Dental composite material and milling blanks made of this composite material

Abstract

Thermally polymerizable dental composite material comprising as (i) inorganic filler component (i.1) 70 to 84 wt.% of at least one dental glass, and optionally (i.2) 1 to 6 wt.% of at least one amorphous silanized metal oxide having a primary particle size of 2 to 45 nm, and, wherein the dental glass has a mean particle size d50 of 0.7 to 1.0 µm, (ii) 10 to 30 wt.% of a mixture of at least two different urethane(meth)acrylates, wherein the mixture comprises at least one difunctional urethane(meth)acrylate with 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 at least one at least tetrafunctional dendritic urethane(meth)acrylate,(iii) 0.01 to 5 wt.-% of at least one di-, tri-, tetra- or multi-functional monomer that is not urethane(meth)acrylate,(iv) 0.01 to 10 wt% of at least one initiator and at least one stabilizer, wherein the total composition of the composite material is 100 wt%.

Description

[0001] The invention relates to a polymerizable dental composite material comprising (i) 70 to 85 wt.% of at least one inorganic filler component comprising at least one dental glass and optionally at least one amorphous metal oxide, (ii) 10 to 30 wt.% of a mixture of at least two different urethane(meth)acrylates, (iii) 0.01 to 5 wt.% of at least one di-, tri-, tetra- or multi-functional monomer that is not a urethane(meth)acrylate, and (iv) 0.01 to 10 wt.% of at least one initiator, an initiator system and optionally stabilizers and optionally pigments, wherein the total composition of the composite material is 100 wt.% and a polymerized composite material with a flexural strength of greater than or equal to 200 MPa and an elastic modulus of 15 to 20 GPa.

[0002] Many dental composites are known to be universally applicable for both direct adhesive restorations and the extraoral fabrication of indirect dental prostheses. Of the dental composite material class, only inorganic-organic hybrid materials with larger proportions of inorganic fillers, such as dental glass and / or mineral nano-agglomerates, are generally suitable for this purpose. The microfiller composites with pre-polymer fillers, introduced in the 1980s, are not suitable for use in the posterior region (Classes I and II) due to their limited wear resistance (abrasion resistance).

[0003] A high filler content is advantageous for achieving excellent mechanical properties of the cured composite while simultaneously reducing polymerization shrinkage during curing. These properties are also crucial for the long-term success of the dental restoration material.

[0004] The excellent material properties of dental composites with polycyclic structural elements for direct adhesive restoration, especially the low shrinkage force with high flexural strength, are well known.

[0005] The object of the invention was to provide a dental composite material suitable for the production of larger material blocks, particularly geometric shapes such as milling blocks. Furthermore, the object was to provide a dental composite material exhibiting a homogeneous, monochromatic coloration both before and after polymerization. This homogeneous, monochromatic coloration should also be achievable with larger material blocks. Additionally, polychromatic, i.e., multicolored, material blocks with defined coloration should be producible. Moreover, a dental composite material should be provided that is easily flowable in the unpolymerized state yet exhibits excellent mechanical properties in the polymerized state and displays minimal shrinkage during polymerization, even when producing larger material blocks.Furthermore, the composite material should not develop cracks or pores during curing, even in large-volume material blocks.

[0006] Starting with prior art composites based on urethane derivatives, the filler system, the monomer mixture, and the pigment system had to be modified. The wide particle size distribution, advantageous for high filler density and excellent mechanical properties, could not be maintained. According to the invention, a narrow particle size distribution was developed. The mean value of the particle size distribution was adjusted to a range of 0.7 to 1 µm. The lower packing density and reduced filler surface area enable improved flowability (lower structural viscosity).

[0007] Bulky molded parts for the production of larger material blocks cannot be photopolymerized due to the limited penetration depth of light into the composite material. For this reason, the initiator system had to be adapted and further developed by using at least one thermally initiable peroxide. Furthermore, it was necessary to avoid discoloration of existing photoinitiators due to thermal reactions or the significantly increased material dimensions in the blocks. Therefore, conventional blue-light photoinitiators, such as the champerquinone initiator system, were excluded to prevent color changes due to the composite layer thickness. When selecting the initiator system, it is crucial to ensure that the reaction kinetics of, for example, a peroxide do not induce stresses in the large material blocks, thus preventing internal cracking, given the low thermal conductivity of the materials.

[0008] The shaping of the material blocks is achieved by placing the polymerizable dental composite material into a mold, hereinafter referred to as the mold, particularly under pressure. The applied pressure is preferably between 500 and 300 MPa or N / mm². 2The polymerization is carried out at elevated temperature, preferably in the range of approximately 90 to 150°C. Polymerization is performed in a closed mold to minimize, and preferably avoid, the formation of air bubbles. Preferably, polymerization is carried out under a pressure of 120 to 320 MPa, preferably up to and including 300 MPa, at a temperature of 100 to 180°C, preferably around 140°C, for at least 10 minutes to 10 hours. Alternatively, polymerization is carried out at a temperature of 120 to 140°C and a pressure of 280 to 320 MPa for 5 to 20 minutes. Preferred material blocks have a dimension of at least 1 cm in all spatial directions and are in geometrically shaped form.

[0009] Surprisingly, it was found that composites based on a urethane monomer with an alicyclic structural element, such as tetrahydrodicyclopentadiene, are exceptionally well-suited for the fabrication of indirect dental prostheses, as thermally initiated polymerization allows for surprisingly high flexural strengths. The high level of polymer strength compared to the previously described photopolymerization in the case of light-cured dental composites was unexpected and not anticipated. At the same time, the low-shrinkage crosslinking of the relatively large amount of composite in a single process step is advantageous for preventing stress cracks in the block / blank. High crosslinking densities, which are desirable for material strength, can often render the polymerized components unusable due to high shrinkage stresses.

