Dental composite material

Abstract

The present invention provides a polymerizable dental composite material comprising: (i) 40 to 90% by weight of an inorganic filler component comprising at least one dental glass and optionally at least one amorphous metal oxide; (ii) 10 to 60% by weight of at least one urethane(alkyl)acrylate of idealized Formula I; (iii) 0.01 to 15% by weight of at least one difunctional, trifunctional, tetrafunctional, or polyfunctional monomer that is not a urethane(alkyl)acrylate; (iv) 0.01 to 10% by weight of at least one initiator, initiator system, and optionally at least one stabilizer and optionally at least one pigment; and a polymerizable dental composite material comprising the above compound, the total composition of which is 100% by weight, as well as a polymerized composite material for producing a direct or indirect dental restoration.

Description

[Technical field]

[0001] The present invention relates to a polymerizable dental composite material, comprising: (i) a polymerizable polymerizable composition having an average particle size d 50 and optionally at least one amorphous metal oxide; (ii) 10 to 60% by weight of at least one urethane(alkyl)acrylate of formula I, in particular a mixture of at least two different urethane(alkyl)acrylates, in particular urethane(meth)acrylates; (iii) 0.01 to 15% by weight of at least one di-, tri-, tetra- or polyfunctional monomer which is not a urethane(alkyl)acrylate, in particular which is not a urethane(meth)acrylate; and (iv) 0.01 to 10% by weight of at least one initiator, initiator system, and optional stabilizer and optional pigment, the total composition of the composite being 100% by weight, as well as a polymerized composite having high fracture toughness and preferably high flexural strength.

[0002] A large number of dental composite materials are known that are commonly available for the extraoral production of directly bonded restorations and indirect dentures. From the material classification of dental composites, essentially only inorganic-organic hybrid materials with a high proportion of inorganic fillers are suitable for this purpose, e.g. dental glasses and / or mineral nanoaggregates. Microfiller composites with prepolymer fillers, introduced in the 1980s, are not suitable for use in the posterior region (behind the canines) (classes I and II) due to the limited loads that can be applied to the material (flexural strength).

[0003] Commercially available dental composite materials are usually based on crosslinking monomers having structural units of bisphenol A (e.g., bis-GMA, bis-EMA) and other monomers having a viscosity reducing effect (e.g., TEGDMA, UDMA, etc.). Dental composite materials without BPA structural units can be obtained using radical crosslinked TCD urethane monomers, and further, 1.0 MPa·m 0.5 is characterized by a significantly improved fracture toughness (ISO 13586:2000) exceeding. Since the fracture of dental composite materials under chewing pressure is still a common reason for the damage of this group of restorative materials, this surprisingly high fracture toughness (1.5…2.4 MPa·m 0.5 ) suggests advantages in long-term use.

[0004] In order to achieve very good mechanical properties of the cured composite material and at the same time reduce the polymerization shrinkage occurring during curing, a high filler content is advantageous. These properties are also decisive for the long-term success of denture materials.

[0005] The material properties of ester dental composite materials having excellent polyalicyclic structural elements for direct bonding restorations, especially low shrinkage force and high flexural strength, are well known.

[0006] The object of the present invention was to provide a dental composite material that is not only suitable for manufacturing dental filling materials, but also suitable for manufacturing large blocks of material, particularly geometric shaped bodies such as milling blocks. Furthermore, the composite material needs to have good values of fracture toughness, which represents a measure of the force applied to crack propagation in the material. In addition, it was an object to provide a dental composite material having a uniform single-color coloring before and after polymerization. In this context, not only when manufacturing dental fillings, but also a uniform single-color coloring needs to be achievable with larger blocks of material. Furthermore, it is necessary to be able to manufacture multi-colored blocks of material, i.e., blocks of material in defined colors. In addition, it is necessary to provide a dental composite material that exhibits sufficient flow characteristics in the non-polymerized state and can be transferred in the polymerized state with excellent mechanical properties by ultraviolet or visible light. It is also necessary to provide a dental composite material with little shrinkage in the polymerized state even when manufacturing larger material blocks. Furthermore, the composite material should not generate cracks or pores during curing, even in large volume material blocks.

[0007] Starting from prior art composite materials, new composite materials containing novel urethane derivatives having three rings have been developed. The present invention relates to the composite material according to claim 1, the polymerized composite material according to claims 11 and 12, and the use according to claim 14, and the preferred embodiments are described in detail in each of the dependent claims and the description.

[0008] The particle size distribution may be relatively wide for high filler packing density and excellent mechanical properties depending on the required filler content, or can be made quite narrow for specific applications. The average value of the particle size distribution may be in the range of 0.5 μm to 10 μm, preferably in the range of 0.7 μm to 7.5 μm. In this context, the particle size distribution of the dental glass fraction has a particle size distribution d in the range of 0.7 μm to 2.0 μm, particularly 1.2 to 2.0 μm (micrometers). 50It can be set based on a content of 5 to 75% by mass based on the total of the composition of the dental glass, preferably these have a d of 1.8 μm plus / minus 0.25 μm 50 and particularly preferably a d of 20 μm or less 99 or a d of 10 μm or less 99 It has. In an alternative form, in order to optimally adjust the packing density, an additional dental glass fraction having a smaller and / or larger particle size distribution different from the above can be added. The adjusted packing density enables optimal setting of mechanical properties and reduction of shrinkage.

[0009] Composite materials with reduced shrinkage of TCD esters and good flexural strength are known. Surprisingly, in a radiation-cured composite material containing a polymerization product of an urethane of the idealized formula I, particularly the idealized formula Ia, preferably after radiation curing, very good fracture toughness values (measured according to ISO 13586:2000) may be shown. Similarly, in a thermoset composite material containing a polymerization product of an urethane of the idealized formula I, surprisingly good flexural strength values (measured according to ISO 13586:2000) may be obtained.

[0010] Since a surprisingly high flexural strength (in accordance with DIN ISO 404902019) can also be achieved by photochemically initiated polymerization, it has surprisingly been found that composite materials based on urethane monomers having an alicyclic structural element such as tetrahydrodicyclopentadiene are very suitable for the production of indirect dentures. The high level of material strength compared to the photopolymerization of the photocurable dental composite materials already described is surprising, and such a significantly increased value was unexpected.

