EP4048708A1

EP4048708A1 - Polymerizable composition

Info

Publication number: EP4048708A1
Application number: EP20800601.5A
Authority: EP
Inventors: Andreas Utterodt; Christoph Meier; Nelli Schönhof; Jutta Schneider; Kurt Reischl; Raif KOCOGLU; Michael Eck
Original assignee: Kulzer GmbH; Kulzer and Co GmbH
Current assignee: Kulzer GmbH
Priority date: 2019-10-31
Filing date: 2020-10-29
Publication date: 2022-08-31
Also published as: WO2021083995A1; DE102019129551A1; US20240182744A1; JP2023501959A

Abstract

The invention relates to a polymerizable composition comprising (i) 0 to 90 wt.% of at least one inorganic filler component, (ii) 5 to 99.98 wt.% of at least one urethane(alkyl)acrylate of the idealized formula I, (iii) 0.01 to 25 wt.% of at least one di-, tri-, tetra- or multifunctional monomer which is not urethane(alkyl)acrylate, and (iv) 0.01 to 10 wt.% of at least one initiator, an initiator system, optionally at least one stabilizer, and optionally at least one pigment, wherein the total composition of the composition is 100 wt.%. The invention also relates to a polymerized composition with improved fracture toughness.

Description

Polymerizable composition

The invention relates to a polymerizable composition comprising

(i) 0 to 90% by weight of at least one inorganic filler component,

(ii) 5 to 99.98% by weight of at least one urethane (alkyl) acrylate of the idealized formula I,

(iii) 0.01 to 25% by weight of at least one di-, tri-, tetra- or multi-functional monomer that is not a urethane (alkyl) acrylate,

(iv) 0.01 to 10% by weight of at least one initiator, an initiator system and optionally at least one stabilizer and optionally at least one pigment, the total composition of the composition being 100% by weight and a polymerized composition with improved fracture toughness and preferably higher Flexural strength and optionally low shrinkage when producing large three-dimensional articles or objects larger than 5 cm in at least one of the three dimensions.

The object of the invention was to provide a polymerizable composition which is suitable for the production of three-dimensional articles obtainable in generative processes, in particular for use in stereolithography, DLP processes or multi-jet processes (MJM) or polyjet processes. In addition, the composition should be suitable for the production of larger blocks of material, in particular geometric shaped bodies, such as milling blocks or large generatively available three-dimensional shaped bodies or articles. In addition, the polymerized composition should have very good values for the fracture toughness, which is a measure of the force to be used for crack propagation in a material. A further object was to provide a composition which has a homogeneous, monochrome coloration before and after the polymerization. It should not only be possible to produce small items, but also a homogeneous, monochrome coloration for larger items. Furthermore, it should be possible to produce polychrome, ie multicolored blocks of material with a defined coloring, in casting processes or in generative processes. In addition, a composition is to be provided which is easily flowable in the non-polymerized state and yet has excellent mechanical properties in the state polymerized by means of UV radiation or Vis radiation. The aim is also to provide a composition which, in the polymerized state, exhibits low shrinkage, even when larger blocks of material are produced. Based on the prior art, a composition with a new urethane derivative with a tricycle was developed. The invention relates to a composition according to claim 1, a polymerized composition according to claim 13 and the use according to claim 14. Preferred embodiments are explained in the dependent claims and in detail in the description.

The particle size distribution can, depending on the desired filler content, be rather broad for a high packing density and excellent mechanical properties, or it can also be designed rather narrow for specific applications.

Compositions with reduced shrinkage and good flexural strength of TCD esters are known. Surprisingly, very good values for the fracture toughness (measured according to ISO 13586: 2000) could also be shown for radiation-cured compositions comprising polymerization products of urethanes of the idealized formula I, in particular the idealized formula Ia, preferably after radiation curing.

The invention relates to a polymerizable composition comprising

(i) 0 to 90% by weight of at least one inorganic filler component,

(ii) 5 to 99.98% by weight comprising at least one urethane acrylate, the urethane acrylate having at least one urethane acrylate with a divalent alicyclic group of the idealized formula I. and / or mixtures of these urethanes of the formula I and optionally mixtures of the isomers of the aforementioned compounds with R ¹ and R ² each independently selected from H and alkyl having 1 to 8 carbon atoms,

(iii) 0.01 to 25% by weight of at least one di-, tri-, tetra- or multi-functional monomer that is not a urethane acrylate and / or a urethane alkyl acrylate, (iv) 0.01 to 10% by weight of at least one initiator, an initiator system and optionally at least one stabilizer and optionally at least one pigment, the total composition of the polymerizable composition being 100% by weight.

(Ii) preferably comprises a mixture of at least two, preferably three, different urethane acrylates. Particularly preferred is (ii) in combination with (iii) selected from a di-, tri-, tetra- or multifunctional methacrylic ester of polyethers, preferably dimethacrylate triethylene glycol, dimethacrylate tetraethylene glycol, and / or bis (2'-oxa-3'-oxo- pentyl-4'-ene) tetrahydrodicyclopentadiene and isomers thereof.

A preferred composition comprises

(i) 5 to 90% by weight of an inorganic filler component comprising at least one glass, a crystalline silicate such as quartz, feldspar, metal oxide such as crystalline and / or amorphous metal oxides, mixed oxide such as crystalline or amorphous mixed oxides, silicon dioxide, zirconium dioxide, zinc oxide and / or mixtures of at least two of the components mentioned, the components having an average particle size of 0.2 μm to 10 μm, and optionally at least one amorphous metal oxide with an average primary particle size of 10 nm to 115 nm, in particular with a primary particle size of 2 nm to 100 nm, particularly preferably from 2 to 45 nm, and

(ii) 5 to 85% by weight, in particular 10 to 85% by weight, of the at least one urethane acrylate or a mixture of urethane acrylates;

(iii) 0.01 to 25% by weight of at least one di-, tri-, tetra- or multi-functional monomer that is not a urethane acrylate and / or a urethane alkyl acrylate,

(iv) 0.01 to 10% by weight of at least one initiator, an initiator system and optionally at least one stabilizer and optionally at least one pigment, the overall composition of the composition being 100% by weight.