[0010] The invention relates to a polymerizable dental composite material, in particular a thermally polymerizable composite material, comprising (i) 70 to 85 wt.% of at least one inorganic filler component comprising at least one dental glass and optionally at least one amorphous metal oxide, (ii) 10 to 30 wt.% of a mixture of at least two different urethane(meth)acrylates, preferably a mixture of at least three different urethane(meth)acrylates, in particular of di- to deca-functional urethane(meth)acrylates, (iii) 0.01 to 5 wt% at least one di-, tri-, tetra- or multi-functional monomer that is not a urethane (meth)acrylate, (iv) 0.01 to 10 wt% of at least one initiator, one initiator system and optionally at least one stabilizer and optionally at least one pigment, wherein in particular the at least one pigment comprises both fluorescent and colour pigments, wherein the total composition of the composite material is 100 wt%.

[0011] In one embodiment, it is preferred that the thermally polymerizable composite material is also photochemically polymerizable. For the purposes of this invention, a thermally polymerizable composite material is understood to be a composite material that can be polymerized at temperatures greater than or equal to 60 to 150 °C, preferably at temperatures greater than or equal to 70 to 150 °C, and particularly preferably at temperatures between 90 and 150 °C. According to the invention, it is further preferred that the volume shrinkage is less than or equal to 1.5%.

[0012] Polymerization of the composite material according to the invention yields a polymerized composite material with a flexural strength of 200 MPa or greater than or equal to 200 MPa, in particular 210 MPa or greater than or equal to 230 MPa, and a modulus of elasticity of 15 to 20 GPa, particularly both dry and after water storage with thermocycling. The polymerized composite material is preferably in the form of a block, particularly a milling blank with a dimension of at least 10 mm in all spatial directions.

[0013] The following are preferred dental glasses: aluminosilicate glasses or fluoroaluminosilicate glasses, barium aluminum silicate, strontium silicate, strontium borosilicate, lithium silicate and / or lithium aluminum silicate, as well as mixtures of at least two of the aforementioned dental glasses. Amorphous metal oxides or mixtures of amorphous metal oxides, such as amorphous spherical fillers based on oxides or mixed oxides, like amorphous SiO2, ZrO2, or mixed oxides of SiO2 and ZrO2, can be used.

[0014] According to a preferred embodiment, the dental composite material comprises at least one dental glass, in particular a radiopaque dental glass, of a mean particle size d 50 from 0.7 to 1.0 µm, preferably with a mean particle size of 0.8 to 0.95 µm, in particular with d 50 of 0.90 µm optionally plus / minus 0.05 µm, preferably plus / minus 0.05 µm, and preferably with d 99less than or equal to 10 µm. A mean particle size of d is particularly preferred. 50 of approximately 0.85 µm, optionally plus / minus 0.1 µm, in particular plus / minus 0.05 µm, preferably in particular plus / minus 0.03 µm, and preferably with d 99 less than or equal to 10 µm. A particularly preferred dental glass comprises barium aluminum borosilicate glass. Furthermore, a barium aluminum borosilicate glass with a refractive index of n = 1.52 to 1.55, preferably 1.53, is particularly preferred. A particularly preferred particle size distribution may be in the range of d 10 with greater than or equal to 0.2 µm to d 99 less than or equal to 5 µm, preferably with d 10 greater than or equal to 0.4 µm to d 99 smaller than 2.5 µm and a mean diameter d 50 from 0.8 to 1.00 µm.

[0015] According to a preferred embodiment, the dental composite material (i) comprises at least one inorganic filler component in 70 to 85 wt.%, wherein at least one dental glass of a medium particle size d 50 from 0.7 to 1.0 µm of greater than or equal to 70 to 80 wt.% with respect to the composite material, in particular of greater than or equal to 71 to 76 wt.%.

[0016] Furthermore, the invention relates to a dental composite material comprising (i) at least one inorganic filler component comprising 70 to 85 wt.%, 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 of a primary particle size of 2 to 45 nm, wherein the amorphous metal oxide comprises precipitated silicon dioxide, zirconium oxide, mixed oxides or mixtures thereof, in particular the metal oxides are silanized.

[0017] To achieve high flexural strength, the dental composite material preferably comprises, as an 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 wt.% of amorphous metal oxide, in particular 3 to 10 wt.%, preferably 4 to 8 wt.%, in the overall composition. The ratio of dental glass to amorphous metal oxide is preferably from 20:1 to 5:1, more preferably from 15:1 to 10:1.

[0018] The inorganic filler component preferably contains 87 to 99 wt.% of at least one dental glass or a mixture of dental glasses, preferably 88 to 99 wt.%, more preferably 92 to 99 wt.%, and optionally 1 to 13 wt.%, in particular 1 to 12 wt.%, preferably 1 to 8 wt.% amorphous metal oxide or a mixture of metal oxides in the filler component.

[0019] According to a particularly preferred design variant, the dental composite material comprises (i) 70 to 85 wt.% of at least one inorganic filler component comprising 60 to 84 wt.%, in particular 66 to 76 wt.%, preferably 66 to 76% or 71 to 76 wt.% to at least one dental glass of a medium particle size d 50 of 0.7 to 1.0 µm and optionally 1 to 25 wt.%, in particular 3 to 8 wt.%, preferably 3 to 8 wt.%, particularly preferably 5 to 6 wt.%, at least one amorphous, silanized metal oxide of a primary particle size of 2 to 45 nm, with respect to the overall composition, (ii) 10 to 30 wt.%, in particular 15 to 30 wt.%, preferably 18 to 22 wt.% of a mixture of at least two different urethane(meth)acrylates, in particular of dibis deca-functional urethane(meth)acrylates, preferably of 15 to 19 wt.% of a difunctional urethane(meth)acrylate with a bivalent alicyclic group and 5 to 6 wt.% of a difunctional urethane(meth)acrylate with a bivalent alkylene group and optionally 0.1 to 2 wt.% of at least one hexafunctional urethane(meth)acrylate or dendritic urethane methacrylate of a mixture of urethane(meth)acrylates, and (iii) 0.01 to 5 wt.%, in particular 0.5 to 3 wt.%, preferably 0.8 to 2.0 wt.% of at least one di-, tri-, tetra- or multi-functional monomer that is not a urethane (meth)acrylate, in particular at least one di-, tri-, tetra- or multi-functional methacrylate ester of polyethers, preferably dimethacrylate triethylene glycol, (iv) 0.01 to 10 wt.%, in particular 0.5 to 5 wt.%, preferably 0.5 to 2 wt.% of at least one thermal initiator, one thermal initiator system and optionally at least one stabilizer and optionally at least one pigment, in particular a pigment mixture comprising a pigment selected from fluorescent and color pigments, wherein the total composition of the composite material is 100 wt.%.

