Overlapping components

Abstract

The present invention provides a polymerizable composition, comprising: (i) 0 to 90% by weight of at least one inorganic filler component; (ii) 5 to 99.98 wt. % of at least one urethane(alkyl)acrylate of idealized Formula I; (iii) 0.01 to 25% 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 wherein the total composition of said composition is 100 wt. %, as well as polymerized compositions having improved fracture toughness.

Description

[Technical Field]

[0001] The present invention provides a polymerizable composition, comprising: (i) 0 to 90% by weight of at least one inorganic filler component; (ii) 5 to 99.98 wt. % of at least one urethane(alkyl)acrylate of idealized Formula I; (iii) 0.01 to 25% 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; wherein the total of the components of the composition is 100% by weight, and the polymerized composition has improved fracture toughness and preferably high flexural strength, respectively, and optionally low shrinkage when fabricating large three-dimensional articles or objects, optionally greater than 5 cm in at least one of three dimensions.

[0002] The object of the present invention was to provide a polymerizable composition suitable for the production of three-dimensional articles obtained by a casting process, particularly for use in stereolithography, DLP, or multi-jet (MJM) or polyjet processes. Furthermore, the composition should also be suitable for the production of large blocks of material, especially geometrically shaped objects such as milled blocks. Furthermore, the polymerizable composition should have a good fracture toughness value, which represents a measure of the force required for crack propagation in the material. Additionally, it was an objective to provide a composition with a uniform, monochromatic coloration before and after polymerization. In this context, it should be possible to achieve a uniform, monochromatic coloration not only when producing small articles, but also in larger articles. Furthermore, it should be possible to produce multicolored, i.e., multicolored blocks of material with defined colorations, by a casting or casting process. Additionally, it is necessary to provide a composition that is free-flowing in the unpolymerized state and has excellent mechanical properties when polymerized by UV or VIS radiation. It is also necessary to provide a composition that exhibits low shrinkage in the polymerized state, even when producing larger blocks of material.

[0003] Based on the prior art, a novel composition has been developed, which comprises a novel urethane derivative having three fused rings. The present invention also relates to a composition according to claim 1, a polymerized composition according to claim 13, and a use according to claim 14. Preferred embodiments are detailed in the respective dependent claims and in the detailed description of the invention.

[0004] The particle size distribution can be fairly broad for high filler packing density and good mechanical properties, or fairly narrow for specific applications, depending on the desired filler content.

[0005] Compositions of TCD esters with reduced shrinkage and good flexural strength are known. Surprisingly, very good values ​​of fracture toughness (measured according to ISO 13586:2000) can be exhibited in radiation-cured compositions comprising the polymerization product of a urethane of idealized Formula I, particularly idealized Formula Ia, preferably after radiation curing.

[0006] The subject of the present invention is (i) 0 to 90% by weight of at least one inorganic filler component; (ii) 5 to 99.98 wt. % of at least one urethane acrylate having a divalent alicyclic group of idealized formula I [ka] [R 1 and R 2 are each independently selected from H and alkyl having 1 to 8 C atoms], and / or at least one urethane acrylate comprising a mixture of urethanes of formula I as above, and optionally a mixture of isomers of said compounds, (iii) 0.01 to 25% by weight of at least one difunctional, trifunctional, tetrafunctional, or polyfunctional monomer that is not a urethane acrylate or 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; The total composition of the composite material is 100% by mass.

[0007] In this case, (ii) preferably comprises at least two, preferably three, different urethane acrylates. Particularly preferably, (ii) combined with (iii) is selected from methacrylic acid esters of di-, tri-, tetra-, or polyfunctional polyethers, preferably dimethacrylate triethylene glycol, dimethacrylate tetraethylene glycol, and / or bis-(2'-oxa-3'-oxo-pentyl-4'-ene)tetrahydrodicyclopentadiene and its isomers.

[0008] A preferred composition is (i) 5 to 90% by weight of an inorganic filler component comprising at least one glass having an average particle size of 0.2 μm to 10 μm, one crystalline silicate, such as quartz, feldspar, a metal oxide, such as a crystalline and / or amorphous metal oxide, a mixed oxide, such as a crystalline and / or amorphous mixed oxide, silicon dioxide, zirconium dioxide, zinc oxide, and / or a mixture of at least two of the aforementioned components, and optionally at least one amorphous metal oxide having an average primary particle size of 10 nm to 115 nm, in particular an average primary particle size of 2 nm to 100 nm, particularly preferably an average primary particle size of 2 to 45 nm, and (ii) 5 to 85% by weight, in particular 10 to 85% by weight, of at least one urethane acrylate or a mixture of urethane acrylates, (iii) 0.01 to 25% by weight of at least one difunctional, trifunctional, tetrafunctional, or polyfunctional monomer that is not a urethane acrylate and / or 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; The total amount of the composition is 100% by mass.

[0009] A further preferred composition is (i) 40 to 90% by weight of an inorganic filler component comprising at least one glass, silicate, quartz, feldspar, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide, and / or zinc oxide having an average particle size of 0.4 μm to 10 μm, and optionally at least one amorphous metal oxide having an average primary particle size of 10 nm to 115 nm; and (ii) 5 to 60% by weight, in particular 5 to 30% by weight, or preferably 10 to 60% by weight, of at least one urethane acrylate having a divalent alicyclic group of idealized formula I [ka] [R 1 and R 2 are each independently selected from H and alkyl having 1 to 8 C atoms], and / or at least one urethane acrylate comprising a mixture of urethanes of formula I as above, and optionally a mixture of isomers of said compounds, (iii) 0.01 to 15% by weight of at least one difunctional, trifunctional, tetrafunctional, or polyfunctional monomer that is not a urethane acrylate or 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; The total composition of the composite material is 100 mass %.