Another preferred composition comprises

(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 with an average particle size of 0.4 μm to 10 μm, and optionally at least one amorphous metal oxide with 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, alternatively preferably 10 to 60% by weight, comprising at least one urethane acrylate, the urethane acrylate having at least one urethane acrylate with a divalent alicyclic group of the idealized formula I and / or mixtures of these urethanes of the formula I and optionally mixtures of the isomers of the aforementioned compounds with R ¹ and R ² each independently selected from H and alkyl having 1 to 8 carbon atoms,

(iii) 0.01 to 15% by weight of at least one di-, tri-, tetra- or multi-functional monomer that is not a urethane acrylate and / or a urethane alkyl acrylate,

The invention furthermore relates to a composition

(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 or mixtures of at least two of the components with an average particle size of 0.4 μm to 10 μm, in particular from 0.4 μm to 7.5 μm, and optionally at least one amorphous metal oxide with an average primary particle size of 10 nm to 115 nm, in particular from 2 to 100 nm , as

(ii) 10 to 35% by weight, in particular 10 to 30% by weight, comprising at least one urethane acrylate, the urethane acrylate having at least one urethane acrylate with a divalent alicyclic group of the idealized formula I.

and / or mixtures of these urethanes of the formula I and optionally mixtures of the isomers of the aforementioned compounds with R ¹ and R ² each independently selected from H and alkyl having 1 to 8 carbon atoms,

(iii) 0.01 to 5% by weight of at least one di-, tri-, tetra- or multi-functional monomer that is not a urethane acrylate and / or a urethane alkyl acrylate,

The invention relates to a polymerizable composition, in particular comprising a photoinitiated or photochemically polymerizable composition

(i) 0 to 90% by weight, in particular 0 to 35% by weight, preferably 0.5 to 35% by weight, of at least one inorganic filler component with an average particle size d ₅₀ of 0.5 μm to 5 μm, preferably 0.7 to 3.5 μm, in particular from 0.7 μm to 3.0 μm, preferably from 0.8 μm to 2.5 μm, and optionally at least one amorphous metal oxide with a primary particle size of 2 to 150 nm,

(ii) 10 to 85% by weight, in particular 10 to 65% by weight, preferably 12 to 65% by weight, of at least one urethane acrylate comprising at least one urethane acrylate with a divalent alicyclic group of the idealized formula I, preferably comprising a mixture of at least two different urethane acrylates, in particular a mixture of at least one difunctional urethane acrylate or difunctional urethane alkyl acrylate with a divalent alicyclic group comprising a urethane of the idealized formula I, and / or mixtures of the urethanes of the formula I and optionally mixtures of isomers of the urethanes of the formula I (see also Formula la), in particular mixtures of the 3,8 / 3,9 / 4,8 / 3,10 / 4,10 isomers and / or the cis and trans isomers of the aforementioned compounds, with R ¹ and R ² each independently selected from H and alkyl having 1 to 8 carbon atoms; preference is given to a mixture of at least three different urethane acrylates and / or urethane alkyl acrylates, in particular comprising d i- to deca-functional urethane acrylates, (iii) 0.01 to 25% by weight, in particular from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, at least one di-, tri-, tetra- or multi- functional monomer that is not a urethane acrylate or urethane (alkyl) acrylate, in particular not a urethane (methyl) acrylate, and is preferably selected from a di-, tri-, tetra- or multifunctional methacrylic ester of 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 isomers thereof,

(iv) 0.01 to 10% by weight of at least one initiator, an initiator system and optionally at least one stabilizer and optionally at least one pigment, the at least one pigment in particular comprising both fluorescent and colored pigments, the overall composition of the composition being 100% by weight. -% is.

The urethanes of the idealized formula I are sold under the CAS no. 94 5656-78-0 (2- propenoic acid, 1,1 '- [(octahydro-4,7-methano-1H-indene-5,? - diyl) bis (methyleneoxycarbonylamino-2,1-ethanediyl)] ester). Alternatively, the formula can be shown as below.

A difunctional urethane acrylate is preferably selected from difunctional urethane acrylates with divalent alkylene groups, preferably comprising difunctional urethane alkyl acrylates with divalent alkylene groups with alkyl 1 to 10 carbon atoms and alkylene 3 to 20 carbon atoms.

A particularly preferred composition comprises

(i) 70 to 85% by weight of an inorganic filler component comprising at least one silicate, quartz, feldspar, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide and / or zinc oxide, optionally a glass, or mixtures of at least two of the components with an average particle size of 0.4 μm to 10 μm, in particular from 0.4 μm to 7.5 μm, and optionally at least one amorphous metal oxide, in particular with 0.05 to less than 10% by weight, preferably less than 4% by weight, especially preferably from 0.05 to 2% by weight, more preferably less than 1% by weight, of amorphous metal oxide in relation to the total composition,

(ii) 10 to 30% by weight of a mixture of at least two different urethane acrylates, the mixture comprising at least one difunctional urethane acrylate and / or urethane alkyl acrylate with a divalent alicyclic group comprising a urethane of the idealized formula I and / or mixtures of these urethanes of the formula I and optionally mixtures of the isomers of the aforementioned compounds with R ¹ and R ² each independently selected from H and alkyl having 1 to 8 carbon atoms,

Another particularly preferred composition comprises as

(i) inorganic filler component with methacrylate groups functionalized filler components selected from silicate, quartz, feldspar, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide and / or zinc oxide, optionally a glass, or mixtures in particular with a mean particle size d ₅₀ of 0.5 μm to 10 μm, preferably 0.7 to 7.5 μm, in particular from 0.7 μm to 5.5 μm, preferably from 0.8 μm to 5.5 μm, 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, of a non-agglomerated amorphous metal oxide, based on the total composition, preferably a primary particle size of 2 to 150 nm, in particular from 2 to 100 nm, preferred from 2 to 45 nm, the amorphous metal oxide comprising silicon dioxide, precipitated silicon dioxide, pyrogenic silica, zirconium oxide, mixed oxides or mixtures of these, in particular the metal oxides are silanized,

(ii) a mixture of at least two different urethane acrylates, in particular a mixture of at least one difunctional urethane acrylate or difunctional urethane alkyl acrylate with a divalent alicyclic group comprising a urethane of the idealized formula I and / or mixtures of the urethanes of the formula I and optionally mixtures of isomers of the urethanes of the formula I (see also formula la), in particular mixtures of the 3,8 / 3,9 / 4,8 / 3,10 / 4,10 isomers and / or the cis and trans isomers of the aforementioned compounds , with R ¹ and R ² each independently selected from H and alkyl having 1 to 8 carbon atoms, a mixture of at least three different ones is preferred Urethane acrylates and / or urethane alkyl acrylates, in particular comprising di- to decafunctional urethane acrylates, and

(iii) at least one di-, tri-, tetra- or multi-functional monomer that is not a urethane acrylate or urethane (alkyl) acrylate, in particular not a urethane (methyl) acrylate, selected from multifunctional methacrylic esters of 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 Isomers thereof and pentaerythritol tetrapropoxy acrylate,

(iv) at least one initiator, one initiator system and optionally at least one stabilizer and optionally at least one pigment, the at least one pigment in particular comprising titanium dioxide.

The proportions of the aforementioned components can assume the amounts mentioned above and below in the overall composition of 100% by weight.