[0020] The di- to deca-functional urethane(meth)acrylates are used as monomers and do not contain peroxy groups.

[0021] According to a particularly preferred embodiment, the dental composite material (ii) comprises 10 to 30 wt.% of a mixture of at least two different urethane(meth)acrylates, preferably of three different urethane(meth)acrylates, comprising at least one difunctional urethane(meth)acrylate with a bivalent alicyclic group and one difunctional urethane(meth)acrylate with a bivalent alkylene group, and optionally at least one at least tetrafunctional dendritic urethane(meth)acrylate, preferably at least one hexafunctional dendritic urethane(meth)acrylate.

[0022] Particularly preferred difunctional urethane(meth)acrylates with 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 the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or the cis- and trans-isomers of the aforementioned compounds.

[0023] The difunctional urethane(meth)acrylate with a bivalent alkylene group is preferably selected from linear or branched urethane dimethacrylates functionalized with a bivalent alkylene group, urethane dimethacrylate-functionalized polyethers with alkylene group(s), such as bis(methacryloxy-2-ethoxycarbonylamino) alkylenes, bis(methacryloxy-2-ethoxycarbonylamino)-substituted polyalkylene ethers, preferably 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane, UDMA with the alternative name HEMA-TDMI. A bis(methacryloxy-2-ethoxycarbonylamino) alkylene is preferred, wherein the alkylene comprises linear or branched C3 to C20, preferably C3 to C6, such as, most preferably, a methyl-substituted alkylene, such as HEMA-TMDI. The bivalent alkylene preferably comprises 2,2,4-trimethylhexamethylene and / or 2,4,4-trimethylhexamethylene.

[0024] The at least tetra-functional dendritic urethane methacrylate includes tetra- to deca-functional dendritic urethane methacrylates.

[0025] It is also preferred if (ii) comprises 10 to 30 wt.% of a mixture of at least two different urethane(meth)acrylates in relation to the overall composition, preferably 15 to 20 wt.%, such as at least one difunctional urethane(meth)acrylate with a bivalent alicyclic group and at least one hexafunctional dendritic urethane(meth)acrylate and optionally at least one difunctional urethane(meth)acrylate with a bivalent alkylene group.

[0026] Preferably, the composite material comprises 5 to 25 wt.%, in particular 15 to 19 wt.%, 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-isomers of the aforementioned compounds, 1 to 15 wt.%, in particular 5 to 6 wt.%, UDMA (1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane), in particular HEMA-TDMI, and 0.1 to 5 wt.%, preferably 0.2 to 2 wt.%, particularly preferably 0.2 to 1 wt.% of at least one tetra- to deca-functional dendritic urethane methacrylate based on the total composition.

[0027] Preferably, the composite material comprises 10 to 20 wt% of a mixture of at least three different urethane (meth)acrylates, selected from 10 to 18 wt% 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 the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or the cis- and trans-isomers of the aforementioned compounds, 3 to 8 wt% of a difunctional urethane (meth)acrylate with a bivalent alkylene group, in particular UDMA or HEMA-TDMI, and 0.1 to 2 wt.%, preferably 0.2 to 2 wt.%, particularly preferably 0.2 to 1 wt.% of at least one tetra- to deca-functional dendritic urethane methacrylate based on the total composition.

[0028] According to a further preferred embodiment, the dental composite material comprises as component (iii) 0.01 to 5 wt.% of at least one di-, tri-, tetra- or multifunctional monomer which is not a urethane acrylate and is selected from di-methacrylic esters of polyethers, tri-, tetra- or multifunctional methacrylic esters of polyethers.

[0029] Preferably, the content of component (iii) is 0.15 to 5 wt.%, particularly preferably 1.0 to 2 wt.%, of a dimethacrylate ester of a polyether, such preferably a dimethacrylate polyethylene glycol or a dimethacrylate polypropylene glycol. Particularly preferred are dimethacrylate triethylene glycol (TEGDMA), diethylene glycol dimethacrylate (DEGMA), and dimethacrylate tetraethylene glycol (TEDMA).

[0030] Water was added to the dental composite material as a stabilizer to improve its consistency and flow properties for processing. Stabilizers were also added to the composite material to prevent premature polymerization and to give the material a certain shelf life. The composite material in component (iv) preferably comprises at least one stabilizer selected from water, at least one benzophenone derivative, preferably an alkoxy-substituted benzophenone, and / or a 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 a concentration of 0.01 to 14 wt.%, particularly preferably 0.7 to 10 wt.%, and especially 0.5 to 2 wt.%. Furthermore, it is preferred if the composite material contains 0.01 to 2 wt% water as a stabilizer, preferably 0.1 to 1.0 wt%.-% contains water.

[0031] The viscosity of the dental polymerizable composite material is preferably in the range of 5 to 20 μH⁺ at 40°C (5 × 10⁻⁵ × 10⁻⁵). 3 up to 20 · 10 3 ), preferably in the range of 5 to 15 E+03. The viscosity according to the invention is an important criterion for the subsequent manufacturing process of the milling blocks in order to accelerate the flow of the composite material into the molds and at the same time avoid the formation of air bubbles.