[0011] The subject matter of the present invention is (i) an average particle size d of particularly 0.5 to 10 μm, preferably 0.7 to 7.5 μm, particularly 0.7 to 5.5 μm, preferably 0.8 to 5.5 μm 50At least one dental glass, and optionally at least one amorphous metal oxide in an amount of from 2% to less than 10% by mass, preferably from 2 to 7.5% by mass, based on the total composition, and 40 to 90% by mass, in particular 70 to 90% by mass, of at least one inorganic filler component, and (ii) at least one urethane acrylate having an idealized divalent alicyclic group of formula I in an amount of 10 to 60% by mass, in particular 10 to 30% by mass, preferably 12 to 20% by mass, preferably a mixture of at least two different urethane acrylates, at least one urethane acrylate, in particular a urethane of idealized formula I

Chemical formula

[0012] The idealized urethane of formula I is described as cas number 94 5656-78-0 (2-propenoic acid, 1,1'-[(octahydro-4,7-methano-1H-inden-5,?-diyl)bis(methyleneoxycarbonylamino-2,1-ethanediyl)]ester). Alternatively, this formula can be illustrated as follows.

[0013]

Chemical formula

[0014] The difunctional urethane acrylate is preferably selected from difunctional urethane alkyl acrylates having a divalent alkylene group containing alkyl of 1 to 10 carbon atoms and alkylene of 3 to 20 carbon atoms, preferably including a divalent alkylene group.

[0015] Particularly preferred dental composite materials are (i) At least one inorganic filler component containing 70 to 85% by mass of at least one dental glass and an optional at least one amorphous metal oxide, (ii) A mixture of at least two different urethane acrylates, including at least one difunctional urethane acrylate and / or urethane alkyl acrylate having a divalent alicyclic group, including the urethane of the idealized formula I, and / or a mixture of the urethane of the above formula I, and / or an optional mixture of isomers of the aforementioned compounds [R 1 and R 2 are each independently selected from H and alkyl having 1 to 8 carbon atoms], (iii) 0.01 to 15% by mass of at least one difunctional, trifunctional, tetrafunctional, or polyfunctional monomer that is not a urethane acrylate and / or not a urethane alkyl acrylate. (iv) 0.01 to 10% by mass of at least one initiator, initiator system, and optionally at least one stabilizer and optionally at least one pigment, containing, with the total composition of the composite material being 100% by mass.

[0016] Even more particularly preferred composite materials are (i) Especially silane-treated, preferably functionalized with methacryloyloxypropyl groups, in particular having an average particle size d of 0.5 to 10 μm, preferably 0.7 to 7.5 μm, especially 0.7 to 5.5 μm, preferably 0.8 to 5.5 μm, 50 of at least one dental glass containing barium aluminosilicate glass, fluorobarium aluminosilicate glass, and / or feldspar, and optionally from more than 1% to 10% by mass, preferably 2 to 7.5% by mass, particularly preferably 3 to 7.5% by mass, of a non-aggregated amorphous metal oxide having a primary particle diameter of 2 to 150 nm, especially 2 to 100 nm, preferably 2 to 45 nm, containing silicon dioxide, precipitated silicon dioxide, calcined silica, zirconium dioxide, mixed oxides, or mixtures thereof, especially a metal oxide treated with silane, comprising 70 to 85% by mass of at least one inorganic filler component, (ii) 10 to 30% by mass, for example up to 29.98% by mass, preferably 12 to 20% by mass, of a mixture of at least two different urethane acrylates, especially a mixture of at least one urethane acrylate or bifunctional urethane alkyl acrylate having a divalent alicyclic group and / or a mixture of urethanes of formula I, including an idealized urethane of formula I, and optionally a mixture of isomers of urethane of formula I (see also formula Ia), especially a mixture of the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or cis- and trans-isomers of the aforementioned compounds [R 1 and R 2is independently selected from H and alkyl having 1 to 8 C atoms, preferably a mixture of at least three different urethane acrylates and / or urethane alkyl acrylates, particularly including bifunctional to decafunctional urethane acrylates, (iii) 0.01 to 5% by mass of at least one difunctional, trifunctional, tetrafunctional or polyfunctional monomer that is not a urethane acrylate or a urethane (alkyl) acrylate, particularly not a urethane (methyl) acrylate, (iv) 0.01 to 10% by mass of at least one initiator, initiator system and optionally at least one stabilizer, and optionally at least one pigment, particularly at least one pigment containing fluorescence and coloring pigments, and the total composition of the composite material is 100% by mass.

[0017] In a modification of one embodiment, the polymerizable composite material is preferably photochemically polymerizable or polymerizable by initiation with light. Alternatively, the polymerizable composite material is preferably thermally polymerizable. A photochemically polymerizable composite material means a composite material polymerizable by UV emission and / or visible light (Vis emission), preferably a composite material polymerizable by a radiation source having an emission maximum in the spectral region of 400 nm to 530 nm, preferably in the spectral region of 440 to 500 nm. Particularly preferably, the irradiation of the composite material is carried out for at least 10 seconds, particularly for each projection surface of the radiation source. Irradiation for 15 seconds or more to 5 minutes per projection surface of the radiation source, preferably 10 to 30 seconds, is more preferable. Suitable radiation sources generally include any ordinary radiation source having an emission wavelength, preferably an emission maximum, in the spectral range of 440 to 480 nm, which is particularly used in the dental field, and having an intensity exceeding 500 mW / cm 2 including. A radiation source equipped with an LED lamp is particularly preferred.

[0018] The thermopolymerizable composite material is understood in this specification to mean a composite material that can be polymerized at 60°C or higher up to 150°C, preferably 70°C or higher up to 150°C, particularly preferably 90 - 150°C. In this connection, according to the present invention, it is even more preferable that the volume shrinkage is 1.5% or less (ISO 17304:2013).

[0019] Furthermore, the subject of the present invention is a dental composite material obtained by polymerizing using i) a UV / Vis radiation source, preferably a Vis radiation source having an emission maximum in the spectral region of 380 nm to 530 nm, preferably having at least one emission maximum in the spectral region of 400 nm to 500 nm, and optionally ii) a pressure of 50 - 300 Mpa and / or a high temperature, preferably 90 - 150°C, or using i) a UV / Vis radiation source, preferably a Vis radiation source having an emission maximum in the spectral region of 380 nm to 530 nm, preferably having at least one maximum in the spectral region of 400 nm to 500 nm, and / or ii) a pressure of 50 - 300 Mpa and / or a high temperature, preferably 90 - 150°C, is also a dental composite material obtained by polymerization.

[0020] In a modification of one embodiment, it is particularly preferred that the inorganic filler component consists of at least dental glass or a mixture of dental glasses, particularly those having the average particle size described above, and amorphous metal oxides, particularly non-aggregated amorphous oxides, preferably silane-treated amorphous metal oxides. The dental glass may preferably be silane-treated. Preferably, the silane treatment includes acrylic functionalization.

[0021] The following dental glasses are preferably considered: aluminosilicate glass or fluoroaluminosilicate glass, fluoroaluminosilicate glass containing a boron component, barium aluminosilicate, strontium silicate, strontium borosilicate, lithium silicate and / or lithium aluminosilicate, and a mixture of at least two of the aforementioned dental glasses. Amorphous spherical fillers based on oxides or mixed oxides such as amorphous SiO2, ZrO2, or a mixed oxide of SiO2 and ZrO2 can be used as metal oxides or as a mixture of amorphous metal oxides.