In one embodiment, it is preferred if the polymerizable composition is photochemically polymerizable. Alternatively, it is preferred if the polymerizable composition is thermally polymerizable. The composition is particularly preferably both photochemically and thermally polymerizable, in particular dual-polymerizable. A photochemically polymerizable composition is understood to mean a composition that can be polymerized by means of a UV and / or Vis radiation source, preferably one by means of a Vis radiation source with emission maxima in the spectral range from 360 nm to 530 nm, preferably with at least one maximum or maxima in the spectral range of 400 to 500 nm, polymerizable composition. The composition is particularly preferably irradiated by means of a pulsed UV and / or Vis radiation source, in particular for greater than or equal to 50 milliseconds, preferably greater than or equal to 10 seconds, in particular per projection surface of the radiation source. Irradiation for greater than or equal to 15 seconds to 5 minutes, preferably for 10 to 30 seconds, per projection surface of the radiation source is further preferred. In principle, all conventional radiation sources with an emission wavelength, preferably emission maxima, in the spectral range from 400 to 480 nm and an intensity of greater than 500 mW / cm ^{2 are} suitable as the radiation source. If very thin layers are applied, as in the multijet process, the pulsed irradiation per radiation pulse can be less than 1 second. A radiation source with an LED light source is particularly preferred. In the present case, a thermally polymerizable composition is understood to mean a composition which can be polymerized at greater than or equal to 60 to 150.degree. C., preferably greater than or equal to 70 to 150.degree. C., particularly preferably from 90 to 150.degree. It is further preferred according to the invention if the volume shrinkage is small.

The invention also relates to a dental composite material obtainable by polymerization i) with a UV / Vis radiation source, preferably with a Vis radiation source with emission maxima in the spectral range from 380 nm to 530 nm, preferably with at least one maximum or maxima in the spectral range from 400 to 500 nm and optionally ii) at a pressure of 50 to 300 MPa and / or elevated temperature, preferably at 90 to 150 ° C., or i) with a UV and / or Vis radiation source, preferably with a Vis radiation source with emission maxima in the spectral range from 380 nm to 530 nm, preferably with at least one maximum or maxima in the spectral range from 400 to 500 nm and / or ii) at a pressure of 50 to 300 MPa and / or elevated temperature, preferably at 90 to 150 ° C.

The following glasses are preferably considered: aluminum silicate glasses or fluoroaluminosilicate glasses, fluoroaluminosilicate glasses containing boron, barium aluminum silicate, strontium silicate, strontium borosilicate, potassium silicate, calcium borosilicate, sodium silicate glass, potassium silicate glass, lithium silicate and / or mixtures of at least two of the aforementioned glasses. Amorphous, spherical fillers based on oxide or mixed oxides, such as amorphous SiO ₂ , ZrO ₂ or mixed oxides of SiO ₂ and ZrO ₂ , can be used as the amorphous metal oxide or as a mixture of amorphous metal oxides. Alternatively, mixed oxides of zirconium dioxide and silicon dioxide, zirconium dioxide or zinc oxide as well as crystalline silicates can be used as filler components in the composition.

The invention also relates to a composition which comprises a filler component selected from filler components functionalized with methacrylate groups, in particular selected from silicate, such as quartz and / or feldspar, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide and / or zinc oxide, optionally a glass , or mixtures of the components, a) an average particle size d ₅₀ of 1.8 μm with plus / minus 0.25 μm and preferably d ₉₉ less than or equal to 20 μm, in particular d ₉₉ less than or equal to 10 μm, or b) a mixture of the aforementioned components of different fractions with mean particle sizes with i) d ₅₀ of 2 to 8 μm, optionally with plus / minus 0.5 μm, in particular with 4 to 6 μm, optionally with plus / minus 0.25 μm, ii) d ₅₀ from 1.0 to 2.0 μm, optionally with plus / minus 0.25 μm, in particular with 1.2 to 2.0 μm, optionally with plus / minus 0.5 μm, preferably with 1.5 μm, optionally with plus / minus 0.15 μm, and iii) d ₅₀ from 0.5 μm to 1.2 μm optionally with plus / minus 0.15 μm, 0.7 to 0.9 μm optionally with plus / minus 0.5 μm, the fractions from i) to ii) to iii) being present in a ratio of 1 to 4: 1: 4 to 8, in particular from 2 to 3: 1: 6 to 7. Particularly preferred is i) d ₅₀ of 5 μm, optionally with plus / minus 0.5 μm, ii) d ₅₀ of 1.8 μm, optionally with plus / minus 0.25 μm and iii) d ₅₀ of 0.85 μm, optionally plus / minus 0.15 μm, the fractions from i) to ii) to iii) being present in a ratio of 1 to 4: 1: 4 to 8, in particular from 2 to 3: 1: 6 to 7.

According to a preferred embodiment, the filler component is selected from filler components functionalized with methacrylate groups, which are selected in particular from silicate, such as quartz and / or feldspar; Metal oxide, mixed oxide, silicon dioxide, zirconium dioxide and / or zinc oxide, optionally a glass, or mixtures of the components, an average particle size d ₅₀ of 0.7 to 2.0 μm, in particular 1.2 to 2.0 μm, preferably with an average Particle size from 1.35 to 1.95 μm, in particular with d ₅₀ of 1.8 μm, optionally plus / minus 0.15 μm, and preferably with d ₉₉ less than or equal to 10 μm. The at least one filler component is particularly preferably selected from filler components functionalized with methacrylate groups, which are in particular selected from silicate, such as quartz and / or feldspar; Metal oxide, mixed oxide, silicon dioxide, zirconium dioxide and / or zinc oxide, optionally a glass, or mixtures of the components with an average particle size of d ₅₀ of about 0.85 μm, optionally plus / minus 0.1 μm, in particular plus / minus 0.05 μm, preferably plus / minus 0.03 μm, and preferably with d ₉₉ less than or equal to 10 μm. A particularly preferred particle size distribution can be in the range from d ₁₀ with greater than or equal to 0.2 μm to d ₉₉ less than or equal to 20 μm, preferably less than or equal to 7.5 μm, preferably with d ₁₀ greater than or equal to 0.4 μm to d ₉₉ less than 7, 5 μm and a mean diameter d ₅₀ of 0.7 to 7.5 μm.

According to a preferred embodiment, the composition (i) comprises 70 to 85% by weight or 5 to 35% by weight of at least one inorganic filler component selected from filler components functionalized with methacrylate groups, which are in particular selected from silicate, such as quartz and / or feldspar; Metal oxide, Mixed oxide, silicon dioxide, zirconium dioxide and / or zinc oxide, optionally a glass, or mixtures of the components with an average particle size d ₅₀ of 0.7 to 2.0 μm of greater than or equal to 50 to 80% by weight in relation to the composition with a Total composition of 100% by weight is present, in particular greater than or equal to 55 to 76% by weight, preferably greater than or equal to 60 to 75% by weight, particularly preferably greater than or equal to 60 to 71% by weight in the total composition of 100% by weight. -%.

