Radiation-curable compositions for use in rapid prototyping or manufacturing processes

Abstract

The subject of the present invention is a polymerizable radiation-curable composition comprising (i) at least (a) one first monomer, the TG (glass transition temperature) of a homopolymer of which is 20° C. or higher, and at least (b) one second monomer, the TG (glass transition temperature) of a homopolymer of which is 100° C. or lower, wherein at least one of the at least one first monomer or the at least one second monomer has an alicyclic group; and (ii) at least one further component comprising at least one photoinitiator in the UV and / or Vis spectral region or a photoinitiator system in the UV and / or Vis spectral region. The subject of the present invention is furthermore blanks in the form of three-dimensional bodies of polymeric compositions, in particular radiation-curable compositions, for producing three-dimensional bodies, such as dental models, dental prosthetic parts, orthopedic instruments or dental preforms, as well as the use of the compositions for producing dental prosthetic parts, orthopedic instruments or dental preforms in rapid prototyping or rapid manufacturing or rapid tooling processes.

Description

[Technical Field]

[0001] The subject of the present invention is a polymerizable radiation-curable composition comprising (i) at least (a) one first monomer, the TG (glass transition temperature) of a homopolymer of which is 120° C. or higher, and at least (b) one second monomer, the TG (glass transition temperature) of a homopolymer of which is 100° C. or lower, wherein at least one of the at least one first monomer or the at least one second monomer comprises at least one difunctional urethane (meth)acrylate selected from difunctional urethane (meth)acrylates having an alicyclic group, in particular a bicyclic group, and optionally a divalent alkylene group; and (ii) at least one further component comprising at least one photoinitiator in the UV and / or Vis spectral region or a photoinitiator system in the UV and / or Vis spectral region. The subject of the present invention is furthermore blanks in the form of three-dimensional bodies of polymeric compositions, in particular radiation-curable compositions, for producing three-dimensional bodies, such as dental models, dental prosthetic parts, orthopedic instruments or dental preforms, as well as the use of the compositions for producing dental prosthetic parts, orthopedic instruments or dental preforms in rapid prototyping or rapid manufacturing or rapid tooling processes.

[0002] In addition to manual manufacturing methods, digital manufacturing methods such as subtractive and additive processes are becoming increasingly important in the dental field. The advantages of additive processes are the savings on expensive raw materials and the faster production of objects. Generative processes are already known in the dental field, for example in the form of laser sintering for the production of crowns and bridges, implant parts or models from CoCr, Ti or polymers.

[0003] No acrylate or acrylate derivative compositions for producing dentures have been available to date that have a corresponding property profile with respect to the mechanical requirements of dentistry in accordance with DIN EN ISO 20795-2 (see Quintessenz Zahntechnik 2017-43(10): p. 1325). Therefore, there is a fundamental need for materials for producing anatomical models, anatomical tabletop models, in particular as a replacement for dental plaster models produced from impressions of a patient's dental condition and gums or dentition, as well as for producing prosthetic parts or final dentures. Furthermore, there is a need for compositions for producing final prosthetic parts, orthopedic appliances, or dental preforms.

[0004] The impression material and model (also referred to herein as anatomical model or working model) are the basis for an accurate denture. An optimal, individualized restoration can only be achieved if the dentist and dental technician adhere to the material-specific requirements when taking the impression and making the model.

[0005] Dental technicians typically use plaster to make models. Plaster meets the requirements for models that are easy to use, accurate, dimensionally stable, and have a smooth surface. Requirements for dental anatomical plaster models include: volume stability, minimal expansion, non-shrinkage, especially during wax extraction, with or without water, storage stability, compatibility with disinfectants, insulating agents, and waxes, a smooth, non-porous surface, sufficient pressure resistance, high edge stability, good abrasion resistance, and high heat resistance.