[0022] The subject matter of the present invention is a) dental glass having an average particle size d of 1.8 μm, plus / minus 0.25 μm 50 , preferably d of 20 μm or less 99 or b) i) d of 2 - 8 μm, optionally plus / minus 0.5 μm, particularly 4 - 6 μm, optionally plus / minus 0.25 μm 50 , ii) d of 1.0 - 2.0 μm, optionally plus / minus 0.25 μm, particularly 1.2 - 2.0 μm, optionally plus / minus 0.5 μm, preferably 1.5 μm, optionally plus / minus 0.15 μm 50 , and iii) d of 0.5 - 1.2 μm, optionally plus / minus 0.15 μm, 0.7 - 0.9 μm, optionally plus / minus 0.5 μm 50 and is also a dental composite material containing a mixture of different fractions of dental glass having an average particle size such that the fraction of i):ii):iii) is present in a ratio of 1 - 4:1:4 - 8, particularly 2 - 3:1:6 - 7. i) d of 5 μm, optionally plus / minus 0.5 μm 50 , ii) d of 1.8 μm, optionally plus / minus 0.25 μm 50 , and iii) d of 0.85 μm, optionally plus / minus 0.15 μm 50is particularly preferred, and the fractions of i) to ii) to iii) are present in a ratio of 1 to 4:1:4 to 8, particularly 2 to 3:1:6 to 7.

[0023] According to a preferred embodiment, the dental composite material has an average particle size d of 1.2 to 2.0 μm 50 , preferably an average particle size of 1.35 to 1.95 μm, particularly 1.8 μm, optionally d of plus / minus 0.15 μm 50 , preferably d of 10 μm or less 99 and includes at least one dental glass, particularly a radiopaque dental glass, having a d. Particularly preferably, it has a d of 0.85 μm, optionally plus / minus 0.1 μm, particularly plus / minus 0.05 μm, preferably plus / minus 0.03 μm 50 and an average particle size, and preferably a dental glass having a d of 10 μm or less is additionally present. Particularly preferred dental glasses include barium aluminosilicate glass. Further, barium aluminosilicate glass having a refractive index of n = 1.52 to 1.55, preferably 1.53, is particularly preferred. A particularly preferred particle size distribution is d of 0.2 μm or more 99 to 20 μm or less, preferably 7.5 μm or less 10 , preferably d of 0.4 μm or more 99 to 7.5 μm or less 10 , and may be in the range of an average diameter d of 0.7 to 7.5 μm 99 . 50

[0024] According to a preferred embodiment, the dental composite material (i) contains 70 to 85% by mass of at least one inorganic filler component, where, based on the composite material with a total composition of 100% by mass, at least one dental glass having an average particle size d of 0.7 to 2.0 μm 50 is present in an amount of 50 to 80% by mass, particularly 55 to 76% by mass, preferably 60 to 75% by mass, particularly preferably 60 to 71% by mass in the total composition of 100% by mass. A combination with 4 to 7.5% by mass of amorphous silicon dioxide in the total composition is more preferred.

[0025] Furthermore, the subject matter of the present invention is a dental composite material containing 70 to 85% by mass of at least one inorganic filler component, which comprises (i) at least one dental glass, especially a barium aluminum silicate glass or a fluoro barium aluminum silicate glass, preferably silane-treated and preferably functionalized with methacryloxypropyl groups, and optionally (ii) at least one non-aggregated amorphous metal oxide having a primary particle size of 2 to 150 nm, especially 2 to 100 nm, preferably 2 to 45 nm. The amorphous metal oxide includes silicon dioxide, precipitated silicon dioxide, calcined silica, zirconium oxide, mixed oxides, or mixtures thereof, and especially the metal oxide is silane-treated.

[0026] To achieve high flexural strength, the dental composite material preferably contains, as the inorganic filler component, (i.1) 66 to 84% by mass, especially 68 to 78% by mass, or 75 to 78% by mass of at least one dental glass, and optionally (i.2) 2 to 10% by mass, especially from 3% to less than 10% by mass, preferably 4 to 8% by mass of amorphous metal oxide, in the whole composition (total 100% by mass). The ratio of dental glass to amorphous metal oxide is preferably 20:1 to 7:1, preferably 15:1 to 10:1.

[0027] Preferably, 85 to 99% by mass, preferably 91 to 99% by mass, or 92 to 99% by mass of at least one dental glass or a mixture of dental glasses, and optionally more than 1% to up to 13% by mass, especially 8 to 15% by mass, or 2 to 8% by mass of amorphous metal oxide or a mixture of metal oxides, especially calcined silica and / or precipitated silicon dioxide, are present in the inorganic filler component.

[0028] In a preferred alternative form, the composite material may contain, in addition to the inorganic filler component, a certain amount of polymer particulate filler. The total amount of such polymer particulate filler can be in the range of 0.01 to 15% by weight, preferably 0.5 to 10% by weight, based on the entire composition of 100% by weight of the composite material. The particle size of the polymer filler is preferably in the range of 10 to 200 micrometers, particularly 30 to 90 micrometers, and particularly preferably 20 to 50 micrometers. The polymer particulate filler is preferably non-spherical. Preferably, the polymer particulate filler is present in the form of crushed polymer.

[0029] According to a variant of a particularly preferred embodiment, the dental composite material, based on the total composition, (i)(i.1) 60 to 84% by weight, particularly 66 to 78% by weight, preferably 66 to 70% by weight, or 75 to 78% by weight, of at least one dental glass having an average particle size d of 0.7 to 7.5 μm, particularly 1.8 μm 50 optionally having the standard deviation described above, and optionally (i.2) 2 to 34% by weight, particularly 3% to 15% by weight, preferably 3 to 10% by weight, particularly preferably 4 to 10% by weight, more preferably 1 to 7.5% by weight, of at least one silane-treated amorphous metal oxide and / or calcined silica having a primary particle size of 2 to 100 nm, preferably 2 to 45 nm, containing 70 to 85% by weight of at least one inorganic filler component (ii) 10 to 30% by weight, particularly 15 to 30% by weight, preferably 18 to 22% by weight, of a mixture of at least three different urethane acrylates and / or urethane alkyl acrylates, particularly a mixture of bifunctional to decafunctional urethane acrylates and / or the corresponding urethane alkyl acrylates, preferably 15 to 19% by weight of an idealized urethane of formula I

Chemical formula

[0030] A difunctional to decafunctional urethane acrylate or a difunctional to decafunctional urethane alkyl acrylate is used as a monomer and does not contain a peroxy group.