[0032] To optimally adjust the color and natural aesthetics of the polymerized composite material, 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, particularly non-fluorescent color pigments, is 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 aryl carboxylic acid esters, aryl carboxylic acids, coumarin, rhodamine, naphthanide linimide, or a derivative of the respective substance. Inorganic fluorescent pigments may include CaAl4O7:Mn. 2+ , (Ba0.98Eu0.02)MgAl 10 O 17 , BaMgF4:Eu 2+ , Y(1.995)Ce(0.005)SiO5.

[0033] The composite may include organic pigments as well as inorganic pigments, in particular diethyl 2,5-dihydroxyterephthalate, N,N'-bis(3,5-xylyl)perylene-3,4:9,10-bis(dicarbimide), copper phthalocyanine, titanate pigment, in particular chromium antimontitanate (rutile structure), spinel black, in particular pigments based on iron oxide black (Fe3O4) 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)2O4) cobalt zinc caluminate blue spinel and / or titanium oxide. The pigments, comprising fluorescent and color pigments, are preferably present in the overall composition at a concentration of 0.01 to 10 wt.%, particularly preferably 0.01 to 5 wt.%, and preferably 0.01 to 1 wt.%.

[0034] The selection of pigments must be specifically tailored to the dental composite composition to achieve a homogeneous color in both the polymerizable and polymerized composite. The fabrication of large material blocks also requires careful coordination of both pigment selection and concentration to prevent unwanted discoloration resulting from the size of the polymerized material blocks.

[0035] Suitable initiators include peroxides, hydroxyperoxides, or mixtures thereof. Appropriate thermal initiators can be used as radical starters in the temperature range of 70 to 150 °C, preferably 90 to 150 °C. Preferred thermal initiators comprise at least one initiator selected from: tert-butyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, dicumyl peroxide, dicumyl hydroperoxide, azobisisobutyronitrile, or a benzylbarbituric acid derivative.

[0036] According to a further particularly preferred embodiment, the dental composite material comprises component (i) which forms the filler component, wherein the filler component comprises (i.1) 85 to 95 wt.% of at least one dental glass, in particular 90 to 94.5 wt.%, preferably 92 to 94.5 wt.% and optionally (i.2) 5 to 15 wt.% of amorphous metal oxide, in particular 5 to 10 wt.%, preferably 5.5 to 8 wt.%, in the filler component, wherein (i.1) and (i.2) constitute 100 wt.% of the filler component.

[0037] According to a further particularly preferred embodiment, the dental composite material comprises components (ii) and (iii) forming the monomer component, wherein the monomer component comprises (ii.1) 55 to 75 wt.% 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-isomers of the aforementioned compounds, and (ii.2) 21 to 38 wt.% of at least one difunctional urethane (meth)acrylate with a bivalent alkylene group, as well as optional (ii.3) 0.1 to 14 wt.%, in particular 0.2 to 9 wt.% of at least one tetra to deca functional dendritic urethane methacrylate, in particular one dendritic hexafunctional urethane methacrylate, wherein the urethane (meth)acrylates and (iii) 1 to 10 wt% of at least one di-, tri-, tetra- or multi-functional monomer other than urethane(meth)acrylate, wherein the monomers (ii.1), (ii.2), (ii.3) and (iii) constitute 100 wt% in the monomer component.

[0038] The invention also relates to a polymerized dental composite material obtainable by polymerization of the composite material according to the invention, in particular by polymerization of the composite material at a pressure of 500 to 300 MPa (= [N / mm²]). 2 ]), particularly at 50 to 300 MPa, preferably at 100 to 300 MPa, especially preferably at 120 to 200 MPa, preferably at 120 to 170 MPa, and / or at elevated temperature, preferably at 90 to 150 °C. Polymerization preferably takes place in a mold, which preferably has a geometric shape. Polymerization under elevated pressure minimizes or avoids the formation of air bubbles in the polymerized composite material.

[0039] The shrinkage of the polymerizable composite material is preferably less than 2.0%, particularly less than 1.5%, and most preferably less than or equal to 1.4%. (Bonded-Disc Method - Dental Materials, Watts et al, (2004) 20, 88-95; 23 °C, Translux Energy, 60 s exposure).

[0040] The polymerized composite material preferably has no voids or cracks larger than or equal to 200 nm; in particular, a material block has no voids or cracks. The polymerized composite material has a density of 2.0 g / cm³ or greater. 3 on, in particular a density of greater than or equal to 2.1 g / cm³ 3 .

[0041] Surprisingly, the polymerized dental composite material, which is obtainable in particular by thermal polymerization of the composite material, exhibits 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, and more preferably greater than or equal to 250 MPa according to EN ISO 6872:2008. The flexural strength of the composite material (test specimen after 7 days of dry storage, without storage in water) is preferably greater than or equal to 200 MPa, greater than or equal to 240 MPa, greater than or equal to 250 MPa, more preferably greater than or equal to 255 MPa, more preferably greater than or equal to 260 MPa, and in particular less than or equal to 300 MPa.The flexural strength after 7 days of storage in water with thermocycling is preferably greater than or equal to 200 MPa, more preferably greater than or equal to 210 MPa, more preferably greater than or equal to 220 MPa, and most preferably greater than or equal to 230 MPa up to less than or equal to 300 MPa according to EN ISO 6872:2008, wherein the storage in water was carried out analogously to Dent. Materials J. 2014; 33(5) 705-710 with 5000 cycles. The flexural strength and the modulus of elasticity were prepared and measured according to Dent. Materials J. 2014; 33(4 / 5), 705 to 710 (dry and after 7 days of storage in water with thermocycling with up to 10,000 cycles, typically 5,000 cycles), i.e., according to EN ISO 6872:2008 or with additional water storage.

[0042] The ISO 6872 standard was developed for testing ceramic materials that were available as CAD / CAM blocks. Since composite materials are now also manufactured and processed in the same dimensions, a comparable analogous test using water immersion should be performed. Due to the dimensions of the test specimens, they cannot be produced from a single block according to the composite standard (ISO 4049).