[0010] Furthermore, the subject of the present invention is (i) 65 to 85% by weight, in particular 70 to 85% by weight, of an inorganic filler component comprising at least one glass, silicate, quartz, feldspar, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide, and / or zinc oxide having an average particle size of 0.4 μm to 10 μm, preferably 0.4 to 7.5 μm, or a mixture of at least two of these components, and optionally at least one amorphous metal oxide having an average primary particle size of 10 nm to 115 nm, in particular 2 to 100 nm; and (ii) 10 to 35% by weight, in particular 10 to 30% by weight, of at least one urethane acrylate having a divalent alicyclic group of idealized formula I [ka] [R 1 and R 2 are each independently selected from H and alkyl having 1 to 8 C atoms], and / or at least one urethane acrylate comprising a mixture of urethanes of formula I as above, and optionally a mixture of isomers of said compounds, (iii) 0.01 to 5% by weight of at least one difunctional, trifunctional, tetrafunctional, or polyfunctional monomer that is not a urethane acrylate and / or 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; The total composition of the composite material is 100 mass %.

[0011] The subject of the present invention is (i) 0 to 90% by mass, particularly 0 to 35% by mass, and preferably 0.5 to 35% by mass of an average particle size d 50 and optionally at least one amorphous metal oxide having a primary particle size of 2 nm to 150 nm; (ii) mixtures of at least one urethane acrylate, in particular at least one difunctional urethane acrylate having a divalent alicyclic group comprising an idealized urethane of formula I, and difunctional urethane alkyl acrylates, comprising from 10 to 85% by weight, in particular from 10 to 65% by weight, preferably from 12 to 65% by weight, of at least one urethane acrylate having an idealized divalent alicyclic group of formula I, preferably a mixture of at least two different urethane acrylates, and / or mixtures of urethanes of formula I, and optionally mixtures of isomers of urethanes of formula I (see also formula Ia), in particular mixtures of the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or cis- and trans-isomers of said compounds [R 1 and R 2 are each independently selected from H and alkyl having 1 to 8 C atoms], preferably mixtures of at least three different urethane acrylates and / or urethane alkyl acrylates, in particular including di- to deca-functional urethane acrylates, (iii) 0.01 to 25% by weight, in particular 0.01 to 10% by weight, preferably 0.1 to 5% by weight, of at least one di-, tri-, tetra- or polyfunctional monomer which is not a urethane acrylate or a urethane(alkyl)acrylate, in particular not a urethane(meth)acrylate, preferably a methacrylic acid ester of a di-, tri-, tetra- or polyfunctional polyether, preferably selected from dimethacrylate triethylene glycol, dimethacrylate tetraethylene glycol, 2,2-bis-[4-(2-hydroxy-3-methacryloyloxy-propoxy)phenyl]propane and / or bis-(2'-oxa-3'-oxo-pentyl-4'-ene)tetrahydrodicyclopentadiene and its isomers, (iv) 0.01 to 10% by weight of at least one initiator, initiator system, and optionally a stabilizer and optionally at least one pigment, in particular a fluorescent pigment and a colored pigment; The total of the components of the composition is 100% by weight.

[0012] The idealized urethane of formula I is given as cascode number 94 5656-78-0 (2-propenoic acid, 1,1'-[(octahydro-4,7-methano-1H-indene-5,?-diyl)bis(methyleneoxycarbonylamino-2,1-ethanediyl)] ester). Alternatively, this formula can be depicted graphically as follows: [ka]

[0013] The difunctional urethane acrylate is preferably selected from difunctional urethane acrylates having a divalent alkylene group, preferably including difunctional urethane alkyl acrylates having a divalent alkylene group containing alkyl 1 to 10 C atoms and alkylene 3 to 20 C atoms.

[0014] Particularly preferred compositions are (i) 70 to 85% by weight, based on the total weight of the composition, of an inorganic filler component comprising at least one silicate, quartz, feldspar, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide, and / or zinc oxide having an average particle size of 0.4 μm to 10 μm, in particular 0.4 to 7.5 μm, optionally glass, or a mixture of at least two of these components, and optionally at least one amorphous metal oxide, in particular 0.05% to less than 10% by weight, preferably less than 4% by weight, particularly preferably 0.05 to 2% by weight, and even more preferably less than 1% by weight of amorphous metal oxide; (ii) 10 to 30 weight percent of a mixture of at least two different urethane acrylates, represented by idealized formula I, where R 1 and R 2are each independently selected from H and alkyl having 1 to 8 C atoms], and / or mixtures comprising mixtures of urethanes of formula I as described above, and optionally mixtures of isomers of said compounds, (iii) 0.01 to 5% by weight of at least one difunctional, trifunctional, tetrafunctional, or polyfunctional monomer that is not a urethane acrylate and / or 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; The total amount of the composition is 100% by mass.

[0015] Further particularly preferred compositions are (i) As an inorganic filler component, an average particle size d of 0.5 μm to 10 μm, preferably 0.7 to 7.5 μm, particularly 0.7 to 5.5 μm, preferably 0.8 to 5.5 μm 50 a filler component functionalized with methacrylate groups selected from silicates, quartz, feldspar, metal oxides, mixed oxides, silicon dioxide, zirconium dioxide and / or zinc oxide, optionally glass, or mixtures thereof, and optionally at least 0.05 to 4% by weight, in particular 0.05 to 2% by weight, preferably 0.05 to 1% by weight, based on the total composition, of amorphous metal oxides comprising silicon dioxide, precipitated silicon dioxide, pyrogenic silica, zirconium oxide, mixed oxides, or mixtures thereof, preferably with a primary particle size of 2 to 150 nm, in particular 2 to 100 nm, preferably 2 to 45 nm, in particular non-aggregated amorphous metal oxides including silanized metal oxides, (ii) mixtures of at least two different urethane acrylates, in particular mixtures of at least one difunctional urethane acrylate or difunctional urethane alkyl acrylate having a divalent cycloaliphatic group, including idealized urethanes of formula I, and / or mixtures of urethanes of formula I, and optionally mixtures of isomers of urethanes of formula I (see also formula Ia), in particular mixtures of the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or cis- and trans-isomers of said compounds [R 1 and R 2 are each independently selected from H and alkyl having 1 to 8 C atoms], preferably mixtures of at least three different urethane acrylates and / or urethane alkyl acrylates, in particular including di- to deca-functional urethane acrylates, (iii) at least one di-, tri-, tetra- or polyfunctional monomer which is not a urethane acrylate or urethane(alkyl)acrylate, in particular not a urethane(methyl)acrylate, selected from methacrylic acid esters of polyfunctional polyethers, preferably dimethacrylate triethylene glycol, dimethacrylate tetraethylene glycol, 2,2-bis-[4-(2-hydroxy-3-methacryloyloxy-propoxy)phenyl]propane and / or bis-(2'-oxa-3'-oxo-pentyl-4'-ene)tetrahydrodicyclopentadiene and its isomers, and pentaerythritol tetrapropoxyacrylate, (iv) at least one initiator, initiator system, and optionally at least one stabilizer, and optionally at least one pigment, in particular at least one pigment comprising titanium dioxide; Includes.