[0006] The object of the present invention was to provide a composition that has good radiation curing properties, particularly UV and / or Vis radiation curing properties, and exhibits good polymerization depth upon radiation curing. Furthermore, it is desirable that the radiation curing composition have good mechanical properties both at ambient room temperature and at elevated temperatures, so that the composition can be used for the production of anatomical models, particularly dental models. Therefore, it is desirable that the composition meets the requirements of a model material for model casting, implant dentistry, saw-cut and master models, and for producing accurate crossbite models. Therefore, it was also an objective of the present invention to provide a radiation-curable composition usable in additive / generative processes that satisfies the following requirements for printed 3D objects in the cured state: mechanical properties and dimensional stability are maintained at temperatures between 45°C and 55°C in a pressure pot, dimensional stability is maintained during deep drawing processes and cleaning, for example, using a steam jet device, the photocurable composition is storage stable without significant viscosity changes over the storage period, sufficient reactivity upon irradiation with a laser, LED, or DLP projector, the workpiece / object can be printed with sufficient geometric accuracy / resolution, the mixture is color stable, and exhibits no or only slight thixotropy. Therefore, it was an objective of the present invention to provide a radiation-curable composition that, when tested in the polymerized state in water at 55°C, has a flexural strength of at least 40 MPa and a flexural modulus, equivalent to modulus, of at least 800 MPa.

[0007] Further requirements for dental stone models are outlined below for the various work steps: the combination of the model with the action of heat and water: casting of the plastic saddle in model casting (20 minutes in a water bath at 55°C), completion of the partial prosthesis / model casting (20-30 minutes in a water bath at 55°C), completion of the complete prosthesis (injection technique parajet / cuvette technique - 30 minutes in a water bath at 55°C), completion of the complete prosthesis, tamping press technique (30-40 minutes in a water bath at 100°C), deep drawing splint (20-30 minutes at 55°C), steam for cleaning (70-110°C), extraction (3-5 minutes at 80-100°C), veneering with paraveneer (55°C, 2 bar, 20 minutes).

[0008] Combination of models with insulation and mechanical action: introduction into the articulator, i.e. mechanical loading of the model in the articulator, insulation against prosthetic plastic, insulation against veneering composites, insulation against wax, UV plastic and / or wax, dipping wax shielding.

[0009] Combination of models with the action of heat without water: deep drawing (155-170°C / 1-2 min), fixing of models with a hot glue gun, fixing of models with adhesive wax, blocking with UV plastic and / or wax, dipping wax, deep drawing sheets and manual curing of composites with Hi Lite Power / 3D (2 times for 90 seconds each and once for 180 seconds), curing of occlusal splints with Hi Lite Power / 3D (2 times for 5 minutes each), milling stumps for milling techniques (heat resistant to accumulated heat).

[0010] Behavior of the polymerizing compositions in other work steps: dimensional stability and good cleaning properties in ultrasonic baths with isopropanol, discoloration and cleaning in articulating foils (Bausch, red, blue, black), discoloration and cleaning in articulating sprays (various manufacturers), wear resistance at the preparation margins (crowns, bridges, model casting clamp teeth), breakage / wear resistance (in articulators - plaster vs. plastic, plastic vs. plastic).

[0011] The situational model and all working models form the basis for all subsequent dental technical work. To meet high aesthetic requirements, the resin mixture for the final dentures, e.g., working models, orthodontic models, must be dimensionally and thermally stable. If you want to replace the plaster model with a printed plastic model to take advantage of the digital workflow, the plastic model must have the same positive properties as the plaster. However, various physical and chemical boundary conditions affect the thermoplastic properties of plastics. It is important to keep the thermoplastic properties within limits by optimally selecting the monomers.

[0012] So far, no materials exist that possess all the thermal stabilities mentioned, which means that they can only be used in some dental technology applications.

[0013] The present invention was therefore based on the problem of providing a composition comprising a monomer with particularly high thermal and dimensional stability, so that the polymerized composition can withstand high temperatures when used as a molded part in a pressure pot and during the deep drawing of occlusal splints, which must be withstood multiple times during the production of aligners.

[0014] The problem of the present invention is solved by a composition according to claim 1, a polymeric composition according to claim 12, a blank according to claim 14, and a use according to claim 15. Preferred embodiments are disclosed in the dependent claims and in more detail in the description.