[0043] While the flexural strength of a dental composite is not limited to high values ​​(> 100 MPa), a balanced / optimal elasticity is advantageous for its application. Ideally, the modulus of elasticity should correspond to that of the dentin of the tooth structure to minimize failure during intended use. Materials that are too brittle (with a high modulus of elasticity) tend to chip or fracture. Materials that are too elastic (low modulus of elasticity) deform under chewing forces, and the cementation detaches (debonding).

[0044] The material properties (flexural strength and modulus of elasticity) of human dental hard tissue are known from the literature (Dwayne D. Arola et al. Biomaterials 27(2006) 2131-2140) as a function of orientation (anisotropic material properties due to crystallite orientation). The modulus of elasticity of human dental hard tissue ranges from 15 to 19 GPa, depending on the orientation. Therefore, the aim was to provide a composite with a modulus of elasticity that is in the range of human dental hard tissue, preferably in the range of 15 to 20 GPa, in order to mimic tooth-like properties.

[0045] The invention therefore relates to a polymerized dental composite material with a modulus of elasticity greater than or equal to 15 to 20 GPa, preferably 16 to 21 GPa, after 7 days of dry storage, and optionally greater than or equal to 15 GPa after 7 days of storage in water with thermocycling for 5000 cycles, measured according to EN ISO 6872:2008, in particular according to the method disclosed 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 measured according to this method in Table 3. Preferably the modulus of elasticity is 15 to 20 GPa, preferably 16 to 20 GPa (measured after 7 days of storage in water with thermocycling 5000 cycles) and / or the modulus of elasticity is preferably 17 to 21 GPa, preferably 18 to 21 GPa (7 days dry). Table 1: Extract from Table 3 of Dent. Mater. J. 2014; 33(5) 705-710 condition Block HC Cerasmart Gradia Block Lava Ultimate Vita Enamic Vitablocs Mark II Flexural strength [MPa] Dry 170,5 242,0 204,0 170,5 140,7 126,6 Water 121,5 197,3 188,4 141,9 133,0 121,1 Water / TC 117,6 194,3 165,1 120,1 134,6 129,0 E-modulus [GPa] Dry 9,6 10,0 14,7 14,5 28,5 51,5 Water 7,8 9,0 13,5 12,8 28,3 52,8 Water / TC 7,2 8,7 13,2 12,2 28,6 54,9

[0046] According to a particularly preferred embodiment, the invention relates to a polymerized dental composite material comprising 70 to 85 wt.% of at least one inorganic filler component comprising at least one dental glass of a medium particle size d 50from 0.7 to 1.0 µm 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 with a bivalent alkylene group, at least one tetra- to deca-functional dendritic urethane methacrylate, and at least one di-, tri-, tetra- or multifunctional methacrylate of polyethers, preferably dimethacrylate triethylene glycol, and - 0.01 to 10 wt.-% of at least one pigment, in particular at least one fluorescent pigment and at least one organic color pigment and / or at least one inorganic color pigment, wherein the color pigments preferably do not fluorescent, wherein the total composition of the composite material is 100 wt.%.

[0047] The polymerized dental composite material is preferably in the form of a material block, particularly as a three-dimensional material block in the form of a geometric shape, especially as a milling blank with an adapter for clamping in an automated material removal device, particularly preferably in the form of a cylinder, a cuboid, or preferably a cube. Furthermore, it is preferred that the edges and / or corners of the shape are rounded. The dimensions of the cylinder are preferably: a height of ≥ 10 mm to ≤ 15 mm with a radius of ≥ 3 mm to ≤ 7 mm, or alternatively, a height of ≥ 10 mm to ≤ 20 mm and a radius of ≥ 5 mm to ≤ 7 mm.The dimensions of the cuboid are preferably greater than or equal to 4 mm for a, b, and c, particularly greater than or equal to 10 mm, and a less than or equal to 20 mm, particularly less than or equal to 18 mm, b less than or equal to 14 mm, and c less than or equal to 20 mm, particularly less than or equal to 18 mm. Preferably, a three-dimensional material block has an edge length of at least 10 mm, preferably 14 mm. Material blocks used as milling blocks preferably have the shape of cuboids, wherein the cuboids preferably have a volume of 12 mm × 14 mm × 17 or 18 mm, alternatively 14 × 14 mm, or 15 × 15 mm, and a height of 17 to 18 mm. One to all edges and corners can be straight or rounded.

[0048] Furthermore, the invention relates to the use of a dental composite material for the fabrication of dental prosthetic restorations, in particular for the fabrication of indirect dental prostheses, in a material-absorbing process, especially in a process in which the polymerized composite material is removed by milling, cutting, polishing, fracturing, chipping and / or drilling, and particularly preferably in a process in which the polymerized composite material is removed by means of laser energy. A particularly preferred use for the material is its use in a process for the fabrication of dental prosthetic restorations in a material-absorbing process in which the material is removed by means of laser energy.The particle size, and preferably the particle size distribution, has been specifically adapted to a process in which the polymerized composite material is ablated using laser energy, enabling the fabrication of prosthetic restorations. A particular advantage of the dental material according to the invention is that it allows for a significant simplification of the process in the fabrication of indirect dental prostheses. This is achieved by the dentist or dental technician performing at least one intraoral scan in the patient's oral cavity and then directly fabricating a prosthetic dental restoration, such as a crown or inlay, using the digital dental information thus obtained, taking into account other device parameters, etc. The fabricated dental prosthesis can then be inserted into the patient's mouth, cemented, and, if necessary, slightly modified.For example, an intraoral scan is taken before grinding down a tooth to create a tooth stump for a crown, as well as another intraoral scan of the tooth stump.