[0031] According to a modification of a particularly preferred embodiment, the dental composite material contains (ii) a mixture of at least three different urethane acrylates and / or urethane alkyl acrylates, preferably a mixture of at least three different urethanes, in an amount of 10 to 30% by mass. The mixture contains at least one difunctional urethane acrylate and / or urethane alkyl acrylate of the idealized formula I (see also formula Ia)

Chemical formula

[0032] According to a variant of a particularly preferred embodiment, the dental composite material comprises (ii) a mixture comprising at least one difunctional urethane acrylate and / or urethane alkyl acrylate comprising the idealized urethane of formula I, and / or a mixture of the urethanes of formula I, and optionally the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or cis- and trans-isomers of the aforementioned compounds [R 1 and R 2is independently selected from H and alkyl having 1 to 8 C atoms each, for example bis-(2’,7’-dioxa-3’,8’-dioxo-4’-aza-decyl-9’-ene) tetrahydrodicyclopentadiene, bis-(2’,7’-dioxa-3’,8’-dioxo-4’-aza-9’-methyl-decyl-9’-ene) tetrahydrodicyclopentadiene, and optionally 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, a mixture of at least one difunctional urethane acrylate having a divalent alicyclic group and / or at least one difunctional urethane (meth)acrylate having a divalent alicyclic group, and optionally a mixture of 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or cis- and trans-isomers of the aforementioned compounds, and at least one additional difunctional urethane (meth)acrylate, in particular at least one difunctional urethane acrylate having a divalent alicyclic group and / or a urethane methacrylate having a divalent alicyclic group, and optionally at least one at least pentafunctional dendritic urethane acrylate and / or the corresponding urethane methacrylate, preferably at least one hexafunctional dendritic urethane acrylate and / or urethane methacrylate, and contains 10 to 30% by mass of a mixture of at least two different urethane acrylates selected therefrom. Particularly preferred is at least three different urethane (meth)acrylates selected from urethane acrylate and urethane methacrylate (based on the entire composition of 100% by mass).

[0033] According to a variant of a particularly preferred embodiment, the dental composite material contains (ii) a mixture of at least two different urethane (meth)acrylates, preferably a mixture of three different urethane (meth)acrylates.

[0034] The term (alkyl) acrylate or (meth) acrylate or urethane (alkyl) acrylate containing (alkyl) in parentheses, or the term urethane (meth) acrylate containing (meth) in parentheses, means that it may include acrylate or urethane acrylate with or without an alkyl group or a methyl group. The alkyl group preferably contains 1 to 10 C atoms, preferably 1 to 2 C atoms, in the urethane alkyl acrylate. The alkyl group preferably contains 1 to 10 C atoms, preferably 1 to 2 C atoms, in the (alkyl) acrylate.

[0035] According to a variant of a particularly preferred embodiment, the dental composite material contains ii) at least a bifunctional urethane (meth) acrylate of general formula I, and at least one bifunctional urethane (meth) acrylate having a divalent alkylene group, and optionally at least one at least tetrafunctional dendritic urethane (meth) acrylate, preferably at least one hexafunctional dendritic urethane (meth) acrylate, in an amount of 10 to 30% by mass of a mixture of at least two different urethane (alkyl) acrylates, preferably a mixture of at least three different urethane (meth) acrylates.

[0036] According to the present invention, the urethane acrylate having a divalent alicyclic group is the urethane of the idealized formula I

Chemical formula

[0037] The difunctional urethane(alkyl)acrylate, urethane(alkyl)acrylate having a divalent alkylene group, or urethane(meth)acrylate having a divalent alicyclic group is preferably a linear or branched urethane dimethacrylate functionalized with a divalent alkylene group, a urethane dimethacrylate functionalized polyether having an alkylene group, for example bis(methacryloxy-2-ethoxycarbonylamino)alkylene, bis(methacryloxy-2-ethoxycarbonylamino)-substituted polyalkylene ether, preferably 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane, UDMA (also known as HEMA-TDMI). Bis(methacryloxy-2-ethoxycarbonylamino)alkylene in which the alkylene is linear or branched C3-C20, preferably C3-C6, is preferred, for example, particularly preferably an alkylene substituted with a methyl group such as HEMA-TMDI. The divalent alkylene preferably contains 2,2,4-trimethylhexamethylene and / or 2,4,4-trimethylhexamethylene.

[0038] The at least tetrafunctional dendritic urethane methacrylate includes tetrafunctional to decafunctional dendritic urethane methacrylate.

[0039] (ii) A mixture of at least two different urethane (meth)acrylates, based on the total composition, in an amount of 10 to 30% by mass, preferably 15 to 20% by mass, for example at least one bifunctional urethane of general formula I and at least one hexafunctional dendritic urethane (meth)acrylate, and it is also preferred to include at least one bifunctional urethane (meth)acrylate having an optional divalent alkylene group.

[0040] Preferably, the composite material contains, based on the total composition, 5 to 25% by mass, especially 15 to 19% by mass, of bis-(2’,7’-dioxa-3’,8’-dioxo-4’-aza-decyl-9’-ene) tetrahydrodicyclopentadiene, bis-(2’,7’-dioxa-3’,8’-dioxo-4’-aza-9’-methyl-decyl-9’-ene) tetrahydrodicyclopentadiene, and / or mixtures thereof, and optional 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or mixtures of cis- and trans-isomers of the aforementioned compounds, 1 to 15% by mass, especially 5 to 6% by mass, of each of UDMA (1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane), or HEMA-TMDI, and 0.1 to 5% by mass, preferably 0.2 to 2% by mass, especially preferably 0.1 to 1% by mass, of at least one tetrafunctional to decafunctional dendritic urethane methacrylate.

[0041] Preferably, based on the total composition, the composite material comprises 10-18% by mass of bis(2’,7’-dioxa-3’,8’-dioxo-4’-aza-decyl-9’-ene)tetrahydrodicyclopentadiene, bis-(2’,7’-dioxa-3’,8’-dioxo-4’-aza-9’-methyl-decyl-9’-ene)tetrahydrodicyclopentadiene, and / or mixtures thereof, and optionally 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or mixtures of cis- and trans-isomers of the aforementioned compounds, 3-8% by mass of a bifunctional urethane (meth)acrylate having a divalent alkylene group, in particular UDMA or HEMA-TMDI respectively, and 0.1-2% by mass, preferably 0.2-2% by mass, particularly preferably 0.1-1% by mass of a mixture of at least three different urethane (meth)acrylates selected from at least one tetrafunctional to decafunctional dendritic urethane methacrylate, containing 10-20% by mass.

[0042] According to a more preferred embodiment, the dental composite material, as component (iii), instead of a urethane (alkyl) acrylate, contains 0.01-5% by mass of at least one bifunctional, trifunctional, tetrafunctional, or polyfunctional monomer selected from diesters of polyethers dimethacrylic acid, bis-(2’-oxa-3’-oxo-pentyl-4’-ene)tetrahydrodicyclopentadiene or its isomers, and methacrylic acid esters of trifunctional, tetrafunctional, or polyfunctional polyethers.