[0015] The subject of the present invention is a polymerizable radiation-curable composition comprising (i) the monomers, which include at least (a) one first monomer, the TG (glass transition temperature) of a homopolymer of which is 120° C. or higher, and at least (b) one second monomer, the TG (glass transition temperature) of a homopolymer of which is 100° C. or lower, and at least one of the at least one first monomer or the at least one second monomer having an alicyclic group, in particular an at least bicyclic alicyclic group; and (ii) at least one further component, which at least one further component comprises at least one photoinitiator in the UV and / or Vis spectral region or a photoinitiator system in the UV and / or Vis spectral region.

[0016] The term "monomer" is understood to mean a mixture of the mentioned monomers, for example, in particular, a mixture comprising a first monomer and a second monomer. A first monomer is understood to mean not only (i) the first monomer but also (ii) a mixture of the first monomer, and a second monomer is understood to mean not only (i) the second monomer but also (ii) a mixture of the second monomer. TG is advantageously determined by DSC.

[0017] Particularly preferred compositions have a viscosity at ambient room temperature that is suitable for use in generative radiation curing processes. Thus, the composition advantageously has a viscosity of less than 5000 mPas. Particularly preferred is a viscosity of less than 3000 mPas, especially from 500 to 2500 mPas, at ambient room temperature (about 20°C to 23°C).

[0018] According to a preferred embodiment, the composition comprises a mixture of first and second monomers, the first monomer comprising a difunctional acrylate with a divalent alicyclic group and a difunctional methacrylate with a divalent alicyclic group, in particular a divalent bicyclic acrylate or a divalent bicyclic methacrylate, preferably a divalent tetrahydrodicyclopentadiene, and the second monomer comprising at least one monofunctional acrylate with an alicyclic group and / or a monofunctional methacrylate with an alicyclic group, particularly preferred is a mixture of a monofunctional acrylate with a bicyclic alicyclic group and a difunctional acrylate with a bicyclic alicyclic group. Likewise preferred are the methacrylates of each of these monomers.

[0019] According to another preferred embodiment, (i) as the monomer: (a) in particular as at least one first monomer at least one triacrylate derived from 1,3,5-tris(hydroxyalkyl)isocyanurate, in which the hydroxyalkyl groups each independently contain 1 to 8 C atoms, in particular have 3 to 8 C atoms, are linear, branched and / or cyclic, in particular have 1 to 6 C atoms, preferably 1 to 4 C atoms, preferably 1 to 3 C atoms, particularly preferably are hydroxyethyl, and optionally (b) a difunctional acrylate having a divalent alicyclic group and a difunctional methacrylate having a divalent alicyclic group, and optionally (c) in particular as at least one second monomer at least one monofunctional acrylate having an alicyclic group and / or a monofunctional methacrylate having an alicyclic group; A composition comprising:

[0020] Optionally, (d) as a monomer, advantageously as at least one third monomer, at least one disubstituted 4,4'-di(oxabenzole)dialkylmethane of formula I may be present in the composition: [ka] where R 1 , R 2 , R 5 and R 6 are each independently selected from H or C1-C4 alkyl, and R 3 and R 4 are each divalent C1-C4 alkylene, n=0-6, and m=0-6. Depending on the substitution pattern, this disubstituted 4,4'-di(oxabenzole)dialkylmethane of Formula I is the first or third monomer. n and m=2, and R 1 , R 2 , R 5 and R 6 is methyl and R 4 and R 3 When R is ethylene, it is the third monomer. In Formula I, n=2 and m=2, and R 1 , R 2 , R 5 and R 6 is methyl and R 4 and R 3 When is ethylene, this monomer is a third monomer and may be present in the total composition at 0 to 50% by weight.

[0021] where the monomer (d) is a group R 1 ~R 6 and can be the first or third monomer depending on the choice of subscripts n and m, and since the TG can be 120°C or higher, it is the first monomer. The third monomer has a TG of 100°C or higher and advantageously less than 120°C, and is advantageously used at 0-40% by weight or less in the total composition. When the TG is 30°C or higher but less than 50°C, the monomer is present at 0-10% by weight or less in the total composition.