[0016] The amounts of the above components can be allocated to the above and below contents within the total composition of 100% by mass.

[0017] In one embodiment variant, the polymerizable compositions are preferably photochemically polymerizable. Alternatively, the polymerizable compositions are preferably thermally polymerizable. Particularly preferably, the compositions are photochemically and thermally polymerizable, in particular dual-polymerizable. Photochemically polymerizable compositions are understood to mean compositions that can be polymerized by a UV and / or Vis radiation source having an emission maximum in the spectral range of 360 nm to 530 nm, preferably in the spectral range of 400 to 500 nm. Particularly preferably, the composition is irradiated by a pulsed UV and / or Vis radiation source, in particular for 50 milliseconds or more, preferably 10 seconds or more, per projection of the radiation source. Irradiation for 15 seconds to 5 minutes, preferably 10 to 30 seconds, per projection of the radiation source is even more preferred. Suitable radiation sources typically have an emission wavelength, preferably an emission maximum, in the spectral range of 400 to 480 nm, and a power of 500 mW / cm. 2 The pulsed irradiation may be in the amount of less than 1 second per radiation pulse if very thin layers are used. Radiation sources comprising LED lamps are particularly preferred.

[0018] A thermally polymerizable composition is understood in the present specification to mean a composition that can be polymerized at temperatures from 60° C. to 150° C., preferably from 70° C. to 150° C., particularly preferably from 90 to 150° C. In this connection, it is further preferred according to the invention that the volume shrinkage rate is small.

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

[0020] The following glasses are preferably considered: aluminum silicate or fluorosilicate glasses, boron-containing aluminum fluorosilicate glasses, barium aluminum silicate, strontium silicate, strontium borosilicate, calcium silicate, calcium borosilicate, sodium silicate glasses, potassium silicate glasses, lithium silicate and / or lithium aluminum silicate, as well as mixtures of at least two of the aforementioned glasses. Amorphous spherical fillers based on oxides or mixed oxides, such as amorphous SiO, ZrO, or mixed oxides of SiO and ZrO, can be used as metal oxides or mixtures of amorphous metal oxides. Alternatively, mixed oxides of zirconium dioxide and silicon dioxide, zirconium dioxide or zinc oxide, and crystalline silicates can also be used as filler components in the composition.

[0021] The subject of the present invention is a) Mean particle size d of 1.8 μm, plus / minus 0.25 μm 50 , preferably d of 20 μm or less 99 or b) i) a d of 2 to 8 μm, optionally plus / minus 0.5 μm, in particular 4 to 6 μm, optionally plus / minus 0.25 μm50 ii) a d of 1.0 to 2.0 μm, optionally plus or minus 0.25 μm, in particular 1.2 to 2.0 μm, optionally plus or minus 0.5 μm, preferably 1.5 μm, optionally plus or minus 0.15 μm. 50 and iii) d between 0.5 and 1.2 μm, optionally plus or minus 0.15 μm, d between 0.7 and 0.9 μm, optionally plus or minus 0.5 μm. 50 a mixture of different fractions of the aforementioned components having an average particle size of: i) to ii) to iii) in which the fractions i) to ii) to iii) are present in a ratio of 1-4:1:4-8, in particular 2-3:1:6-7, The composition also contains a filler component selected from filler components functionalized with methacrylate groups, in particular silicates such as quartz and / or feldspar, metal oxides, mixed oxides, silicon dioxide, zirconium dioxide, and / or zinc oxide, optionally glass, or a mixture of components, i) a 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) a d of 0.85 μm, optionally plus / minus 0.15 μm. 50 is particularly preferred, with the fractions i) to ii) to iii) being present in a ratio of 1-4:1:4-8, especially 2-3:1:6-7.

[0022] According to a preferred embodiment, the filler component has an average particle size d of 0.7 to 2.0 μm, in particular 1.2 to 2.0 μm. 50 , preferably with an average particle size of 1.35 to 1.95 μm, in particular 1.8 μm, optionally with a d of plus / minus 0.15 μm 50 , preferably d of 10 μm or less 99Preferably, at least one filler component is selected from filler components functionalized with methacrylate groups, in particular silicates, such as quartz and / or feldspar, metal oxides, mixed oxides, silicon dioxide, zirconium dioxide, and / or zinc oxide, optionally glass, or mixtures of these components, with an average particle size of about 0.85 μm, optionally plus / minus 0.1 μm, in particular plus / minus 0.05 μm, preferably plus / minus 0.03 μm. 50 , and preferably d of 10 μm or less 99 The filler components functionalized with methacrylate groups are selected from silicates, such as quartz and / or feldspar, metal oxides, mixed oxides, silicon dioxide, zirconium dioxide, and / or zinc oxide, optionally glass, or mixtures of components, with an average particle size of 0.2 μm or more. Particularly preferred particle size distributions are those with a d of 0.2 μm or more. 10 to 20 μm or less, preferably 7.5 μm or less 99 , preferably d of 0.4 μm or more 10 to 7.5 μm or less d 99 , and an average diameter d of 0.7 to 7.5 μm 50 may be in the range of

[0023] According to a preferred embodiment, the composition comprises: (i) a mean particle size d of 0.7 to 2.0 μm; 50 and 70 to 85% by weight or 5 to 35% by weight of at least one inorganic filler component selected from methacrylate-functionalized filler components, in particular silicates, such as quartz and / or feldspar, metal oxides, mixed oxides, silicon dioxide, zirconium dioxide, and / or zinc oxide, optionally glass, or mixtures of components, which is present in an amount of 50 to 80% by weight, in particular 55 to 76% by weight, preferably 60 to 75% by weight, and particularly preferably 60 to 71% by weight of the total 100% composition, based on the total 100% composition.

