urethane acrylate oligomer
• 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, Genomer 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 di-, tri-, tetra- or multi-functional monomer which is not a urethane (meth) acrylate is preferably 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, decandioldi ( meth) acrylate, dodecanediol di (meth) acrylate, hexyldecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acryl
• Typical 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, hexyldecandioldi (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 tetra-functional monomers or multi-crosslinkers 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 acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate, isodecyl acrylate, polypropylene glycol mono-acrylate, tetrahydrofu
• 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 one 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-dibenzylaminobenzoic acid diethyl ester or c) at least one initiator system selected from redox systems, in particular a combination selected from dibenzoyl peroxide, dilauroyl per
• 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 a 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 benzyldibutylammonium chloride.
• 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 .-%.
• 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) for 7 days.
• the second group was stored in 37 ° C deionized water for 7 days
• the third Group was stored in 37 ° C deionized water for 7 days followed by 5000 thermal cycles (5 ° C to 55 ° C, 30 s retention time) by means of a thermocycling 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).
• a three-point bending test with a span of 12.0 mm and a crosshead speed of 1.0 mm / min was carried out at room temperature (23 ⁇ 2 ° C) by means of a universal testing machine (AG-X, Shimadzu Corp., Kyoto, Japan ) carried out. Flexural strength and flexural modulus were calculated using software (TRAPEZIUM X, Shimadzu Corp., Kyoto, Japan).
• the hardness test was carried out with the Zwick universal device: The measured values of samples according to the invention are in the range from 800 to 850.
• Example 2 244 MPa 259 MPa 209 MPa 216 MPa
• Example 3 236 MPa 262 MPa 209 MPa 224 MPa Table 5: modulus of elasticity (modulus of elasticity)

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• 2017
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