[0022] Advantageously, the composition comprises only 0 to 7.5% by weight, preferably not in a significant proportion, advantageously 0 to 0.05% by weight, of at least one acrylic acid ester having an additional carboxy group, for example at least one acrylic acid ester having at least one additional anhydride group of the carboxy group and / or at least one derivative of said acrylic acid ester.

[0023] A further preferred embodiment of the composition comprises (i) monomers comprising: (a) at least one first monomer or a mixture of first monomers, each of which has a homopolymer TG (glass transition temperature) of 120° C. or higher, the first monomer or the mixture of first monomers comprising at least one diacrylate ester based on a tricyclodecane dialkanol, the alkanol containing 1 to 6 C atoms, or a mixture thereof; and (b) at least one second monomer or a mixture of second monomers, each of which has a homopolymer TG (glass transition temperature) of 120° C. or higher, the first monomer or the mixture of first monomers comprising at least one diacrylate ester based on a tricyclodecane dialkanol, the alkanol containing 1 to 6 C atoms, or a mixture thereof; the TG (glass transition temperature) of the homopolymer of said monomer is 100°C or less, and the second monomer or mixture of second monomers comprises at least one monofunctional acrylate ester based on a tricyclodecane alkanol (synonymous with (octahydro-4,7-methano-1H-indenyl)alkanol) containing 1 to 6 C atoms, or a mixture thereof, and optionally at least one difunctional urethane (meth)acrylate selected from difunctional urethane (meth)acrylates having a divalent alkylene group, wherein optionally (i) in the composition there are present 15 to 25% by weight of monofunctional acrylate esters based on tricyclodecane alkanols, the alkanols of which contain 1 to 6 C atoms, and optionally 5 to 15% by weight of diacrylate esters based on tricyclodecane dialkanols, the alkanols of which contain 1 to 6 C atoms, whereby the total composition is 100% by weight, or (ii) 5 to 15% by weight of diacrylate esters based on tricyclodecane dialkanols, the alkanols of which contain 1 to 6 C atoms, and 15 to 25% by weight of monofunctional acrylate esters based on tricyclodecane alkanols, the alkanols of which contain 1 to 6 C atoms, are present, and in particular in (ii) there is no triacrylate derived from 1,3,5-tris(hydroxyalkyl) isocyanurate, wherein the total composition is 100% by weight, or (iii) 15 to 45% by weight of a mixture comprising a monofunctional acrylate ester based on a tricyclodecane alkanol, the alkanol of which contains 1 to 6 C atoms, and a diacrylate ester based on a tricyclodecane dialkanol, the alkanol of which contains 1 to 6 C atoms, is present, and in particular in (iii) no triacrylate derived from 1,3,5-tris(hydroxyalkyl) isocyanurate is present, wherein the total composition is 100% by weight.

[0024] Furthermore, the composition may advantageously comprise, as at least a first monomer (a.1), at least one triacrylate derived from a 1,3,5-tris(hydroxyalkyl)isocyanurate, such as 1,3,5-tris(2-hydroxyethyl)isocyanurate triacrylate, 1,3,5-tris(2-hydroxymethyl)isocyanurate triacrylate, 1,3,5-tris(2-hydroxyethyl)isocyanurate trimethacrylate, 1,3,5-tris(2-hydroxymethyl)isocyanurate trimethacrylate, or a mixture comprising at least two of these monomers.

[0025] A preferred first monomer comprises (b) and is selected from tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, tricyclodecane diethanol diacrylate, tricyclodecane diethanol dimethacrylate, and / or mixtures thereof. The tricyclodecane monomers may include all structural isomers of these monomers.