Also preferably in combination with an amorphous silicon dioxide with 4 to 7.5% by weight in the total composition. The amorphous metal oxide is preferably a non-agglomerated amorphous metal oxide with a primary particle size of 2 to 150 nm, in particular from 2 to 100 nm, preferably from 2 to 45 nm, the amorphous metal oxide being silicon dioxide, precipitated silicon dioxide, fumed silica, zirconium oxide, mixed oxides or mixtures this includes, in particular the metal oxides are silanized.

In a preferred alternative, in addition to the inorganic filler component, the composition can comprise a content of a polymeric, particulate filler. The total content of such a polymeric, particulate filler can be from 0.01 to 15% by weight, preferably from 0.5 to 10% by weight, in the total composition of the composition of 100% by weight. The particle sizes of the polymeric filler are preferably in the range from 10 to 200 micrometers, in particular from 30 to 90 micrometers, particularly preferably from 20 to 50 micrometers.

According to a particularly preferred embodiment, the composition comprises as component (ii) a mixture of at least three different urethane acrylates and / or urethane alkyl acrylates, in particular of di- to deca-functional urethane acrylates and / or corresponding urethane alkyl acrylates, preferably from 15 to 19% by weight at least a difunctional urethane acrylate and / or urethane alkyl acrylate comprising a urethane of the idealized formula I. and / or a mixture of these urethanes of the formula I and the isomers, in particular mixtures the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers of the formula la and / or the cis- and trans-isomers of the aforementioned compounds, with R ¹ and R ² respectively independently selected from H and alkyl with 1 to 8 carbon atoms, and to 5 to 6 wt .-% of a difunctional urethane acrylate with divalent alkylene group and / or difunctional urethane alkyl acrylate with divalent alkylene group with alkyl 1 to 10 carbon atoms and Alkylene 3 to 20 carbon atoms, and optionally 0.1 to 2% by weight 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 multi-functional monomer that is not a urethane acrylate or a urethane alkyl acrylate, in particular at least one di-, tri-, tetra- or multifunctional methacrylic ester of polyethers, 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'-en) tetrahydro-dicyclopentadiene and isomers thereof, and

(iv) at least one initiator or one initiator system, preferably a) at least one photoinitiator for the UV and / or Vis range or a photoinitiator system for the UV and / or Vis range and optionally at least one stabilizer, and / or b) at least one thermal initiator or a thermal initiator system and c) optionally at least one stabilizer and iv) optionally at least one pigment. Preferably in accordance with the abovementioned contents in the overall composition.

The di- to deca-functional urethane acrylates or di- to deca-functional urethane alkyl acrylates are used as monomers and do not contain any peroxy groups.

According to a particularly preferred embodiment, the composition (ii) comprises 5 to 99.98% by weight, in particular 5 to 85% by weight, of a mixture of at least three different urethane acrylates and / or urethane alkyl acrylates, preferably of at least three different urethanes, where the mixture at least one difunctional urethane acrylate and / or urethane alkyl acrylate comprising a urethane of the idealized formula I, see also formula la, and / or mixtures of these urethanes of the formula I and optionally mixtures of 3.8 / 3.9 / 4.8 / 3.10 - / 4,10 isomers and / or the cis and trans isomers of the aforementioned compounds, with R ¹ and R ² each independently selected from H and alkyl having 1 to 8 carbon atoms, preferably H or methyl, and a difunctional one Urethane acrylate with divalent alkylene group and / or urethane alkyl acrylate with divalent alkylene group with alkyl of 1 to 10 carbon atoms, preferably with alkyl equal to methyl, and alkylene with 3 to 20 carbon atoms, preferably of three different urethane (alkyl) acrylates , and optionally at least one at least tetra-functional dendritic urethane (alkyl) acrylate, preferably at least one hexafunctional dendritic urethane (alkyl) acrylate, in particular urethane (meth) acrylate.

According to a particularly preferred embodiment, the composition (ii) comprises 5 to 99.98% by weight of a mixture of at least two different urethanes selected from a mixture comprising at least one difunctional urethane acrylate and / or urethane alkyl acrylate comprising a urethane of the idealized formula I and / or Mixtures of these urethanes of the formula I and optionally mixtures of the 3,8 / 3,9 / 4,8 / 3,10 / 4,10 isomers and / or the cis and trans isomers of the aforementioned compounds with R ¹ and R ² each independently selected from H and alkyl having 1 to 8 carbon atoms, such as bis (2 ', 7'-dioxa-3', 8'-dioxo-4'-aza-decyl-9'- en) tetrahydrodicyclopentadiene, bis- (2 ', 7'-dioxa-3', 8'-dioxo-4'-aza-9'-methyl-decyl-9'-en) tetrahydrodicyclopentadiene, and optionally at least one difunctional urethane acrylate with bivalent alicyclic group and / or urethane (meth) acrylate with divalent alicyclic group, which is selected from bis- (4 ', 7'-dioxa-3', 8'-dioxo-2'-aza-decyl-9'-e n) tetrahydrodicyclopentadiene, bis- (4 ', 7'-dioxa-3', 8'-dioxo-2'-aza-9'-methyl-decyl-9'-ene) tetra-hydrodicyclopentadiene and / or mixtures of these and optionally Mixtures of the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or the cis- and trans- isomers of the aforementioned compounds, and at least one further difunctional urethane (meth) acrylate, in particular at least one difunctional urethane acrylate with a bivalent alkylene group and / or urethane methacrylate with a bivalent alkylene group, and optionally at least one at least one at least tetrafunctional dendritic urethane acrylate and / or corresponding urethane methacrylate, preferably at least one hexafunctional dendritic urethane acrylate and / or urethane methacrylate. At least three different urethane (meth) acrylates are particularly preferred selected from urethane acrylates and urethane methacrylates (based on the total composition of 100% by weight. The term (alkyl) acrylate or (meth) acrylate or urethane (alkyl) acrylate with (alkyl) in brackets or urethane (meth) acrylate with (meth) in brackets means that the term includes acrylates or urethane acrylates with and without alkyl groups or methyl groups can. The alkyl groups preferably contain 1 to 10 carbon atoms, preferably 1 to 2 carbon atoms, in the urethane alkyl acrylates mentioned. The alkyl groups preferably contain 1 to 10 carbon atoms, preferably 1 to 2 carbon atoms, in the (alkyl) acrylates mentioned.