[0049] Furthermore, the polymerized composite material can be used for the fabrication of dental prosthetic restorations, including crowns, inlays, onlays, superstructures, artificial teeth, denture teeth, dental bridges, dental bars, spacers, abutments, and veneers. The polymerizable composite material can also be used as a composite material for the fabrication of direct adhesive dental restorations.

[0050] The following are also preferably considered as urethane(meth)acrylates according to the invention: (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 polyether, aromatic urethane diacrylate oligomers, aliphatic urethane diacrylate oligomers, aliphatic urethane diacrylates, hexafunctional aliphatic urethane resins, aliphatic urethane triacrylate, aliphatic urethane acrylate oligomer, unsaturated aliphatic urethane acrylates.Difunctional and multifunctional urethane(meth)acrylates are preferred, in particular urethane di(meth)acrylates, especially the at least one (iii) urethane dimethacrylate selected from linear or branched alkyl-functionalized urethane dimethacrylates, urethane dimethacrylate functionalized polyethers, in particular bis(methacryloxy-2-ethoxycarbonylamino) alkylenes, bis(methacryloxy-2-ethoxycarbonylamino) substituted polyethers, preferably 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane. Suitable urethane (meth)acrylates are available under the following brand names: Ebecryl 230 (aliphatic urethane diacrylate), Actilane 9290, Craynor 9200 (di-urethane acrylate oligomer), Ebecryl 210 (aromatic urethane diacrylate oligomers), Ebecryl 270 (aliphatic urethane diacrylate oligomer), Actilane 165, Actilane 250, Genomer 1122 (monofunctional urethane acrylate), Photomer 6210 (CAS No.52404-33-8 (aliphatic urethane diacrylate), Photomer 6623 (hexafunctional aliphatic urethane resin), Photomer 6891 (aliphatic urethane triacrylate), UDMA, Roskydal LS 2258 (aliphatic urethane acrylate oligomer), Roskydal XP 2513 (unsaturated aliphatic urethane acrylate). The urethane (meth)acrylates may preferably be selected from the aforementioned urethane (meth)acrylates or from a mixture of at least two different, preferably at least three different, aforementioned urethane (meth)acrylates.

[0051] 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, decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, hexyldecanediol di(meth)acrylate, trimethylol propane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, as well as butanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate. ethoxylated / propoxylated bisphenol A di(meth)acrylate, a mixture containing at least one of these (meth) acrylates and / or copolymers comprising one or at least two of the aforementioned monomers.

[0052] Typical difunctional monomers, also known as crosslinkers or multi-crosslinkers, include 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, hexyldecanediol di(meth)acrylate, as well as butanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylates, and ethoxylated / propoxylated bisphenol-A di(meth)acrylates. The following difunctional monomers can also be added as diluents (low-viscosity acrylates). Tri- and tetra-functional monomers or multi-crosslinkers include trimethylolpropane tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, and pentaerythritol tetraacrylate.

[0053] In addition to the di-, tri- or multi-functional monomer or monomers, 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 monomethacrylate, tetrahydrofuryl methacrylate, polypropylene glycol monomethacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, n-hexyl acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate, isodecyl acrylate, polypropylene glycol monoacrylate, tetrahydrofuryl acrylate, polypropylene glycol monomethacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate. Hydroxypropyl methacrylate, benzyl,Furfuryl or phenyl (meth)acrylate, a mixture containing at least one of these (meth)acrylates and / or copolymers comprising one or at least two of the aforementioned monomers.

[0054] Furthermore, the invention relates to 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 crosslinking agents. Such additives—like pigments, stabilizers, and regulators—are used in relatively small quantities, e.g., a total of 0.01 to 3.0 wt.%, particularly 0.01 to 1.0 wt.% based on the total mass of the material. Suitable stabilizers include, for example, hydroquinone monomethyl ether or 2,6-di-tert-butyl-4-methylphenol (BHT).

[0055] 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-dibenzylaminobenzoic acid diethyl ester; or c) at least one initiator system selected from redox systems, in particular a combination selected from dibenzoyl peroxide, dilauroyl peroxide and camphorquinone with amines selected from N,N-dimethyl p-toluidine. NN-Dihydroxyethyl-p-toluidine and p-Dimethylaminobenzoic acid diethyl ester.Alternatively, the initiator system can be a redox system comprising a peroxide and a reducing agent selected from ascorbic acid, an ascorbic acid derivative, barbituric acid or a barbituric acid derivative, sulfinic acid, or a sulfinic acid derivative. A redox system comprising (i) barbituric acid or thiobarbituric acid or a barbituric acid or thiobarbituric acid derivative, (ii) at least one copper salt or copper complex, and (iii) at least one compound with an ionic halogen atom is particularly preferred. A redox system comprising 1-benzyl-5-phenylbarbituric acid, copper acetylacetonate, and benzyldibutylammonium chloride is particularly preferred. Polymerization in the two-component denture base material is preferably initiated via a barbituric acid derivative.

[0056] Suitable initiators for the polymerization reaction of cold- or autopolymerizing starting mixtures are, in principle, those that can initiate radical polymerization reactions. 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.

[0057] To accelerate the initiation of radical polymerization by peroxides, suitable activators, such as aromatic amines, can be added. Examples of suitable amines include N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidine, and diethyl p-dibenzylaminobenzoate. These amines typically act as co-initiators and are usually present in amounts up to 0.5 wt%.