[0043] Preferably, the content of component (iii) is 0.15-15% by mass, particularly 0.15-5% by mass, particularly preferably 1.0-2% by mass, and component (iii) is selected from diesters of polyethers dimethacrylic acid, for example, preferably polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate. Triethylene glycol dimethacrylate (TEGDMA), diethylene glycol dimethacrylate (DEGMA), and tetraethylene glycol dimethacrylate (TEDMA) are particularly preferred.

[0044] To improve the consistency and flow characteristics for the workability of process engineering, water can be added as a stabilizer to the dental composite material. The stabilizer is preferably added to the composite material to prevent premature polymerization and give the material a certain shelf life. The composite material contains, as a preferred stabilizer in component (iv), 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 three stabilizers. The stabilizer is preferably present in the range of 0.01 to 10% by mass, particularly preferably 0.7 to 10% by mass, especially 0.5 to 2% by mass throughout the composition. Further, the composite material preferably contains 0.01 to 2% by mass of water as a stabilizer, preferably 0.1 to 1.0% by mass of water.

[0045] For optimal adjustment of the color and natural aesthetic appearance of the polymerized composite material, at least one pigment including at least one fluorescent pigment and optionally at least one organic coloring pigment and / or at least one inorganic coloring pigment, particularly a non-fluorescent coloring pigment, is added to the composite material. The at least one fluorescent pigment is preferably an organic fluorescent pigment, particularly in a suitable case, a non-polymerizable organic fluorescent pigment containing an aryl carboxylic acid ester, an aryl carboxylic acid, coumarin, rhodamine, naphthalene imide, or a derivative of each substance. Inorganic fluorescent pigments include CaAl4O7:Mn 2+ , (Ba0.98Eu0.02)MgAl 10 O 17 , BaMgF4:Eu 2+ , and may include Y(1.995)Ce(0.005)SiO5.

[0046] The composite material contains, as pigments, in particular coloring pigments, organic pigments, and inorganic pigments, in particular pigments based on diethyl 2,5-dihydroxyterephthalate, N,N'-bis(3,5-xylyl)perylene 3,4:9,10-bis(dicarboximide), copper phthalocyanine, titanium pigments, in particular antimony chromium titanate (rutile structure), spinel black, in particular iron (Fe)-based black pigment (Fe3O4) partially substituted with chromium and copper or nickel and chromium or manganese, zinc iron chromium spinel, brown spinel, ((Zn,Fe)(Fe,Cr)2O4), cobalt zinc aluminate blue spinel, and / or titanium oxide. Pigments including fluorescent pigments and coloring pigments are preferably present in the whole composition in an amount of 0.01 to 10% by mass, particularly preferably 0.01 to 5% by mass, preferably 0.01 to 1% by mass.

[0047] The selection of the pigment needs to be particularly adapted to the dental composite material composition in order to achieve a uniform color in both the polymerizable composite material and the polymerized composite material. Also, the production of large blocks of the material requires adjustment with respect to the selection and concentration of the pigment to avoid undesirable discoloration due to the dimensions of the polymerized blocks of the material.

[0048] According to a further particularly preferred embodiment, the dental composite material contains a component (i) forming a filler component, and the filler component contains, in the filler component, (i.1) 85 to 95% by mass, in particular 90 to 94.5% by mass, preferably 92 to 94.5% by mass of at least one dental glass, and optionally (i.2) 5 to 15% by mass, in particular 5 to 10% by mass, preferably 5.5 to 8% by mass of amorphous metal oxide, and the sum of (i.1) and (i.2) is 100% by mass of the filler component.

[0049] According to an even more particularly preferred embodiment, the dental composite material comprises components (ii) and (iii) that form a monomer component, and the monomer component comprises (ii.1) 40 to 75% by mass of at least one urethane of formula I, in particular bis(2’,7’-dioxa-3’,8’-dioxo-4’-aza-decyl-9’-ene) tetrahydrodicyclopentadiene, bis(2’,7’-dioxa-3’,8’-dioxo-4’-aza-9’-methyl-decyl-9’-ene) tetrahydrodicyclopentadiene, and / or mixtures thereof, and optionally 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers of the aforementioned compounds and / or mixtures of cis- and trans-isomers, and (ii.2) 21 to 38% by mass of at least one bifunctional urethane (meth)acrylate having a divalent alkylene group, and (ii.3) 0.1 to 10% by mass, in particular 0.2 to 9% by mass, of at least one tetrafunctional to decafunctional dendritic urethane methacrylate, in particular hexafunctional dendritic urethane methacrylate, and (iii) 1 to 14% by mass of at least one bifunctional, trifunctional, tetrafunctional, or polyfunctional monomer that is not a urethane (alkyl) acrylate, and the total of monomers (ii.1), (ii.2), (ii.3), and (iii) is 100% by mass in the monomer component.

[0050] According to a further preferred embodiment, the composite material may comprise (iv) 0.01 to 2% by mass of a photoinitiator for the UV and / or Vis spectral region or a photoinitiator system for the UV and / or Vis spectral region (visible light), and 0.01 to 2% by mass of a stabilizer.

[0051] Another subject of the present invention is a polymerized dental composite material obtained by polymerization of the composite material according to the present invention, in particular by UV and / or Vis radiation, preferably by Vis radiation, and particularly preferably by polymerization with a radiation source having a radiation maximum in the spectral range of 400 nm to 530 nm.

[0052] According to a particularly preferred embodiment, the subject matter of the invention is an average particle size d in the range from 0.8 to 5.5 μm 50 , preferably d of 20 μm or less, preferably less than 7.5 μm 99 of at least one dental glass and an optional at least one silane-treated amorphous metal oxide, in particular precipitated silicon dioxide and / or calcined silica having a primary particle size of 2 to 150 nm, preferably 2 to 100 nm, particularly preferably 2 to 45 nm, containing at least one inorganic filler component in an amount of 70 to 85% by mass, a polymerized mixture containing at least one bisurethane of formula I, at least one diurethane (meth)acrylate having a divalent alkylene group, at least one tetrafunctional to decafunctional dendritic urethane methacrylate, and at least one bifunctional, trifunctional, tetrafunctional, or polyfunctional methacrylic acid ester of a polyether, preferably based on dimethacrylate triethylene glycol, at least one polymer, in particular a copolymer, in an amount of 10 to 30% by mass, and at least one pigment, in particular at least one fluorescent pigment and at least one organic coloring pigment and / or at least one inorganic coloring pigment in an amount of 0.01 to 10% by mass, the coloring pigment preferably not being fluorescent, and the total of the composition of the composite material being 100% by mass.