According to a particularly preferred embodiment, the composition (ii) comprises 5 to 99.98% by weight, in particular 61 to 99.98% by weight, alternatively 5 to less than 10% by weight, in each case a mixture of at least two different urethanes (Alkyl) acrylates, preferably of at least three different urethane (meth) acrylates, comprising at least one difunctional urethane acrylate and / or one difunctional urethane methacrylate of the general formula I and at least one difunctional urethane acrylate and / or one difunctional urethane methacrylate with a divalent alkylene group and optionally at least one at least tetrafunctional dendritic urethane acrylate and / or tetrafunctional dendritic urethane methacrylate, preferably at least one hexafunctional dendritic urethane acrylate and / or urethane methacrylate, components (i) 0% by weight to 38.98% by weight, alternatively 94.98% by weight. -% to 89.98% by weight, (iii) 0.01 to 10% by weight and (iv) 0.01 to 10% by weight corresponding end of the disclosure and the total composition is 100% by weight.

According to the invention, the urethane acrylate with a divalent alicyclic group is selected from urethanes of the idealized formula I and / or mixtures of these urethanes of the formula I and optionally mixtures of the 3.8- / 3.9- / 4.8- / 3.10- / 4, 10-isomers and / or the cis- and trans-isomers of the aforementioned compounds, with R ¹ and R ² each independently selected from H and alkyl having 1 to 8 carbon atoms, such as preferably bis (2 ', 7'- dioxa-3 ', 8'-dioxo-4'-aza-decyl-9'-en) tetrahydro-dicyclopentadiene, bis- (2', 7'-dioxa-3 ', 8'-dioxo- 4'-aza- 9'-methyl-decyl-9'-ene) tetrahydrodicyclo-pentadiene, particularly preferably bis- (2 ', 7'-dioxa-3', 8'-dioxo-4'-aza-decyl-9'-ene) tetrahydrodicyclopentadiene . The urethane of the formula I can be obtained by reacting the corresponding tetrahydrodiclylopentadiene, which is disubstituted by hydroxymethylene groups, with the corresponding isocyanate of an acrylate derivative, such as 2-isocyanatoethyl methacrylate. The difunctional urethane acrylate, urethane (alkyl) acrylate, urethane (alkyl) acrylate with a divalent alkylene group or urethane (meth) acrylate with a divalent alkylene group is preferably selected from linear or branched urethane dimethacrylates functionalized with a divalent alkylene group, urethane dimethacrylate functionalized polyethers polyalkylene ethers substituted by alkylene group (s), such as bis (methacryloxy-2-ethoxycarbonylamino) alkylene, bis (methacryl-oxy-2-ethoxycarbonylamino), preferably 1,6-bis (methacryloxy-2-ethoxycarbonylamino) -2,4 , 4-trimethylhexane, UDMA with alternative designation HEMA-TDMI. A bis (methacryloxy-2-ethoxycarbonylamino) alkylene is preferred, alkylene comprising linear or branched C3 to C20, preferably C3 to C6, such as particularly preferably an alkylene substituted by methyl groups, such as HEMA-TMDI. The divalent alkylene preferably includes 2,2,4-trimethylhexamethylene and / or 2,4,4-trimethylhexamethylene.

The at least tetra-functional dendritic urethane methacrylate comprises tetra- to deca-functional dendritic urethane methacrylates.

The composition preferably comprises 5 to 65% by weight, in particular 40 to 70% by weight, alternatively 5 to less than 10% by weight bis- (2 ', 7'-dioxa-3', 8) as component (i) '- dioxo-4'-aza-decyl-9'-ene) tetrahydrodicyclopentadiene, bis- (2', 7'-dioxa-3 ', 8'-dioxo-4'-aza-9'-methyl-decyl-9 '-en) tetrahydrodicyclopentadiene, and / or mixtures of these and optionally mixtures of the 3,8 / 3,9 / 4,8 / 3,10 / 4,10 isomers and / or the cis and trans isomers of the aforementioned compounds, and 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-TDMI and optionally 0.1 to 5% by weight, preferably 0.2 to 2% by weight, particularly preferably 0.2 to 1% by weight, of at least one tetra- to deca-functional dendritic urethane methacrylate based on the total composition.

According to a further preferred embodiment, the composition comprises as component (iii) 0.01 to 5% by weight of at least one di-, tri-, tetra- or multi-functional monomer that is not a urethane (alkyl) acrylate and is selected from Di Methacrylic esters of polyethers, bis- (2'-oxa-3'-oxo-pentyl-4'-ene) tetrahydrodicyclopentadiene and isomers thereof and tri-, tetra- or multifunctional methacrylic esters of polyethers.

The content of components (iii) is preferably 0.15 to 15% by weight, in particular 0.15 to 5% by weight, particularly preferably 1.0 to 2% by weight, with component (iii) is selected from di-methacrylic esters of polyethers, such as, preferably, dimethacrylate-polyethylene glycol, dimethacrylate-polypropylene glycol. Dimethacrylate-triethylene glycol (TEGDMA), diethylene glycol dimethacrylate (DEGMA) and dimethacrylate-tetraethylene glycol (TEDMA) are particularly preferred.

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

To optimally adjust the color and the aesthetics of the polymerized composition, at least one pigment comprising at least one fluorescent pigment and optionally at least one organic color pigment and / or at least one inorganic color pigment, such as titanium dioxide, in particular non-fluorescent color pigments, can be added. The at least one fluorescent pigment is preferably an organic fluorescent pigment, in particular a non-polymerizable organic fluorescent pigment, possibly comprising aryl carboxylic acid esters, aryl carboxylic acids, coumarin, rhodamine, naphthane imide or a derivative of the respective substance. Inorganic fluorescent pigments can include CaAI ₄ 0 ₇ : Mn ²⁺ , (Ba0.98Eu0.02) MgAl ₁₀ O ₁₇ , BaMgF ₄ : Eu ²⁺ , Y (1.995) Ce (0.005) SiO ₅ .

As pigments, in particular colored pigments, the composition can comprise organic pigments and inorganic pigments, in particular comprising diethyl-2,5-dihydroxyterephthalate, N, N'-bis (3,5-xylyl) perylene-3,4: 9,10-bis (dicarbimide), copper phthalocyanine, titanate pigment, especially chromium antimony titanate (rutile structure), spinel black, especially pigments based on iron oxide black (Fe ₃ O ₄ ), with iron (Fe) partly replaced by chromium and copper or nickel and chromium or manganese is substituted, zinc iron chrome spinel, brown spinel, ((Zn, Fe) (Fe, Cr) ₂ O ₄ )

Cobalt zinc aluminate blue pinel and / or titanium oxide. The pigments comprising fluorescent and colored pigments are preferably present in the total composition in an amount of from 0.01 to 10% by weight, particularly preferably from 0.01 to 5% by weight, preferably from 0.01 to 1% by weight.

According to a further preferred embodiment, the composition can comprise: (iv) 0.01 to 2% by weight of photoinitiator for the UV and / or Vis range or a photoinitiator system for the UV and / or Vis range, and 0.01 to 2% by weight % Stabilizer by weight.

The invention also provides a polymerized composition obtainable by polymerization of the composition according to the invention, in particular polymerization by means of UV and / or Vis radiation, preferably by means of Vis radiation, particularly preferably by means of a radiation source which has emission maxima in the spectral range from 400 nm to 530 nm .