[0024] More preferably, each of these is combined with 4 to 7.5% by weight of amorphous silicon dioxide in the total composition. Preferably, the amorphous metal oxide is a 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, and the amorphous metal oxide comprises silicon dioxide, precipitated silicon dioxide, pyrogenic silica, zirconium oxide, mixed oxides, or mixtures thereof, especially silanized metal oxides.

[0025] In a preferred alternative embodiment, the composition may contain, in addition to the inorganic filler component, a certain amount of polymeric particulate filler. The total amount of such polymeric particulate filler may be 0.01 to 15% by weight, preferably 0.5 to 10% by weight, based on the total composition of 100% by weight of the composition. The particle size of the polymeric filler is preferably in the range of 10 to 200 micrometers, particularly 30 to 90 micrometers, and particularly preferably 20 to 50 micrometers.

[0026] According to a particularly preferred embodiment variant, the composition comprises, as component (ii), a mixture of at least three different urethane acrylates and / or urethane alkyl acrylates, in particular a mixture of di- to deca-functional urethane acrylates and / or corresponding urethane alkyl acrylates, preferably 15 to 19% by weight of the urethane of the idealized formula I [ka] and / or mixtures of urethanes of formula I and isomers thereof, in particular of formula Ia [ka] the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers of the compound and / or a mixture of the cis- and trans-isomers of the compound [R 1 and R 2are each independently selected from H and alkyl having 1 to 8 C atoms], and 5 to 6% by weight of a difunctional urethane acrylate having a divalent alicyclic group containing alkyl 1 to 10 C atoms and alkylene 3 to 20 C atoms, and optionally 0.1 to 2% by weight of each of at least one hexafunctional urethane acrylate and / or hexafunctional urethane methacrylate or dendritic urethane methacrylate, and (iii) at least one di-, tri-, tetra- or polyfunctional monomer which is neither a urethane acrylate nor a urethane alkyl acrylate, in particular at least one methacrylic acid ester of a di-, tri-, tetra- or polyfunctional polyether, preferably dimethacrylate triethylene glycol, dimethacrylate tetraethylene glycol, 2,2-bis-[4-(2-hydroxy-3-methacryloyloxy-propoxy)phenyl]propane, pentaerythritol tetrapropoxyacrylate and / or bis-(2'-oxa-3'-oxo-pentyl-4'-ene)tetrahydro-dicyclopentadiene and its isomers, and (iv) at least one initiator or initiator system, preferably a) 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 / or b) at least one thermal initiator or thermal initiator system, and c) optionally at least one stabilizer, and iv) optionally at least one pigment, preferably depending on the above content in the overall composition.

[0027] Di- to deca-functional urethane acrylates or di- to deca-functional urethane alkyl acrylates are used as monomers and do not contain peroxy groups.

[0028] According to a particularly preferred embodiment variant, the composition comprises (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 5 to 99.98% by weight, in particular 5 to 85% by weight, of at least one difunctional urethane acrylate and / or urethane alkyl acrylate composition comprising a urethane of idealized formula I (see also formula Ia) and / or a mixture of urethanes of said formula I, and optionally a mixture of the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or cis- and trans-isomers of said compounds [R 1 and R 2 are each independently selected from H and alkyl having 1 to 8 C atoms, preferably H or methyl], as well as difunctional urethane acrylates and / or urethane alkyl acrylates having a divalent alkylene group with alkyl of 1 to 10 C atoms, preferably alkyl equal to methyl, and alkylene having 3 to 20 C atoms, preferably three different urethane(alkyl)acrylates, and optionally at least one at least tetrafunctional dendritic urethane(alkyl)acrylate, preferably at least one hexafunctional dendritic urethane(alkyl)acrylate, in particular a urethane(meth)acrylate.

[0029] According to a particularly preferred embodiment variant, the composition comprises (ii) a mixture comprising at least one difunctional urethane acrylate and / or urethane alkyl acrylate, comprising an idealized urethane of formula I, and / or a mixture of said urethanes of formula I and optionally a mixture of the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or cis- and trans-isomers of said compounds [R 1 and R 2are each independently selected from H and alkyl having 1 to 8 C atoms], for example at least one difunctional urethane acrylate having a divalent alicyclic group selected from 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-decyl-9'-ene)tetrahydrodicyclopentadiene, and / or mixtures thereof; The composition comprises 5 to 99.98% by weight of a mixture of at least two different urethane acrylates selected from at least one difunctional urethane (meth)acrylate having a divalent cycloaliphatic group, optionally a mixture of the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or cis- and trans-isomers of said compound, and at least one additional difunctional urethane (meth)acrylate, in particular at least one difunctional urethane acrylate having a divalent cycloaliphatic group and / or a urethane methacrylate having a divalent cycloaliphatic group, and optionally at least one at least pentafunctional dendritic urethane acrylate and / or corresponding urethane methacrylate, preferably at least one hexafunctional dendritic urethane acrylate and / or urethane methacrylate. Particularly preferred are at least three different urethane (meth)acrylates selected from urethane acrylates and urethane methacrylates (based on 100% by weight of the total composition).