[0053] Furthermore, the polymerized composite material can be used to produce direct dental restorations, indirect dental restorations, dental prosthetic restorations, such as crowns, inlays, onlays, superstructures, artificial teeth, dental bridges, dental bars, spacers, abutments, or veneers. The polymerized composite material can further be used as a composite material for producing directly adherent dental restorations.

[0054] The following are also considered to be preferred urethane (meth)acrylates according to the present invention: (ii) at least one urethane (meth)acrylate, in particular urethane dimethacrylate, preferably bis(methacryloxy-2-ethoxycarbonylamino)alkylene, diurethane acrylate oligomer, alkyl-functional urethane dimethacrylate oligomer, aromatic-functionalized urethane dimethacrylate oligomer, aliphatic unsaturated urethane acrylate, bis(methacryloxy-2-ethoxycarbonylamino)-substituted polyether, aromatic urethane diacrylate oligomer, aliphatic urethane diacrylate oligomer, aliphatic urethane diacrylate, hexa-functional aliphatic urethane resin, aliphatic urethane triacrylate, aliphatic urethane acrylate oligomer, unsaturated aliphatic urethane acrylate. In particular, difunctional and polyfunctional urethane (meth)acrylates such as urethane di(meth)acrylate are preferred, and at least one (iii) urethane dimethacrylate is particularly preferably selected from linear or branched alkyl-functional urethane dimethacrylate, urethane dimethacrylate-functionalized polyether, in particular 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 brand names: Ebecryl 230 (aliphatic urethane diacrylate), Actilane 9290, Craynor 9200 (diurethane acrylate oligomer), Ebecryl 210 (aromatic urethane diacrylate oligomer), Ebecryl 270 (aliphatic urethane diacrylate oligomer), Actilane 165, Actilane 250, Genomer 1122 (monofunctional urethane acrylate), Photomer 6210 (cas number 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)acrylate can preferably be selected from the urethane (meth)acrylates described above or from a mixture of at least two different, preferably at least three different, urethane (meth)acrylates described above.

[0055] At least one difunctional, trifunctional, tetrafunctional, or polyfunctional monomer that is not a urethane (alkyl)acrylate, particularly not a urethane (meth)acrylate, is preferably the following monomer, particularly bis-(2'-oxa-3'-oxo-pentyl-4'-ene) tetrahydrodicyclopentadiene (tricyclo[5.2.1. 02,6(esters of decan-dimethanol with two kinds of acrylates) and their isomers, 1,4-butanediol dimethacrylate (1,4-BDMA) or pentaerythritol tetraacrylate, bis-GMA monomer (bisphenol 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, hexyl decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and butanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, ethoxylated / propxylated bisphenol A di(meth)acrylate, a mixture containing at least one of these (meth)acrylates, and / or a copolymer containing one or at least two of the aforementioned monomers, is selected from at least one of monomer mixtures containing them.

[0056] Typical bifunctional monomers, also called crosslinking agents and / or multi-crosslinking agents, include tri- or tetra-ethylene glycol di(meth)acrylate, BDMA, 1,4-butanediol dimethacrylate (1,4-BDMA), bis-GMA monomer (the addition product of methacrylic acid and bisphenol A diglycidyl ether), diethylene glycol di(meth)acrylate, bisphenol A di(meth)acrylate, decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, hexyl decanediol di(meth)acrylate, and butanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, ethoxylated / propoaxylated bisphenol A di(meth)acrylate. The following bifunctional monomers can also be added as diluents (low-viscosity acrylates). Trifunctional and tetrafunctional monomers and / or multi-crosslinking agents include trimethylolpropane tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol tetraacrylate.

[0057] In addition to the bifunctional, trifunctional, or polyfunctional monomers containing at least one monomer, the following monomers, in particular methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, n-hexyl methacrylate, 2-phenoxyethyl methacrylate, isobornyl methacrylate, isodecyl methacrylate, polypropylene glycol monomethacrylate, tetrahydrofurfuryl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, n-hexyl acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate, isodecyl acrylate, tetrahydrofurfuryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, a monomer mixture of benzyl-, furfuryl-, or phenyl (meth)acrylate, a mixture containing at least one of these (meth)acrylates, and / or at least one of the copolymers containing one or at least two of the aforementioned monomers may be present in the composite material.

[0058] Furthermore, the subject of the present invention is a composite material preferably additionally containing at least one or more substances from the group consisting of fillers, pigments, stabilizers, modifiers, antibacterial additives, UV absorbers, thixotropic agents, catalysts, and crosslinking agents. A relatively small amount, for example, a total of 0.01 to 3.0% by mass, particularly 0.01 to 1.0% by mass, based on the total composition of the composite material, of the said additives (similarly for pigments, stabilizers, and modifiers) is used. Suitable stabilizers include, for example, hydroquinone monomethyl ether or 2,6-di-tert-butyl 4-methylphenol (BHT).

[0059] Preferably, the composite material contains, as component (iv), 0.01 to 10% by mass, particularly 0.5 to 5% by mass, preferably 0.5 to 2% by mass of at least one initiator or initiator system, preferably i) at least one photoinitiator for the UV and / or Vis spectral region, or a photoinitiator system for the UV and / or Vis spectral region, and optionally at least one stabilizer, and optionally additional conventional additives, optional pigments or dyes.

[0060] Particularly preferred photoinitiators include alpha-hydroxy phenyl ketone, benzyl dimethyl ketal or 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, ethyl 2,4,6-trimethylbenzoyl phenylphosphinate, and mixtures of at least two photoinitiators, bisacylphosphine oxides (BAPO). Alternatively, camphorquinone containing an amine selected from N,N-dimethyl p-toluidine, N,N-dihydroxyethyl p-toluidine, and diethyl p-dimethylaminobenzoate is also included.

[0061] Typical stabilizers include 2,6-di-tert-butyl 4-methylphenol (BHT) or hydroquinone monomethyl ether (MEHQ), 2-hydroxy-4-methoxybenzophenone, HALS (hindered amine light stabilizer), benzotriazole ultraviolet absorber (UVA), and hydroxyphenyltriazine (HPT). Particularly suitable stabilizers are, for example, hydroquinone monomethyl ether or 2,6-di-tert-butyl 4-methylphenol (BHT).

[0062] Peroxides, hydroxyl peroxides, optional azo compounds, or mixtures containing them are suitable as initiators, especially thermal initiators or initiator systems. Suitable thermal initiators can be used as radical initiators in the temperature range of 70 to 150 °C, preferably 90 to 150 °C. Preferred thermal initiators are dilauroyl peroxide, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, dicumyl peroxide, dicumyl hydroperoxide, 2,2'-azobisisobutyronitrile, benzyl barbituric acid derivatives, and particularly preferably, at least one initiator selected from tert-butyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, dicumyl peroxide, dicumyl hydroperoxide, azobisisobutyronitrile, benzyl barbituric acid derivatives such as phenylbenzyl barbituric acid, cyclohexylbenzyl barbituric acid.