According to a particularly preferred embodiment, the invention relates to a polymerized composition comprising 0 to 90% by weight of at least one inorganic filler component with an average particle size d ₅₀ in the range from 0.2 μm to 10 μm, preferably from 0.5 to 3.5 μm , and preferably d ₉₉ less than or equal to 20 μm, preferably less than 7.5 μm and optionally at least one amorphous, silanized metal oxide, in particular precipitated silicon dioxide and / or fumed silica with a primary particle size of 2 to 150 nm, preferably 2 to 100 nm, particularly preferred from 2 to 45 nm, 5.01 to 99.98% by weight of at least one polymer, in particular a copolymer based on a polymerized mixture comprising at least one bis-urethane of the formula I and at least one di-urethane (meth) acrylate divalent alkylene group, at least one tetra- to deca-functional dendritic urethane methacrylate, and at least one di-, tri-, tetra- or multifunctional Methacrylic esters of polyethers, 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 color pigment and / or at least one inorganic color pigment, the color pigments preferably not fluorescing, whereby the overall composition of the composition Is 100% by weight.

Furthermore, the polymerized composition can be used for the production of technical components that are particularly exposed to high mechanical loads, such as plastic templates, nails, screws and other components that are familiar to the specialist, etc ..

The following also preferably come into consideration as urethane (meth) acrylates according to the invention: (ii) at least one urethane (meth) acrylate, in particular a urethane dimethacrylate, preferably a bis (methacryloxy-2-ethoxycarbonylamino) alkylene, diurethane acrylate oligomers, alkyl-functional urethane dimethacrylate oligomers, aromatic-functionalized Urethandimeth-acrylate oligomers, aliphatic unsaturated urethane acrylates, bis (methacryloxy-2-ethoxycarbonylamino) substituted polyethers, aromatic urethane diacrylate oligomer, aliphatic urethane diacrylate oligomer, aliphatic urethane diacrylates, hexafunctional aliphatic urethane resins, aliphatic urethane triacrylate, aliphatic urethane acrylate oligomer, unsaturated aliphatic urethane acrylates. Preference is given to difunctional and multifunctional urethane (meth) acrylates, such as in particular urethane di (meth) acrylates, particularly preferably the at least one (iii) urethane dimethacrylate selected from linear or branched alkyl-functionalized urethane dimethacrylates, urethane dimethacrylate-functionalized polyethers, in particular bis (methacryloxy-2- ethoxycarbonylamino) alkylene, bis (methacryloxy-2-ethoxycarbonylamino) substituted polyethers, preferably 1,6-bis (methacryloxy-2-ethoxycarbonylamino) 2,4,4-trimethylhexanes. Suitable urethane (meth) acrylates are available under the following brand names: Ebecryl 230 (aliphatic urethane diacrylate), Actilane 9290, Craynor 9200 (di-urethane acrylate oligomer), Ebecryl 210 (aromatic urethane diacrylate oligomer), Ebecryl 270 (aliphatic urethane diacrylate oligomer), Actilane urethane diacrylate oligomer 165, Actilane 250, Genomer 1122 (monofunctional urethane acrylate), Photomer 6210 (Cas No. 52404-33-8, aliphatic urethane diacrylate), Photomer 6623 (hexafunctional aliphatic ureth resin), Photomer 6891 (aliphatic urethane triacrylate), UDMA, Roskydal LS 2258 (aliphatic urethane acrylate oligomer), Roskydal XP 2513 (unsaturated aliphatic urethane acrylate). The urethane (meth) acrylates can preferably be selected from the aforementioned urethane (meth) acrylates or from a mixture of at least two different, preferably at least three different, aforementioned urethane (meth) acrylates.

The at least one di-, tri-, tetra- or multi-functional monomer that is not a urethane (alkyl) acrylate, in particular not a urethane (meth) acrylate, is preferably selected from at least one of the following monomers, in particular comprising a mixture of monomers Bis- (2'-oxa-3'-oxo-pentyl-4'-ene) tetrahydrodicyclopentadiene and Isomers thereof, 1,4-butanediol dimethacrylate (1,4-BDMA) or pentaerythritol tetraacrylate, bis-GMA monomer (bisphenyl-A-glycidyl methacrylate), triethylene glycol dimethacrylate (TEGDMA) and diethylene glycol dimethacrylate (DEGMA), Tetraethylene glycol di (meth) acrylate, decanediol di (meth) acrylate, dodecanediol di (meth) acrylate, hexyldecanediol di (meth) acrylate, trimethylol propanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate and butanediol di (meth) acrylate, Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, ethoxylated / propoxylated bisphenol A di (meth) acrylates, a mixture containing at least one of these (meth) acrylates and / or copolymers comprising one or at least two of the aforementioned monomers.

Typical difunctional monomers, also referred to as crosslinkers or multiple crosslinkers, are tri- or tetraethylene glycol di (meth) acrylate, BDMA, 1,4-butanediol dimethacrylate (1,4-BDMA), bis-GMA monomer (bisphenyl-A-glycidyl methacrylate , an addition product of methacrylic acid and bisphenol A diglycidyl ether), diethylene glycol di (meth) acrylate, bisphenol A di (meth) acrylate, decanediol di (meth) acrylate, dodecanediol di (meth) acrylate, hexyldecanediol di (meth) acrylate, as well as butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylates, ethoxylated / propoxylated bisphenol A di (meth) acrylates. The following difunctional monomers can also be added as diluents (low viscosity acrylates): Tri- and tetra-functional monomers or multiple crosslinkers including trimethylolpropane tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraacrylate.

In addition to the di-, tri- or multi-functional monomer or monomers, at least one of the following monomers can be present in the composition comprising at least one monomer, in particular a mixture of monomers of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, n-hexyl methacrylate, 2 -Phenoxyethyl methacrylate, isobornyl methacrylate, isodecyl methacrylate, polypropylene glycol mono methacrylate, tetrahydrofuryl methacrylate, 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, methacrylate, benzyl acrylate, furfuryl acrylate, acrylate containing at least one of these (mixture), methyl acrylate, furfuryl acrylate, one of these acrylates, one of these (mixture), benzyl-, furfuryl- or phenyl (methacrylate) acrylate, one of these (mixture) of these acrylates, one of these (mixture) of benzyl, furfuryl or phenyl and / or copolymers comprising one or at least two of the aforementioned monomers. The invention also relates to a composition which preferably additionally contains at least one or more substance (s) from the groups of fillers, pigments, stabilizers, regulators, antimicrobial additives, UV absorbers, thixotropic agents, catalysts and crosslinkers. Such additives - like pigments, stabilizers and regulators - are used in rather small amounts, e.g. B. a total of 0.01 to 3.0, especially 0.01 to 1.0 wt .-% based on the total composition of the composition. Suitable stabilizers are e.g. B. hydroquinone monomethyl ether or 2,6-di-tert-butyl-4-methylphenol (BHT).