[0030] The terms (alkyl)acrylate or (meth)acrylate or urethane(alkyl)acrylate containing (alkyl) in parentheses, or the term urethane(meth)acrylate containing (meth) in parentheses, mean that they may include acrylates or urethane acrylates with or without alkyl or methyl groups. In the urethane alkyl acrylates, the alkyl group preferably contains 1 to 10 C atoms, preferably 1 to 2 C atoms. In the (alkyl)acrylates, the alkyl group preferably contains 1 to 10 C atoms, preferably 1 to 2 C atoms.

[0031] According to a particularly preferred embodiment variant, the composition comprises ii) at least difunctional urethane acrylates and / or difunctional urethane methacrylates of general formula I and at least one difunctional urethane acrylate and / or difunctional urethane methacrylate having divalent alkylene groups, and optionally at least one at least tetrafunctional dendritic urethane acrylate and / or tetrafunctional dendritic urethane methacrylate, preferably at least one hexafunctional dendritic acrylate and / or urethane methacrylate. A mixture of at least two different urethane acrylates, preferably at least three different urethane (meth)acrylates, each containing urethane methacrylate, is present in an amount of 5 to 99.98% by weight, particularly 61 to 99.98% by weight, or alternatively 5% to less than 10% by weight, with component (i) being present in an amount of 0% to 38.98% by weight, alternatively 94.98% to 89.98% by weight, (iii) being present in an amount of 0.01 to 10% by weight, and (iv) being present in an amount of 0.01 to 10% by weight, adapted in accordance with the present disclosure, the total of the composition being 100% by weight.

[0032] According to the present invention, the urethane acrylates having divalent cycloaliphatic groups are idealized urethanes of formula I, and / or mixtures of urethanes of formula I, and optionally mixtures of the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or cis- and trans-isomers of said compounds [R 1 and R 2are each independently selected from H and alkyl having 1 to 8 C atoms, for example, preferably selected from 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, particularly preferably bis-(2',7'-dioxa-3',8'-dioxo-4'-aza-decyl-9'-ene)tetrahydrodicyclopentadiene. Urethanes of formula I can be obtained by reacting the corresponding tetrahydrodicyclopentadiene, which is twice substituted with hydroxymethylene groups, with the corresponding isocyanate of an acrylic derivative, such as 2-isocyanatoethyl methacrylate.

[0033] The difunctional urethane (alkyl)acrylate, urethane (alkyl)acrylate having a divalent alkylene group, or urethane (meth)acrylate having a divalent alicyclic group is preferably selected from linear or branched urethane dimethacrylates functionalized with divalent alkylene groups, and urethane dimethacrylate-functionalized polyethers having alkylene groups, 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, and UDMA (also known as HEMA-TDMI). Bis(methacryloxy-2-ethoxycarbonylamino)alkylenes in which the alkylene groups are linear or branched and contain C3 to C20, preferably C3 to C6, are preferred, and methyl-substituted alkylenes, such as HEMA-TMDI, are particularly preferred. Divalent alkylene preferably includes 2,2,4-trimethylhexamethylene and / or 2,4,4-trimethylhexamethylene.

[0034] The at least tetrafunctional dendritic urethane methacrylates include tetrafunctional to decafunctional dendritic urethane methacrylates.

[0035] Preferably, the composition contains, as component (i), from 5 to 65% by weight, in particular from 40 to 70% by weight, or alternatively from 5% to less than 10% by weight, 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 of the aforementioned compounds, based on the total composition. The composition comprises a mixture of 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or cis- and trans-isomers, 1 to 15% by weight, in particular 5 to 6% by weight, of UDMA (1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane) or HEMA-TMDI, and optionally 0.1 to 5% by weight, preferably 0.2 to 2% by weight, and particularly preferably 0.1 to 1% by weight, of at least one tetrafunctional to decafunctional dendritic urethane methacrylate.

[0036] According to a further preferred embodiment, the composition contains as component (iii) 0.01 to 5% by mass of at least one di-, tri-, tetra-, or polyfunctional monomer which is not a urethane(alkyl)acrylate and is selected from dimethacrylate esters of polyethers, bis-(2'-oxa-3'-oxo-pentyl-4'-ene)tetrahydrodicyclopentadiene and its isomers, and methacrylate esters of tri-, tetra-, or polyfunctional polyethers.

[0037] Preferably, the content of component (iii) is 0.15 to 15% by mass, particularly 0.15 to 5% by mass, and particularly preferably 1.0 to 2% by mass, and component (iii) is selected from dimethacrylate esters of polyethers, such as, preferably, dimethacrylated polyethylene glycol and dimethacrylated polypropylene glycol. Dimethacrylated triethylene glycol (TEGDMA), diethylene glycol dimethacrylate (DEGMA), and dimethacrylated tetraethylene glycol (TEDMA) are particularly preferred.

[0038] Water can be added to the composition as a stabilizer to improve consistency and flow properties for process engineering processability. The stabilizer is preferably added to the composition to prevent premature polymerization and provide the material with a certain shelf life. The composition preferably contains, as the stabilizer in component (iv), at least one stabilizer selected from water, at least one benzophenone derivative, preferably an alkoxy-substituted benzophenone and / or phenol derivative, such as 2-hydroxy-4-methoxybenzophenone, 2,6-bis(1,1-dimethyl)-4-methylphenol, or a mixture of three stabilizers. The stabilizer is preferably present in an amount of 0.01 to 10% by weight, particularly preferably 0.7 to 10% by weight, and especially preferably 0.5 to 2% by weight, of the total composition. Furthermore, the composition preferably contains 0.01 to 2% by weight of water as a stabilizer, preferably 0.1 to 1.0% by weight.

[0039] For optimal adjustment of the color and natural aesthetic appearance of the polymerized composition, at least one pigment can be added, including at least one fluorescent pigment and optionally at least one organic color pigment and / or at least one inorganic color pigment, such as titanium dioxide, in particular non-fluorescent color pigments. The at least one fluorescent pigment is preferably an organic fluorescent pigment, in particular a non-polymerizable organic fluorescent pigment, where appropriate, including arylcarboxylic acid esters, arylcarboxylic acids, coumarins, rhodamines, naphthalene imides, or derivatives of the respective substances. Inorganic fluorescent pigments are preferably CaAl4O7:Mn 2+, (Ba0.98Eu0.02)MgAl 10 O 17 , BaMgF4:Eu 2+ , Y(1.995)Ce(0.005)SiO5.