[0063] The following initiators and / or initiator systems for self-polymerization or low-temperature polymerization are: a) at least one initiator, in particular at least one peroxide and / or azo compound, in particular LPO: dilauroyl peroxide, BPO: dibenzoyl peroxide, t-BPEH: tert-butyl peroxy-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 diethyl p-dimethylaminobenzoate, or c) at least one initiator system selected from redox systems, in particular a combination comprising dibenzoyl peroxide, dilauroyl peroxide, and camphor quinone, and an amine selected from N,N-dimethyl p-toluidine, N,N-dihydroxyethyl p-toluidine, and diethyl p-dimethylaminobenzoate. Alternatively, the initiator may be a redox system comprising a peroxide and a reducing agent selected from ascorbic acid, ascorbic acid derivatives, barbituric acid or barbituric acid derivatives, sulfinic acid, sulfinic acid derivatives, particularly preferably a redox system comprising (i) barbituric acid or thiobarbituric acid or barbituric acid derivatives or thiobarbituric acid derivatives, (ii) at least one copper salt or copper complex, and (iii) at least one compound having an ionic halogen atom, particularly preferably a redox system comprising 1-benzyl 5-phenylbarbituric acid, copper acetylacetonate, and benzyl dibutylammonium chloride. Particularly preferably, the polymerization in the two-component complementary base material is initiated by a barbituric acid derivative.

[0064] Generally, initiators for the polymerization reaction of starting mixtures for low-temperature polymerization or self-polymerization are considered to be those capable of initiating radical polymerization reactions. Preferred initiators are peroxides and azo compounds, such as the following: LPO: dilauroyl peroxide, BPO: dibenzoyl peroxide, t-BPEH: tert-butyl peroxy-2-ethylhexanoate, AIBN: 2,2’-azobis-(isobutyronitrile), DTBP: di-tert-butyl peroxide.

[0065] To accelerate the initiation of radical polymerization by peroxides, suitable activators, such as aromatic amines, can be added. Examples of suitable amines are N,N-dimethyl p-toluidine, N,N-dihydroxyethyl p-toluidine, and diethyl ester of p-dibenzylaminobenzoic acid. In this context, amines usually function as co-initiators and are usually present in an amount of up to 0.5% by mass.

[0066] The following exemplary embodiments are intended to illustrate the present invention without limiting the present invention to these examples.

[0067] Examples Exemplary embodiments: Test method for determining fracture toughness in accordance with ISO-13586:2000 Test specimens (CT specimens) in accordance with ASTM E1820-13 and ISO13586:2000. An alternative ratio of W / B2 ≤ W / B ≤ 4 is used.

[0068] The fracture toughness of the composition to be measured is determined using test specimens (CT specimens) having dimensions of W (in accordance with ASTM 1820-13) and w (in accordance with ISO 13586) = 10 mm, B (in accordance with ASTM 1820-13), and h (in accordance with ISO 13586:2000) = 5 mm, using the ratio or proportion of the dimensions of the test specimens in accordance with the standards ASTM E1820-13 and ISO 13586.

[0069] First, a test piece (cuboid) with a thickness of 5 mm and a base area / deck area of 12.0 × 12.5 mm is manufactured. Photocuring or photopolymerization is performed by irradiating blue light, respectively, and a total of 5 spots (projection surfaces) are each irradiated for 20 seconds (Translux 2 Wave, KULZER GmbH).

[0070] Using a 1 mm rotary cutting tool, a notch (about 0.55 W) is formed centered and perpendicular to the longitudinal end. The hole opened perpendicular to the base / deck area is opened to receive a pin by a 2 mm diameter cutting tool placed at the same position as that given to the test piece of (ASTM 1820 - 13 and ISO 13583:2000).

[0071] A cut is made with a pair of scissors blades above the centrally placed notch to form cracks with a diameter ≦ 8 μm. The length of the crack (a i ) is measured by an optical microscope before measurement. The changing crack length a i is measured under the influence of a specified mechanical force.

Brief Description of the Drawings

[0072]

Figure 1a

Figure 1b

[0073] Explanation of Symbols w = distance between the center points of two holes and the end of the test piece on the opposite side; B = width of the entire test piece; l1 = length; l2 = distance between the center points of two holes symmetrically arranged with respect to the crack surface + / - 0.005w; R = radius; h = thickness; a = crack length; P = force B = 1.25w ± 0.01w; l1 = 1.2w ± 0.01w, l2 = 0.55w ± 0.0005w, R = 0.125w ± 0.005w, 0.4w < h < 0.6w; 0.45w ≤ a ≤ 0.55w The pins and holes are intended to have smooth surfaces and loose fits to avoid friction.

[0074]

Number

[0075] Subsequently, the test piece is fixed to a universal testing machine (Zwick / Roell) using a metal pin guided through the hole. Subsequently, a defined tensile force (P) is applied to the test piece via the pin until it is broken at a speed of 1 mm / min. Tensile force (P), thickness (B), width (W), and crack length a i , fracture toughness K Ic is calculated according to the following formula.

[0076]

Table 1

[0077]

Table 2

[0078]

Table 3

[0079]

Table 4

[0080]

Table 5

[0081]

Table 6

[0082] A method of irradiating the surface of a test piece with blue light (emission maximum approximately 440 - 460 nm) on five projection surfaces of the surface of the test piece, one sample from each of those in Table 4 for 20 seconds. The thermosetting for additional polymerization shown in Table 4 was carried out at 95°C for about 3 hours.

[0083]

Table 7

[0084] The results of the fracture toughness measurement on a test piece with only radiation polymerization of a comparative example containing bis - GMA as a component in the polymer matrix show values (VG3a, VG3b) for very low fracture toughness, and even when combined with heat curing at 98°C for 3 hours following the preceding irradiation, it cannot be significantly improved further (VG3c, VG3d).

[0085] Even in the examples having TCD ester as a component of the polymer matrix in Examples VG1 and VG2, values already improved as compared with a matrix based on bis - GMA are shown. When using the composite material according to the present invention based on bis-(2’,7’ - dioxo - 3’,8’ - dioxo - 4’ - azadecyl - 9’ - ene)tetrahydrodicyclopentadiene and its isomers in the polymer matrix, significantly excellent values of 1.9 and 2.3 MPa·m 1 / 2 for fracture toughness are obtained.