As component (iv) the composition contains preferably 0.01 to 10 wt .-%, in particular from 0.5 to 5 wt .-%, preferably 0.5 to 2 wt .-% of at least one initiator or initiator system, preferably i) at least one photoinitiator for the UV and / or Vis range or a photoinitiator system for the UV and / or Vis range and optionally at least one stabilizer, and optionally further customary additives, optionally pigment (s) or dye (s).

Particularly preferred photoinitiators include alpha-hydroxyphenyl ketone, benzil dimethyl ketal or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid ethyl ester, and mixtures of at least two of the photoinitiators, Bisacylphosphine oxides (BAPO). Or camphorquinone with amines selected from N, N-dimethyl-p-toluidine, N-N-dihydroxyethyl-p-toluidine and p-dimethylaminobenzoic acid diethyl ester.

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 (UVAs) and hydroxy Phenyl Triazines (HPT). Particularly suitable stabilizers are, for. B. hydroquinone monomethyl ether or 2,6-di-tert-butyl-4-methylphenol (BHT).

Suitable initiators, in particular thermal initiators or initiator systems, are peroxides, hydroxyperoxides, optionally azo compounds, or mixtures comprising these. Suitable thermal initiators can be used as free radical initiators in the temperature range from 70 to 150.degree. C., preferably from 90 to 150.degree. Preferred thermal initiators include at least one initiator selected from: dilauroyl peroxide, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, dicumyl peroxide, dicumyl hydroperoxide, 2,2'-azobis-isobutyronitrile, benzylbarbituric acid derivative, particularly preferred tert-butyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, dicumyl peroxide, dicumyl hydroperoxide, azobisisobutyronitrile, benzylbarbituric acid derivatives, such as phenylbenzylbarbituric acid, cyclohexylbenzylbarbituric acid.

The following initiators and / or initiator systems for auto- or cold polymerization include 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 per-2-ethylhexanoate, AIBN: 2,2'-azobis- (isobutyronitrile), DTBP: di-tert-butyl peroxide, and optionally b) at least one activator, in particular at least one aromatic amine, such as N, N-dimethyl-p-toluidine, N, N -Dihydroxyethyl-p-toluidine and / or p-dibenzylaminobenzoic acid diethyl ester or c) at least one initiator system selected from redox systems, in particular a combination selected from dibenzoyl peroxide, dilauroyl peroxide and camphorquinone with amines selected from N, N-dimethyl-p-toluidine, N- N- Dihydroxyethyl-p-toluidine and p-dimethylaminobenzoic acid diethyl ester. Alternatively, the initiator system can be a redox system which comprises a peroxide and a reducing agent which is selected from ascorbic acid, ascorbic acid derivative, barbituric acid or a barbituric acid derivative, sulfinic acid, sulfinic acid derivative, a redox system comprising (i) barbituric acid or thiobarbituric acid or a barbituric acid is particularly preferred. or thiobarbituric acid derivative and (ii) at least one copper salt or copper complex and (iii) at least one compound with an ionic halogen atom, a redox system comprising 1-benzyl-5-phenylbarbituric acid, copper acetylacetonate and benzyldibutylammonium chloride is particularly preferred. The polymerization in the 2-component denture base material is particularly preferably started via a barbituric acid derivative.

In principle, initiators for the polymerization reaction of cold or autopolymerizing starting mixtures are those with which radical polymerization reactions can be started. Preferred initiators are peroxides and azo compounds, for example the following: LPO: dilauroyl peroxide, BPO: dibenzoyl peroxide, t-BPEH: tert-butyl per-2-ethylhexanoate, AIBN: 2,2'-azobis (isobutyronitrile), DTBP: di -tert-butyl peroxide.

In order to accelerate the initiation of the radical polymerization by peroxides, suitable activators, e.g. B. aromatic amines can be added. Examples of suitable amines are N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine and p- Dibenzylamino-benzoic acid diethyl ester called. The amines regularly function as co-initiators and are usually present in an amount of up to 0.5% by weight.

The following exemplary embodiments are intended to illustrate the invention without restricting the invention to these examples.

Embodiment:

Test method for the determination of the fracture toughness according to ISO-13586: 2000 test specimens (CT specimens) according to ASTM E 1820-13 and ISO 13586: 2000, with alternative ratios for W / B 2 ≤ W / B ≤ 4.

The fracture toughness of the compositions to be measured is determined on test specimens (CT specimens) with the following 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, using the ratio or proportions of the dimensions of the specimens according to the specifications of ASTM E 1820-13 and ISO 13586.

First, test specimens (cuboids) with a thickness of 5 mm and a base / top area of 12.0 x 12.5 mm are produced. The light curing or photo-polymerization was carried out by means of irradiation with blue light, a total of five spots (projection surfaces) being irradiated for 20 seconds each (Translux 2 Wave, KULZER GmbH).

A groove (approx. 0.55w) aligned centrally and perpendicular to a longitudinal edge is made using a 1 mm rotating cutting tool. Holes made vertically in the base / top surface for receiving pins are drilled with a cutting tool with a diameter of 2 mm, which are arranged in the same position as they are for the test specimens of (ASTM 1820-13 and IOS 13583: 2000 ) is provided.

A razor blade is used to make a cut in the tip of the central groove in order to create a crack with a diameter of less than 8 μm. Before carrying out the measurement, the length of the crack (a,) is measured with an optical microscope. The changing crack length ai is measured under the influence of defined mechanical forces. Fig. 1a: Cross section of the sample body, Fig. 1b: Top view of the sample body. With legend of the reference symbols and labels and description of the measurement setup.

Legend w = distance between the center of the two holes and the opposite edge of the specimen; B = width of the entire test specimen; l1 = length; I2 = distance between the center of the two holes, which are symmetrical to the plane of the crack +/- 0.005w;

R = radius; h = thickness; a = crack length; P = force

B = 1.25w +/- 0.01w; I ₁ = 1.2w +/- 0.01w, l ₂ = 0.55w +/- 0.0005w, R = 0.125w +/- 0.005w,

0.4w <h <0.6w; 0.45w ≤ a ≤ 0.55w

The pins and holes should have a smooth surface and a loose fit to avoid friction.