[0040] The composition may contain pigments, particularly color pigments, organic pigments, and inorganic pigments, such as diethyl 2,5-dihydroxyterephthalate, N,N'-bis(3,5-xylyl)perylene 3,4:9,10-bis(dicarbimidyl), copper phthalocyanine, titanate pigments, especially antimony chromium titanate (rutile structure), spinel black, especially pigments based on iron oxide black (Fe3O4) in which iron (Fe) is partially replaced by 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 dioxide. Pigments, including fluorescent and color pigments, are preferably present in the composition at 0.01 to 10% by weight, particularly preferably 0.01 to 5% by weight, and more preferably 0.01 to 1% by weight.

[0041] According to a further preferred embodiment, the composition comprises: (iv) 0.01 to 2% by weight of a photoinitiator for the UV and / or Vis spectral region or a photoinitiator system for the UV and / or Vis spectral region, and 0.01 to 2% by weight of a stabilizer.

[0042] Another subject of the present invention is a polymerized composition obtainable by polymerization of the composition according to the invention, in particular by polymerization with UV and / or Vis radiation, preferably with Vis radiation, particularly preferably with a radiation source having an emission maximum in the spectral range from 400 nm to 530 nm.

[0043] According to a particularly preferred embodiment, the subject of the invention is a granular material having an average particle size d ranging from 0.2 to 10 μm, preferably from 0.5 to 3.5 μm. 50 , preferably 20 μm or less, preferably less than 7.5 μm 99and optionally at least one silane-treated amorphous metal oxide, in particular precipitated silicon dioxide and / or pyrogenic silica having a primary particle size of 2 to 150 nm, preferably 2 to 100 nm, particularly preferably 2 to 45 nm; a polymerized mixture comprising at least one bis-urethane of formula I; at least one diurethane (meth)acrylate having a divalent alkylene group; and at least one tetrafunctional to decafunctional dendritic urethane methacrylate; A polymerized composition comprising 5.01 to 99.98% by weight of at least one polymer, in particular a copolymer, based on at least one methacrylic acid ester of a di-, tri-, tetra- or polyfunctional polyether, preferably dimethacrylate triethylene glycol, and 0.01 to 25% by weight of at least one pigment, in particular at least one fluorescent pigment, and at least one organic and / or at least one inorganic color pigment, the color pigment preferably not being fluorescent, the total of the components of the composition being 100% by weight.

[0044] Furthermore, the polymerized compositions can be used to manufacture technical components that are subjected to high mechanical loads, such as, in particular, plastic molds, nails, screws, and other components that are well known to those skilled in the art.

[0045] The following are also considered to be preferred 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, a diurethane acrylate oligomer, an alkyl-functional urethane dimethacrylate oligomer, an aromatic-functionalized urethane dimethacrylate oligomer, an aliphatic unsaturated urethane acrylate, a bis(methacryloxy-2-ethoxycarbonylamino) substituted polyether, an aromatic urethane diacrylate oligomer, an aliphatic urethane diacrylate oligomer, an aliphatic urethane diacrylate, a hexafunctional aliphatic urethane resin, an aliphatic urethane triacrylate, an aliphatic urethane acrylate oligomer, an unsaturated aliphatic urethane acrylate. In particular, di- and polyfunctional urethane (meth)acrylates such as urethane di(meth)acrylates are preferred, and the at least one (iii) urethane dimethacrylate is particularly preferably 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 trade 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 (cass 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 may 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.

[0046] The at least one di-, tri-, tetra- or polyfunctional monomer which is not a urethane(alkyl)acrylate, in particular not a urethane(meth)acrylate, is preferably one of the following monomers, in particular bis-(2'-oxa-3'-oxo-pentyl-4'-ene)tetrahydrodicyclopentadiene and its 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, hexyldecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and monomer mixtures containing butanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, ethoxylated / propoxylated bisphenol A di(meth)acrylate, mixtures comprising at least one of these (meth)acrylates, and / or copolymers comprising one or at least two of the foregoing monomers.

[0047] Typical difunctional monomers, also referred to as crosslinkers and / or multi-crosslinkers, include tri- or tetraethylene glycol di(meth)acrylate, BDMA, 1,4-butanediol dimethacrylate (1,4-BDMA), bis-GMA monomer (bisphenol 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)acrylate, and ethoxylated / propoxylated bisphenol A di(meth)acrylate. The following difunctional monomers can also be added as diluents (low-viscosity acrylates): Trifunctional and tetrafunctional monomers and / or multi-crosslinkers include trimethylolpropane tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol tetraacrylate.

[0048] In addition to the at least one di-, tri-, or polyfunctional monomer comprising the monomer, at least one of the following monomers may be present in the composition, in particular methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, n-hexyl methacrylate, 2-phenoxyethyl methacrylate, isobornyl methacrylate, isodecyl methacrylate, polypropylene glycol monomethacrylate, tetrahydrofuryl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, n-hexyl acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate, isodecyl acrylate, tetrahydrofuryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, benzyl-, furfuryl-, or phenyl (meth)acrylate monomer mixtures, mixtures comprising at least one of these (meth)acrylates, and / or copolymers comprising one or at least two of the aforementioned monomers.

[0049] The present invention also relates to compositions that preferably additionally contain at least one substance selected from the group consisting of fillers, pigments, stabilizers, conditioners, antimicrobial additives, UV absorbers, thixotropic agents, catalysts, and crosslinkers. The additives (as well as pigments, stabilizers, and conditioners) are used in relatively small amounts, for example, 0.01 to 3.0% by weight, particularly 0.01 to 1.0% by weight, based on the total composition of the composition. Suitable stabilizers include, for example, hydroquinone monomethyl ether or 2,6-di-tert-butyl 4-methylphenol (BHT).