Claims

1. A composite material for prosthetic dentistry, comprising: (i) an inorganic filler component comprising at least one dental glass and optionally at least one amorphous metal oxide, in an amount of 40 to 90% by mass; (ii) a mixture of at least two different urethane acrylates and / or urethane alkyl acrylates, said mixture comprising a urethane acrylate and / or urethane alkyl acrylate having a divalent alicyclic group of formula I 【Chemical 1】 [R １ and R ２ are each independently selected from H or alkyl having 1 to 8 C atoms] of one kind or a mixture, and and at least one other difunctional urethane acrylate selected from difunctional urethane acrylates and difunctional urethane alkyl acrylates having a divalent alkylene group containing an alkylene group of 1 to 10 C atoms and an alkylene group of 3 to 20 C atoms, and optionally at least one at least tetrafunctional dendritic urethane acrylate and / or at least tetrafunctional dendritic urethane alkyl acrylate, in an amount of 10 to 60% by mass; (iii) at least one difunctional, trifunctional, tetrafunctional or polyfunctional monomer, which is neither a urethane acrylate nor a urethane alkyl acrylate, in an amount of 0.01 to 15% by mass; (iv) at least one initiator, initiator system, and optionally at least one stabilizer and optionally at least one pigment, in an amount of 0.01 to 10% by mass; wherein the total composition of the composite material is 100% by mass. A composite material for prosthetic dentistry.

2. (i) an inorganic filler component comprising at least one dental glass and optionally at least one amorphous metal oxide, in an amount of 70 to 85% by mass; (ii) a mixture of at least two different urethane acrylates and / or urethane alkyl acrylates, said mixture comprising a difunctional urethane acrylate and / or urethane alkyl acrylate having a divalent alicyclic group of formula I 【Chemical 2】 One kind or a mixture thereof [R １ and R ２ are each independently selected from H or alkyl having 1 to 8 C atoms], and 10 to 30% by mass of a mixture containing at least one other bifunctional urethane acrylate selected from bifunctional urethane acrylate having a divalent alkylene group containing an alkyl of 1 to 10 C atoms and an alkylene of 3 to 20 C atoms (iii) at least one difunctional, trifunctional, tetrafunctional or polyfunctional monomer, which is neither a urethane acrylate nor a urethane alkyl acrylate, in an amount of 0.01 to 5% by mass; (iv) at least one initiator, initiator system, and optionally at least one stabilizer and optionally at least one pigment, in an amount of 0.01 to 10% by mass; The composite material for prosthetic dentistry according to claim 1, characterized in that the total composition of the composite material is 100% by mass.

3. The at least one dental glass has an average particle size d of 0.5 to 10 μm ５０ The dental composite material according to claim 1 or 2, characterized in that it has ５０ .

4. a) the dental glass has an average particle size d50 of 1.8 μm, or b) the dental glass contains a mixture of dental glasses having an average particle size of i) d of 2 to 8 μm ５０ , ii) d of 1.0 to 2.0 μm ５０ , and iii) d of 0.5 to 2 μm ５０ and the fractions of i) to ii) to iii) are present in a ratio of 1 to 4:1:4 to 8 A dental composite material according to any one of claims 1 to 3, characterized in that.

5. The amorphous metal oxide contains at least one non-aggregated amorphous metal oxide having a primary particle size of 2 to 150 nm, and the amorphous metal oxide optionally contains precipitated silicon oxide, calcined silica, zirconium oxide, or a mixed oxide. A dental composite material according to any one of claims 1 to 4, characterized in that.

6. The composite material is (i) as an inorganic filler component, based on the total of 100% by mass of the composition of the composite material, (i.1) 70 to 84% by mass of at least one dental glass, and optionally, (i.2) 2 to 10% by mass of amorphous metal oxide, A dental composite material according to any one of claims 1 to 5, characterized by containing.

7. (ii) contains a mixture of at least three different urethane acrylates and / or urethane alkyl acrylates, the mixture comprising at least one bifunctional urethane acrylate and / or urethane alkyl acrylate having a divalent alicyclic group of formula I and a bifunctional urethane alkyl acrylate having a divalent alkylene group containing an alkyl of 1 to 10 C atoms and an alkylene of 3 to 20 C atoms. And optionally at least one at least tetrafunctional dendritic urethane acrylate and / or at least tetrafunctional dendritic urethane alkyl acrylate. A dental composite material according to any one of claims 1 to 6, characterized in that.

8. (iii) is selected from dimethacrylic acid esters of polyethers, methacrylic acid esters of trifunctional, tetrafunctional, or polyfunctional polyethers, and bis-(2'-oxa-3'-oxo-pentyl-4'-ene) tetrahydrodicyclopentadiene. A dental composite material according to any one of claims 1 to 7, characterized in that.

9. The dental composite material according to any one of claims 1 to 8, characterized in that the at least one stabilizer contains water, at least one benzophenone derivative, and / or at least one phenol derivative.

10. The dental composite material according to any one of claims 1 to 9, characterized in that (v) contains 0.01 to 15% by mass of polymer particle fillers, and the total composition of the composite material is 100% by mass.

11. A polymerized dental composite material obtained by polymerizing the composite material according to any one of claims 1 to 10 using i) a UV and / or VIS radiation source and / or ii) a pressure of 50 to 300 MPa and / or iii) a high temperature.

12. An average particle size d of 0.5 to 10 μm ５０ At least one inorganic filler component containing at least one dental glass of ５０ and a silane-treated amorphous metal oxide having a primary particle size of optionally 2 to 150 nm is 40 to 90% by mass, Containing at least one difunctional urethane acrylate having a divalent alicyclic group and / or a urethane alkyl acrylate having a divalent alicyclic group, and / or a urethane alkyl acrylate having a divalent alkylene group containing an alkyl of 1 to 10 C atoms and an alkylene of 3 to 20 C atoms, and at least one other difunctional urethane acrylate selected from difunctional urethane acrylates having a divalent alkylene group, and optionally, at least one polymer based on at least one tetrafunctional dendritic urethane acrylate and / or at least one tetrafunctional dendritic urethane alkyl acrylate, 10 to 60% by mass, At least one tetrafunctional to decafunctional dendritic urethane methacrylate, and at least one difunctional, trifunctional, tetrafunctional, or polyfunctional methacrylic acid ester of a polyether, 0.01 to 15.0% by mass, and At least one pigment, 0.01 to 10% by mass, The polymerized dental composite material according to claim 11, with the total composition of the composite material being 100% by mass.

13. The polymerized dental composite material according to claim 11 or 12, characterized in that the polymerized dental composite material exists in the form of a block of the material or as a milling blank having an adapter for attachment to an automated device removal material.

14. Use of the dental composite material according to any one of claims 1 to 13 as a product for use in a material removal process, for manufacturing dental filling materials, dental prosthetic restorations, or as a bone cement for hoof repair materials, as a bone cement for cementing artificial joint prostheses, orthodontic devices and appliances, or for manufacturing direct adhesive dental restorations.

15. Use according to claim 14 for manufacturing a dental prosthetic restoration comprising a crown, inlay, onlay, superstructure, artificial tooth, dental bridge, dental bar, spacer, abutment, or veneer.

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