[0058] The following exemplary embodiments are intended to illustrate the invention without limiting the invention to these examples. Example of implementation: Three-point bending test

[0059] 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 produced using a low-speed diamond saw (Isomet, Buehler, Lake Bluff, IL, USA). All specimens were wet-ground and polished with #600 and #1000 diamond wheels (Maruto, Tokyo, Japan) and #1000 diamond blades (Maruto) mounted on a metallographic lapping machine (Dia-Lap ML-150P, Maruto) to achieve the required dimensions of 4.0 ± 0.2 × 14.0 ± 0.2 × 1.2 ± 0.2 mm. To minimize edge breakage in the rod-shaped samples during the bending test, a 0.15 mm wide chamfer was applied using a lapping machine with a #1000 diamond blade. After polishing, all samples were stored in a desiccator with silica gel for 7 days prior to the bending test.From each CAD / CAM block, three groups of ten samples each were randomly generated. 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 deionized water at 37°C for 7 days, while the third group was stored in deionized water at 37°C for 7 days followed by 5000 thermal cycles (5°C to 55°C, residence time 30 s) using a thermocycling device (HA-K178, Tokyo Giken Inc., Tokyo, Japan). The width and thickness of each sample were measured with 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) using a universal testing machine (AG-X, Shimadzu Corp., Kyoto, Japan).The flexural strength and flexural modulus were calculated using the software (TRAPEZIUM X, Shimadzu Corp., Kyoto, Japan). The flexural modulus (E) was calculated using the following formula: . E = F L 3 / 4 b h 3 d where F is the load at a suitable point in the straight part of the spring characteristic curve, L is the span (12.0 mm), b is the width of the specimen, h is the thickness of the specimen, and d is the bending at load F. The bending strength (σ) was calculated using the following formula: σ = 3 F 1 L / 2 b h 2 where F1 is the maximum load during the bending test.

[0060] The hardness test was carried out using the Zwick universal device: The measured values ​​of samples according to the invention are in the range of 800 to 850.

[0061] The following are comparative examples of the light-curing products Venus Diamond (VD) and Venus Pearl (VP) according to ISO 4049 and ISO 6872 (Exposure was carried out spotwise according to the method described in EN ISO 4049:2009 7.11 with a Translux 2Wave (1200 mW / cm²)). 2 ) by an exposure time of 20 seconds per exposure point.) was measured and compared to the inventive example 1. Table 2: Comparison of Example 1 with Venus products Comparative examples Example 1 Venus Diamond (VD) Venus Pearl (VP) Flexural strength [MPa] according to EN ISO 6872 (24 h / dry) 267 MPa 182 MPa 195 MPa Modulus of elasticity [GPa] according to EN ISO 6872 (24 h / dry) 16.3 GPa 15.6 GPa 15.8 GPa Flexural strength [MPa] according to EN ISO 4049 (24 h / water / 37°C) 174 MPa 149 MPa Module [GPa] according to EN ISO 4049 (24 h / water / 37°C) 12.0 GPa 11.4 GPa

[0062] Polymerization Example 1: 130 °C, Pressure: 300 MPa for 12 minutes Polymerization examples 2 and 3: 3 hours at 95 °C Table 3: Compositions according to the invention, examples 1 to 3 Example 1 Example 2 Example 3 Dental glass mean diameter d 50 0,85 µm 0,85 µm 0,85 µm % by weight g % by weight g % by weight g Dental glass Barium aluminum borofluorosilicate glass (silanized) 74,00% 74 75,60% 75,6 72,36% 72,36 metal oxide amorphous SiO2 5,00% 5 4,70% 4,7 5,32% 5,32 Urethane (meth) acrylate Bis-(4',7'-dioxa-3',8'-dioxo-2'-aza-decyl-9'-ene)-tetra-hydro-dicyclo-pentadiene 12,80% 12,8 12,28% 12,28 14,00% 14 Urethane methacrylate oligomer hexafunctional 0,65% 0,65 0,58% 0,58 0,67% 0,67 7,7,9-Trimethyl-4,13-dioxo-3,14-dioxa-5,12-diaza-hexadecane-1,16-diylbis-methacrylate 4,50% 4,5 4,55% 4,55 5,19% 5,19 di- to multifunctional monomers 1,2-Bis(2-(methacryloyloxy)ethoxy)ethane 0,85% 0,85 0,87% 0,87 1,00% 1 initiator system Tert-butyl peroxy-2-ethyl hexanoate 0,50% 0,5 0,41% 0,41 0,40% 0,4 stabilizer 2-Hydroxy-4-methoxy-benzophenone 0,30% 0,3 0,25% 0,25 0,28% 0,28 Water 0,70% 0,7 0,66% 0,66 0,64% 0,64 pigments Diethyl 2,5-dihydroxyterephthalate, among other things color pigments 0,70% 0,7 0,01% 0,01 0,01% 0,01 Table 4: Flexural strengths (according to EN ISO 6872) initial / dry after 7 days / dry 7 days / water / 37°C after TC / water Example 1 267 MPa 219 MPa Example 2 244 MPa 259 MPa 209 MPa 216 MPa Example 3 236 MPa 262 MPa 209 MPa 224 MPa Table 5: E-modulus (modulus of elasticity) initial / dry after 7 days / dry 7 days / water after TC / water Example 1 16.3 GPa 16.5 GPa Example 2 18.0 GPa 19.9 GPa 18.6 GPa 15.7 GPa Example 3 15.1 GPa 20.1 GPa 18.4 GPa 16.9 GPa Viscosity measurements:

[0063] Rheometer: Anton Paar - Physica MCR 301 Interchangeable plate I-PP-50 / SS sandblasted Measuring plate PP15 / S sandblasted

[0064] PP15; d= 2.5mm tau = 1 - 40000Pa frequency = 1 Hz Temperature = 40°C Waiting time = 5 minutes Weight = 1.1-1.2g GRM manufactured in production (ferroglass) Colored in the FE

[0065] 50 measuring points, measuring point duration 6 s, max. settling time 0 s Table 6a: Viscosity measurements: Resting time before application Memory module[Pa] Amount of viscosity 24h 1,18E+05 1,99E+04 24h 8,82E+04 1,50E+04 24h 7,32E+04 1,25E+04 3 days 1,53E+05 2,55E+04 24h 6,27E+04 1,07E+04 24h 3,68E+04 6,61E+03 24h 4,16E+04 7,43E+03 Table 6b: Mean values ​​of other viscosity measurements measurement Storage module (linear viscoelastic region) Amount of viscosity mean 3,975E+04 7,108E+03 QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited non-patent literature