[0050] Preferably, the composition contains, as component (iv), 0.01 to 10% by weight, in particular 0.5 to 5% by weight, preferably 0.5 to 2% by weight, 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 further customary additives, optionally pigments or dyes.

[0051] Particularly preferred photoinitiators include alpha-hydroxyphenyl ketones, benzil dimethyl ketal or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid ethyl ester, and mixtures of at least two photoinitiators, bisacylphosphine oxides (BAPO), or camphorquinone with an amine selected from N,N-dimethyl p-toluidine, N-N-dihydroxyethyl p-toluidine, and p-dimethylaminobenzoic acid diethyl ester.

[0052] Typical stabilizers include 2,6-di-tert-butyl 4-methylphenol (BHT) or hydroquinone monomethyl ether (MEHQ), 2-hydroxy-4-methoxybenzophenone, HALS (hindered amine light stabilizers), benzotriazole ultraviolet absorbers (UVA), and hydroxyphenyltriazine (HPT). Particularly suitable stabilizers are, for example, hydroquinone monomethyl ether or 2,6-di-tert-butyl 4-methylphenol (BHT).

[0053] Peroxides, hydroxyl peroxides, optionally azo compounds, or mixtures containing them are suitable as initiators, particularly thermal initiators or initiator systems. Suitable thermal initiators can be used as radical initiators at temperatures ranging from 70 to 150°C, preferably from 90 to 150°C. Preferred thermal initiators include at least one initiator selected from dilauroyl peroxide, di-tert-butyl peroxide, tert-butylperoxy-2-ethylhexanoate, dibenzoyl peroxide, dicumyl peroxide, dicumyl hydroperoxide, 2,2'-azobisisobutyronitrile, and benzyl barbituric acid derivatives, particularly preferably tert-butylperoxy-2-ethylhexanoate, dibenzoyl peroxide, dicumyl peroxide, dicumyl hydroperoxide, azobisisobutyronitrile, and benzyl barbituric acid derivatives, such as phenylbenzyl barbituric acid and cyclohexylbenzyl barbituric acid.

[0054] The following initiators and / or initiator systems for autopolymerization or cold polymerization comprise 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-butylperoxy-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 azo compound. or c) at least one initiator system selected from redox systems, in particular combinations selected from dibenzoyl peroxide, dilauroyl peroxide, and camphorquinone, with amines selected from N,N-dimethyl p-toluidine, N,N-dihydroxyethyl p-toluidine, and p-dimethylaminobenzoic acid diethyl ester. Alternatively, the initiator may be a redox system containing a peroxide and a reducing agent selected from ascorbic acid, ascorbic acid derivatives, barbituric acid or barbituric acid derivatives, sulfinic acid, and sulfinic acid derivatives. Particularly preferred is a redox system containing (i) barbituric acid, thiobarbituric acid, or a barbituric acid derivative, (ii) at least one copper salt or copper complex, and (iii) at least one compound having an ionic halogen atom. Particularly preferred is a redox system containing 1-benzyl 5-phenylbarbituric acid, copper acetylacetonate, and benzyl dibutylammonium chloride. Particularly preferred is polymerization in a two-component prosthetic base material initiated by a barbituric acid derivative.

[0055] Generally, initiators for the polymerization reaction of the starting mixture for low-temperature polymerization or autopolymerization are considered to be those capable of initiating a radical polymerization reaction. Preferred initiators are peroxides and azo compounds, such as: LPO: dilauroyl peroxide, BPO: dibenzoyl peroxide, t-BPEH: tert-butylperoxy-2-ethylhexanoate, AIBN: 2,2'-azobis-(isobutyronitrile), DTBP: di-tert-butyl peroxide.

[0056] To accelerate the initiation of radical polymerization by peroxide, a suitable activator, such as an aromatic amine, can be added.Examples of suitable amines are N,N-dimethyl p-toluidine, N,N-dihydroxyethyl p-toluidine, and p-dibenzylaminobenzoic acid diethyl ester.In this context, the amine usually functions as a coinitiator and is usually present in an amount of up to 0.5% by weight.

[0057] The following exemplary embodiments are intended to illustrate the invention without limiting the invention to these examples.

[0058] Example Exemplary embodiments: Test method for determining fracture toughness according to ISO-13586:2000 Test specimens (CT specimens) conforming to ASTM E1820-13 and ISO13586:2000. Uses a substitution ratio of W / B2≦W / B≦4.

[0059] The fracture toughness of the composition to be measured is determined on test specimens having the dimensions W (according to ASTM 1820-13) and w (according to ISO 13586) = 10 mm, B (according to ASTM 1820-13) and h (according to ISO 13586:2000) = 5 mm (CT test specimens), using the ratios or proportions of the test specimen dimensions according to standards ASTM E1820-13 and ISO 13586.

[0060] First, a rectangular test piece with a thickness of 5 mm and a base area / deck area of ​​12.0 × 12.5 mm was prepared. Photocuring or photopolymerization was performed by irradiating five spots (projection surfaces) for 20 seconds each with blue light (Translux 2 Wave, KULZER GmbH).

[0061] A 1 mm rotary cutting tool is used to create a notch (approximately 0.55 W) centered and aligned perpendicular to the longitudinal edge. A hole drilled perpendicular to the base / deck area is drilled with a 2 mm diameter cutting tool positioned in the same location as that applied to the test specimens (ASTM 1820-13 and ISO 13583:2000) to accommodate a pin.

[0062] A razor blade is used to make a crack with a diameter of 8 μm or less at the top of the centrally located notch. The length of the crack (a i ) is measured by optical microscope before the measurement. The length of the crack that changes a i is measured under the influence of a specified mechanical force. [Brief explanation of the drawings]

[0063] [Figure 1a] FIG. 1 is a cross-sectional view of a test specimen, including a legend of reference numbers and labeling, and a description of the measurement setup. [Figure 1b] FIG. 1 is a top view of the test specimen, including a legend of reference numbers and labeling, and a description of the measurement setup.