Klc = [P / h · W0.5] f (ai / W)

The specimens are then attached in a universal test machine (Zwick / Roell) with metallic pins that are passed through the holes. The test specimen is then subjected to a defined tensile force (P) via the pins until it breaks at a speed of 1 mm / min. The tensile force (P), the thickness (B) and the width (W) as well as the crack length aii, the fracture toughness K _Ic are calculated using the following formula. Table 1a: compositions according to the invention Table 1b: compositions according to the invention Table 1c: Examples of compositions according to the invention Table 1d: Examples of compositions according to the invention Table 1e: Examples of compositions according to the invention Table 2: Comparative example (VG) 3 as VG3a and VG3b in variation within the specified ranges

Irradiation method of the surface of the specimen with blue light (emission maximum approx. 440 to 460 nm) with 5 projection areas on the surface of the specimen with 1 x 20 seconds each of the samples in Table 3. The samples thermally cured in Table 3 were previously with UV / Vis -Light irradiated on the surface 1 x 60 seconds on each side and then thermally cured (approx. 3 h at 95 ° C).

Table 3: Results of the measurement of the fracture toughness

The results of the measurement of the fracture toughness on the only radiation-polymerized specimens of the comparative examples with Bis-GMA as a component in the polymer matrix show very low values for the fracture toughness (VG3a, VG3b).

Significantly better values of 1.3 over 1.7 to 2.2 MPa-m ^1/2 for the fracture toughness are obtained with the bis- (2 ', 7'-dioxa-3', 8'-dioxo-4 '-aza-decyl-9'-en) tetrahydrodicyclo- pentadiene and its isomer-based composite materials obtained in the polymer matrix.

Claims

1. A polymerizable composition comprising

(i) 0 to 90% by weight of at least one inorganic filler component,

(iv) 0.01 to 10% by weight of at least one initiator, an initiator system and optionally at least one stabilizer and optionally at least one pigment, the total composition of the polymerizable composition being 100% by weight.

2. The polymerizable composition of claim 1 comprising

(i) 5 to 90% by weight of an inorganic filler component comprising at least one glass, silicate, metal oxide, mixed oxide, silicon dioxide,

Zirconium dioxide, zinc oxide and / or mixtures of at least two of the components mentioned, the components having an average particle size of 0.2 μm to 10 μm, and optionally at least one amorphous metal oxide with an average primary particle size of 10 nm to 115 nm, and

(ii) 10 to 85% by weight of the at least one urethane acrylate or a mixture of urethane acrylates;

(iii) 0.01 to 25% by weight of at least one di-, tri-, tetra- or multi-functional monomer that is not a urethane acrylate and / or a urethane alkyl acrylate, (iv) 0.01 to 10% by weight of at least one initiator, an initiator system and optionally at least one stabilizer and optionally at least one pigment, the overall composition of the composition being 100% by weight.

3. Composition according to claim 1 or 2, comprising

(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 with an average particle size of 0.4 μm to 10 μm, and optionally at least one amorphous metal oxide with an average primary particle size of 10 nm to 115 nm, and

(ii) 10 to 60% by weight comprising at least one urethane acrylate, the urethane acrylate at least one urethane acrylate having a divalent alicyclic group of the idealized formula I. and / or mixtures of these urethanes of the formula I and optionally mixtures of the isomers of the aforementioned compounds with R ¹ and R ² each independently selected from H and alkyl having 1 to 8 carbon atoms,

4. Composition according to any one of claims 1 to 3, comprising

(i) 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 with an average particle size of 0.4 μm to 10 μm, and optionally at least an amorphous metal oxide with an average primary particle size of 10 nm to 115 nm, as well as (ii) 10 to 30 wt .-% comprising at least one urethane acrylate, wherein the

Urethane acrylate at least one urethane acrylate with a divalent alicyclic group of the idealized formula I. and / or mixtures of these urethanes of the formula I and optionally mixtures of the isomers of the aforementioned compounds with R ¹ and R ² each independently selected from H and alkyl having 1 to 8 carbon atoms,

5. Composition according to one of claims 1 to 4, characterized in that the at least one inorganic filler component comprising at least one glass, silicate, feldspar, metal oxide mixed oxide, silicon dioxide, zirconium dioxide has an average particle size d ₅₀ of 0.5 to 10 μm.

6. Composition according to one of claims 1 to 5, characterized in that 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 components with one average particle size of d ₅₀ of 1.8 μm, and preferably d ₉₉ less than or equal to 20 μm, or b) the 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 the Components as a mixture of different fractions with medium particle sizes, with i) d ₅₀ from 2 to 8 μm, ii) d ₅₀ from 1.0 to 2.0 μm, and iii) d ₅₀ from 0.5 μm to 2 μm, being the fractions from i) to ii) to iii) in a ratio of 1 to 4: 1: 4 to 8, in particular from 2 to 3: 1: 6 to 7.

7. Composition according to one of claims 1 to 6, characterized in that the amorphous metal oxide comprises at least one non-agglomerated amorphous metal oxide with a primary particle size of 2 to 150 nm, and the amorphous metal oxide optionally comprises precipitated silicon dioxide, fumed silica, zirconium oxide or mixed oxides .

8. Composition according to one of claims 1 to 7, characterized in that the composition is used as (i) inorganic filler component

(1.1) 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 these filler components, and optionally

(1.2) 0.05 to 5% by weight of amorphous metal oxide, in particular fumed silica and / or precipitated silicon dioxide, based on the total composition of the composition of 100% by weight.

9. Composition according to any one of claims 1 to 8, characterized in that

(ii) a mixture of at least three different urethane acrylates and / or urethane alkyl acrylates, the mixture comprising at least one difunctional urethane with divalent alicyclic group of the formula I and / or isomers thereof and one difunctional urethane acrylate and / or urethane (alkyl) acrylate with divalent alkylene - Group and optionally at least one at least tetrafunctional dendritic urethane acrylate and / or corresponding urethane alkyl acrylate, preferably at least one hexafunctional dendritic urethane acrylate or corresponding urethane alkyl acrylate.

10. Composition according to one of claims 1 to 9, characterized in that

(iii) is selected from di-methacrylic esters of polyethers, tri-, tetra- or multifunctional methacrylic esters of polyethers and 2,2-bis- [4- (2-hydroxy-3-methacryloyloxy-propoxy) phenyl] -propane, bis- (2'-oxa-3'-oxo-pentyl-4'-en) tetrahydrodicyclopentadiene and isomers thereof and optionally pentaerythritol tetrapropoxy acrylate.

11. Composition according to one of claims 1 to 10, characterized in that the at least one stabilizer comprises water, at least one benzophenone and / or at least one phenol derivative.

12. Composition according to one of Claims 1 to 11, characterized in that it comprises (v) 0.01 to 15% by weight of a polymeric, particulate filler, the total composition of the composition being 100% by weight.

13. Polymerized composition obtainable by polymerization of the composition according to one of claims 1 to 12, i) with a UV and / or Vis radiation source, preferably with a Vis radiation source with emission maxima in the spectral range of

380 nm to 530 nm, preferably with at least one maximum or maxima in the spectral range from 400 to 500 nm and / or ii) at a pressure of 50 to 300 MPa and / or elevated temperature, preferably at 90 to 150 ° C.

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