[0000] Bonded disc method - Dental Materials, Watts et al, (2004) 20, 88-95; 23 °C, Translux Energy, 60 s exposure

[0039] EN ISO 6872:2008

[0041] Standard ISO 6872

[0042] ISO 4049

[0061] ISO 6872

[0061] EN ISO 4049:2009 7.11

[0061]

Claims

[1] Polymerizable dental composite material comprising (i) 70 to 85 wt.% of an inorganic filler component comprising at least one dental glass and optionally at least one amorphous metal oxide, (ii) 10 to 30 wt.% of a mixture of at least two different urethane(meth)acrylates, (iii) 0.01 to 5 wt% of at least one di-, tri-, tetra- or multi-functional monomer that is not a urethane (meth)acrylate, (iv) 0.01 to 10 wt% of at least one initiator, one initiator system and optionally at least one stabilizer and optionally at least one pigment, wherein the total composition of the composite material is 100 wt%. [2] Dental composite material according to claim 1, characterized by that the dental glass has a medium particle size d 50 has a thickness of 0.7 to 1.0 µm. [3] Dental composite material according to claim 1 or 2, characterized bythat the amorphous metal oxide comprises at least one non-agglomerated amorphous metal oxide with a primary particle size of 2 to 45 nm, and that the amorphous metal oxide optionally comprises precipitated silicon dioxide, zirconium oxide or mixed oxides. [4] Dental composite material according to any one of claims 1 to 3, characterized by , that the composite material comprises (i) as an inorganic filler component (i.1) 70 to 84 wt.% of at least one dental glass, and optionally (i.2) 1 to 15 wt.% of amorphous metal oxide in relation to the overall composition. [5] Dental composite material according to any one of claims 1 to 4, characterized by, that (ii) comprises a mixture of at least two different urethane(meth)acrylates, wherein the mixture comprises at least one difunctional urethane(meth)acrylate with a bivalent alicyclic group and one difunctional urethane(meth)acrylate with a bivalent alkylene group and optionally at least one at least tetrafunctional dentrist urethane(meth)acrylate, preferably at least one hexafunctional dentrist urethane(meth)acrylate. [6] Dental composite material according to any one of claims 1 to 5, characterized by , that (iii) is selected from di-methacrylic esters of polyethers, tri-, tetra- or multifunctional methacrylic esters of polyethers. [7] Dental composite material according to any one of claims 1 to 6, characterized by , that the at least one stabilizer comprises water, at least one benzophenone and / or at least one phenol derivative. [8] Dental composite material according to any one of claims 1 to 7, characterized by, that the at least one pigment comprises fluorescent pigments, organic color pigments and inorganic color 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 antimontitanate (rutile structure), spinel black, in particular pigments based on iron oxide black (Fe3O4) wherein iron (Fe) is partially substituted by chromium and copper or nickel and chromium or manganese, zinc iron chromium spinel, brown spinel, cobalt zinc caluminate blue spinel and / or titanium oxide. [9] Polymerized dental composite material obtainable by polymerization of the composite material according to any one of claims 1 to 8, in particular by polymerization at a pressure of 50 to 300 MPa and / or elevated temperature, preferably at 90 to 150 °C. [10] Polymerized dental composite material according to claim 9 with a flexural strength of greater than or equal to 200 MPa, in particular with a flexural strength of greater than or equal to 240 MPa after 7 days of dry storage and greater than or equal to 200 MPa after 7 days of storage in water with thermocycling (5000 cycles) according to EN ISO 6872:2008, in particular greater than or equal to 250 MPa (dry) according to EN ISO 6872:2008. [11] Polymerized dental composite material according to claim 9 or 10, characterized by that the modulus of elasticity is greater than or equal to 15 to 20 GPa after 7 days of dry storage and optionally greater than or equal to 15 GPa after 7 days of storage in water with thermocycling (5000 cycles) according to EN ISO 6872 : 2008, preferably greater than or equal to 16 to 21 GPa after 7 days of dry storage and optionally greater than or equal to 15 GPa after 7 days of storage in water with thermocycling (5000 cycles) according to EN ISO 6872 : 2008. [12] Polymerized dental composite material comprising - 70 to 85 wt.% of at least one inorganic filler component comprising at least one dental glass of medium particle size d 50 from 0.7 to 1.0 µm and optionally at least one amorphous, silanized metal oxide with a primary particle size of 2 to 45 nm, - 10 to 30 wt% of at least one polymer based on at least one monomer comprising at least one bis-urethane derivative of tetrahydrodicyclopentadiene, at least one di-urethane (meth)acrylate with a bivalent alkylene group, at least one tetra- to deca-functional dendritic urethane methacrylate, and at least one di-, tri-, tetra- or multifunctional methacrylate of polyethers, preferably dimethacrylate triethylene glycol, and - 0.01 to 10 wt.% at least one pigment, in particular at least one fluorescent pigment and at least one organic color pigment and / or at least one inorganic color pigment, wherein the total composition of the composite material is 100 wt.%. [13] Polymerized dental composite material according to any one of claims 8 to 12, characterized by that the polymerized dental composite material is in the form of a material block, in particular the material block is in the form of a three-dimensional geometric shape, in particular as a milling blank without adapter or as a milling blank with adapter for fixing in an automated material removal device. [14] Use of a dental composite material according to any one of claims 1 to 13 for the production of dental prosthetic restorations in a material-removing process, in particular in a process in which the polymerized composite material is removed by milling, cutting, polishing, breaking, chipping and / or drilling, in particular in a process in which the composite material is removed by means of laser energy or for the production of direct adhesive dental restorations. [15] Use according to claim 14 for the manufacture of dental prosthetic restorations comprising crowns, inlays, onlays, superstructures, artificial teeth, dental bridges, dental bars, spacers, abutments or veneers.