[0064] Explanation of symbols w = distance between the center points of the two holes and the opposite edge of the specimen; B = overall width of the specimen; l1 = length; l2 = distance between the center points of two holes symmetrically placed on the crack plane + / - 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 a loose fit to avoid friction.

[0065]

number

[0066] The specimen is then fixed to a universal testing machine (Zwick / Roell) using a metal pin guided through the hole. A specified tensile force (P) is then applied to the specimen through the pin at a rate of 1 mm / min until fracture. The tensile force (P), thickness (B), width (W), and crack length a i , fracture toughness K Ic is calculated according to the following formula:

[0067] [Table 1]

[0068] [Table 2]

[0069] [Table 3]

[0070] [Table 4]

[0071] [Table 5]

[0072] [Table 6]

[0073] The surface of the test specimen was irradiated with blue light (emission maximum approximately 440-460 nm) at five projection planes on the surface of the test specimen for 1 × 20 seconds for each sample in Table 3. The thermally cured samples in Table 3 were first irradiated with UV / Vis light for 1 × 60 seconds per side, followed by thermal curing (approximately 3 hours at 95°C).

[0074] [Table 7]

[0075] The results of fracture toughness measurements on comparative radiation-polymerized only specimens containing bis-GMA as a component in the polymer matrix show very low values ​​for fracture toughness (VG3a, VG3b).

[0076] The composite material according to the invention, based on bis-(2',7'-dioxa-3',8'-dioxo-4'-azadecyl-9'-ene)tetrahydrodicyclopentadiene and its isomers in a polymer matrix, has a fracture toughness of 1.3 MPa m 1 / 2 ~1.7 MPa m 1 / 2 ~2.2 MPa m 1 / 2 Significantly better values ​​of up to

Claims

1. 1. A polymerizable composition comprising: (i) 70 to 85% by weight of at least one inorganic filler component; (ii) 10 to 30% by mass of a mixture consisting of the following: a), b) and c): a) at least one difunctional urethane having a divalent alicyclic group of formula I 【Chemistry 1】 [R １ and R ２ are each independently selected from H or alkyl having 1 to 8 C atoms, b) difunctional urethane acrylates and / or urethane alkyl acrylates having divalent alkylene groups, and c) at least one at least tetrafunctional dendritic urethane acrylate and / or the corresponding urethane alkyl acrylate; (iii) 0.01 to 5% by weight of at least one difunctional, trifunctional, tetrafunctional, or polyfunctional monomer that is not a urethane acrylate and / or is not a urethane alkyl acrylate; (iv) 0.01 to 10% by weight of at least one initiator, initiator system; wherein the total amount of the polymerizable composition is 100 mass %.

2. The composition described in claim 1, characterized in that (iv) comprises the at least one initiator, initiator system and at least one stabilizer, and / or at least one pigment.

3. The at least one inorganic filler component comprising at least one of glass, silicate, feldspar, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide has an average particle size d of 0.5 to 10 μm. ５０ 3. The composition according to claim 1 or 2, characterized in that it has

4. a) the at least one inorganic filler component comprises at least one glass, silicate, quartz, feldspar, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide, or a mixture comprising at least two of the foregoing components, having an average particle size with a d50 of 1.8 μm, or b) at least one inorganic filler component comprising at least one glass, feldspar, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide, or a mixture comprising at least two of said components, ５０ ii) d of 1.0 to 2.0 μm ５０ , and iii) d of 0.5 to 2 μm ５０ wherein said fractions i) to ii) to iii) are present in a ratio of 1-4:1:4-8; 4. The composition according to claim 1, wherein the composition is a hydroxybenzoate.

5. 5. The composition of claim 1, wherein the metal oxide comprises at least one non-aggregated amorphous metal oxide having a primary particle size of 2 to 150 nm, the amorphous metal oxide comprising precipitated silicon dioxide, pyrogenic silica, zirconium oxide, or a mixed oxide.

6. The composition comprises, based on the total composition of 100% by mass of the composition, (i) an inorganic filler component, (i.1) 70 to 84% by weight of at least one glass, silicate, quartz, feldspar, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide, or a mixture comprising at least two of the aforementioned filler components; 6. The composition according to claim 1, wherein the composition comprises:

7. The composition, (i) as an inorganic filler component, based on the total composition of 100% by mass of the composition, (i.2) 0.05 to 5% by weight of an amorphous metal oxide; The composition of claim 6, further comprising:

8. 8. The composition according to claim 1, wherein (iii) is selected from dimethacrylate esters of polyethers, methacrylate esters of trifunctional, tetrafunctional, or polyfunctional polyethers, and 2,2-bis-[4-(2-hydroxy-3-methacryloyloxy-propoxy)phenyl]propane, bis-(2'-oxa-3'-oxo-pentyl-4'-ene)tetrahydrodicyclopentadiene and its isomers, and pentaerythritol tetrapropoxyacrylate.

9. 9. The composition according to claim 2, wherein the at least one stabilizer comprises water, at least one benzophenone derivative, and / or at least one phenol derivative.

10. 10. The composition of claim 1, wherein the composition comprises (v) 0.01 to 15% by weight of a polymeric particulate filler, the total composition being 100% by weight.

11. 11. A polymerized composition obtainable by polymerizing the composition of any one of claims 1 to 10 using i) a UV and / or VIS radiation source and / or ii) at a pressure of 50-300 MPa and / or at 90-150°C.

12. The polymerized composition of claim 11, wherein the VIS radiation source has an emission maximum in the spectral range of 380 nm to 530 nm.

13. Use of a composition according to any one of claims 1 to 12 in additive manufacturing, radiation-based generative manufacturing, stereolithography processes, SLA processes (laser-based stereolithography processes), DLP processes (digital light processing), or in SLA and DLP processes, LED beamer-based generative manufacturing, radiation- and thermal-based generative manufacturing, thermal generative manufacturing, 3D printing processes, multi-jet manufacturing processes (MJM), and polyjet manufacturing processes.

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