[0026] The other monomer, in particular the third monomer, comprises 0 to 10% by weight or less of a monomer having a TG of 100° C. or more and advantageously less than 120° C. Accordingly, the composition may further comprise (d) at least one disubstituted 4,4′-di(oxabenzole)dialkylmethane of formula I, wherein R 1 , R 2 , R 5 and R 6 are each independently selected from H or C alkyl; R 3 and R 4 are each a divalent C1-C3 alkylene, particularly a C2 alkylene, n=1-6, and m=1-6. 1 and R 2 are methyl, and R 5 and R 6 are the same and are selected from H, methyl and ethyl, in particular R 5 and R 6 are the same and are selected from H and methyl, and R 3 and R 4 are each independently a divalent ethylene or propylene, n=1 to 6, preferably n=2 to 4, m=1 to 6, preferably m=2 to 4, preferably n=2 and m=2, or n=4 and m=4, and mixtures thereof. Depending on the TG height of each of the specifically substituted disubstituted 4,4'-di(oxabenzole)dialkylmethanes of formula I, this monomer may be the first, second, or third monomer. Advantageously, the composition is free of monomers of formula I, particularly those in which n and m are 4 or greater, or contains 0 to 7.5 wt. % or less of such monomers, based on the total composition.

[0027] Below are shown some monomers of Formula I, some with their TGs: ethoxylated (2) bisphenol A dimethacrylate (TG 105° C.), ethoxylated (2) bisphenol A diacrylate, ethoxylated (3) bisphenol A dimethacrylate (TG 115° C.), ethoxylated (3) bisphenol A diacrylate (TG 67° C.), ethoxylated (4) bisphenol A dimethacrylate (TG 90° C.), ethoxylated (4) bisphenol A diacrylate (TG 60° C.), ethoxylated (10) bisphenol A dimethacrylate (TG (−1° C.)), ethoxylated (10) bisphenol A diacrylate (TG 2° C.).

[0028] According to another embodiment, the second monomer or mixture of second monomers may comprise at least one monomer or mixture of second monomers, the TG of the respective homopolymer of which is 30° C. or higher, preferably comprising a second monomer having a TG in the range of 30° C. to 100° C., particularly preferably comprising a second monomer having a TG in the range of 50° C. to 100° C. Further preferred compositions comprise (i) monomers including a first monomer, a second monomer and a third monomer, and additional components advantageously comprising at least one UV, Vis or UV / Vis stabilizer.

[0029] According to another embodiment, the composition includes (i) a monomer, (a) at least one first monomer or mixture of first monomers, wherein the TG (glass transition temperature) of each homopolymer of the corresponding first monomer is 120° C. or higher, is present in an amount of 40 to 99.99 wt. %, and (b) 0 to 60% by weight, in particular 0 to 10% by weight, of at least one second monomer or mixture of second monomers, the TG (glass transition temperature) of the corresponding respective homopolymer of the second monomer being 100° C. or less, - 0.01 to 5% by weight of at least one further component comprising at least one photoinitiator in the UV and / or Vis spectral region or a photoinitiator system in the UV and / or Vis spectral region, and optionally at least one stabilizer in the UV and / or Vis spectral region, and optionally at least one pigment and / or dye, and further customary additives, Here, the total composition is 100% by weight, and in particular the viscosity of the composition at ambient room temperature (about 20° C. to 23° C.) is 3000 mPas or less, in particular 500 to less than 2500 mPas.

[0030] According to yet another embodiment, the composition comprises (i) as a first monomer: (e) at least one difunctional urethane (meth)acrylate selected from difunctional urethane (meth)acrylates having a divalent alkylene group, and / or (f.1) at least one mono-, tri-, tetra- or polyfunctional monomer, in particular not a urethane (meth)acrylate, in particular an acrylate ester and / or methacrylate ester of a polyether, selected from dimethacrylate esters of polyethers, tri-, tetra- or polyfunctional methacrylate esters of polyethers, diacrylate esters of polyethers, tri-, tetra- and / or polyfunctional acrylate esters of polyethers; may include:

[0031] (i) Below: (c) at least one monofunctional acrylate having an alicyclic group and / or a monofunctional methacrylate having an alicyclic group, in particular selected from (octahydro-4,7-methano-1H-indenyl)methanol acrylate, (octahydro-4,7-methano-1H-indenyl)methanol methacrylate, (octahydro-4,7-methano-1H-indenyl)ethanol acrylate and (octahydro-4,7-methano-1H-indenyl)ethanol methacrylate, (f.2) at least one mono-, di-, tri-, tetra- or polyfunctional monomer, in particular not a urethane (meth)acrylate, in particular an acrylate ester and / or methacrylate ester of a polyether, selected from dimethacrylate esters of polyethers, tri-, tetra- or polyfunctional methacrylate esters of polyethers, diacrylate esters of polyethers, tri-, tetra- and / or polyfunctional acrylate esters of polyethers; Preferred are compositions comprising a second monomer comprising:

[0032] Also suitable are trimethylolpropane triacrylate (TG 60° C.), dipentaerythritol pentaacrylate (TG 90° C.), ethoxylated (4) pentaerythritol tetraacrylate (TG 70° C.) and ethoxylated (4) pentaerythritol tetraacrylate (TG 70° C.). The trifunctional monomers may further be selected from the following, preferably in an amount of 0 to 10% by weight, in particular 0.01 to 5% by weight, of the total composition: ethoxylated (20) trimethylolpropane triacrylate (TG -40°C), ethoxylated (3) trimethylolpropane triacrylate, propoxylated (3) trimethylolpropane triacrylate, ethoxylated (6) trimethylolpropane triacrylate (TG -10°C), ethoxylated (9) trimethylolpropane triacrylate (TG -20°C), propoxylated (3) glyceryl triacrylate (TG 20°C), ethoxylated (15) trimethylolpropane triacrylate (TG -30°C). The viscosity of the composition should preferably be less than 3000 mPas.

[0033] Likewise preferred compositions may also comprise, in addition to the first monomer, (iii) in particular 0 to 15% by weight, optionally 1 to 10% by weight, of a third monomer, wherein the third monomer is (f.3) at least one mono-, tri-, tetra- or polyfunctional monomer, in particular not a urethane (meth)acrylate, in particular an acrylate ester and / or methacrylate ester of a polyether, selected from dimethacrylate esters of polyethers, tri-, tetra- or polyfunctional methacrylate esters of polyethers, diacrylate esters of polyethers, tri-, tetra- and / or polyfunctional acrylate esters of polyethers; may include:

[0034] Examples of tetraacrylates contained in the third monomer: pentaerythritol tetraacrylate (TG 105°C), ditrimethylolpropane tetraacrylate (TG 100°C).

[0035] According to yet another embodiment, the composition comprises: (i) a composition comprising: (a) 70 to 99.99% by weight, in particular 80 to 99.99% by weight, of a first monomer or a mixture of first monomers, the TG (glass transition temperature) of the corresponding homopolymer of each first monomer being 120°C or higher, the first monomer or the mixture of first monomers comprising at least one difunctional urethane (meth)acrylate selected from at least one difunctional acrylate having a divalent alicyclic group and / or at least one difunctional methacrylate having a divalent alicyclic group, and optionally a difunctional urethane (meth)acrylate having a divalent alkylene group; - at least (b) one second monomer or a mixture of second monomers, the TG (glass transition temperature) of each homopolymer of which corresponding second monomer is 100°C or less, and which second monomer or mixture of second monomers comprises at least one second monomer or mixture of second monomers, the TG of each homopolymer of which is 30°C or more, preferably a second monomer having a TG in the range from 30°C to 100°C, particularly preferably a second monomer having a TG in the range from 50°C to 100°C, and optionally 0 to 30% by weight, in particular 0 to 20% by weight, preferably 1 to 15% by weight, of a second monomer or mixture of second monomers, in particular a mono- and / or di-functional acrylate and / or methacrylate, preferably a bicyclic alicyclic acrylate and / or methacrylate, and optionally - 0 to 10% by weight of a third monomer, the TG of each homopolymer of which is greater than 100°C, in particular between 105°C and 115°C, in particular less than 118°C, - 0.01 to 5% by weight of at least one further component comprising at least one photoinitiator in the UV and / or Vis spectral region or a photoinitiator system in the UV and / or Vis spectral region, and optionally at least one stabilizer in the UV and / or Vis spectral region, and optionally at least one pigment and / or dye, and further customary additives; The monomer may include:

[0036] Similarly, the composition may comprise: (i)(a) 75 to 99.99% by weight, in particular 80 to 99.99% by weight, of a first monomer or a mixture of first monomers, the TG (glass transition temperature) of the corresponding homopolymer of the first monomer or the mixture of first monomers being 120°C or higher, the first monomer or the mixture of first monomers comprising at least one difunctional urethane (meth)acrylate selected from at least one difunctional acrylate having a divalent alicyclic group and / or at least one difunctional methacrylate having a divalent alicyclic group, and optionally a difunctional urethane (meth)acrylate having a divalent alkylene group; - 0 to 25% by weight, in particular 0 to 20% by weight, preferably 1 to 20% by weight, of at least (b) one second monomer or a mixture of second monomers, the TG (glass transition temperature) of each corresponding homopolymer of the second monomer being 100°C or less, the second monomer or the mixture of second monomers comprising at least one monofunctional acrylate having an alicyclic group and / or a monofunctional methacrylate having an alicyclic group; - 0.01 to 5% by weight of at least one further component comprising at least one photoinitiator in the UV and / or Vis spectral region or a photoinitiator system in the UV and / or Vis spectral region, and optionally at least one stabilizer in the UV and / or Vis spectral region, and optionally at least one pigment and / or dye, and further customary additives; wherein the total composition is 100% by weight, and in particular the viscosity of the composition at ambient room temperature (about 20°C to 23°C) is 3000 mPas or less, in particular 500 to less than 2500 mPas.

[0037] In a particularly preferred composition, the first monomer is present in an amount of 70 to 99.99% by weight, particularly 80 to 99.99% by weight, and may comprise a mixture of 5 to 50% by weight, particularly 5 to 25% by weight, and preferably 5 to 20% by weight of at least one difunctional acrylate having a divalent alicyclic group and / or at least one difunctional methacrylate having a divalent alicyclic group, based on the total composition, and optionally 5 to 50% by weight, particularly 5 to 45% by weight, and preferably 7.5 to 30% by weight of at least one difunctional urethane (meth)acrylate selected from difunctional urethane (meth)acrylates having a divalent alkylene group. Optionally, a further first monomer may be present in the mixture of first monomers.

[0038] Further particularly preferred compositions comprise (i) a monomer and (ii) at least one further component, wherein TG(total) is determined from 1 / TG(total) of the monomer, where 1 / TG(total) is determined according to the formula: 1 / TG(total)=w1 / TG (1) +w2 / TG (2) +w3 / TG (3) +Optionally, w4 / TG (4) +Optionally, w5 / TG (5) +Optionally, wn / TG (n) where w1, w2, w3, w4, w5 and wn are each the weight fraction of each monomer, in particular of each first monomer, of each second monomer or optionally of each third monomer, in 100% by weight of the total mixture of at least first and second monomers, and n=6 to 50, TG(total) is 80°C or higher, in particular 100°C or higher, preferably 120°C or higher and advantageously 170°C or higher, and the viscosity of the composition at ambient room temperature (about 20°C to 23°C) is 3000mPas or lower, in particular less than 500 to 2500mPas.

[0039] wherein (i) the monomers include at least (a) one first monomer, the TG (glass transition temperature) of which homopolymer is 120°C or higher, and at least (b) one second monomer, the TG (glass transition temperature) of which homopolymer is 100°C or lower; the second monomer or mixture of second monomers includes at least one second monomer or mixture of second monomers, each of which homopolymer has a TG of 30°C or higher, preferably a second monomer having a TG in the range of 30°C or higher to 100°C or lower, and particularly preferably a second monomer having a TG in the range of 50°C or higher to 100°C or lower; and (ii) the at least one further component includes at least one photoinitiator in the UV and / or Vis spectral region or a photoinitiator system in the UV and / or Vis spectral region.

[0040] One embodiment particularly includes a polymerized composition obtained by radiation curing of the composition, wherein TG(total) is determined by 1 / TG(total) according to the following formula, and (i) the monomers are present in the total composition according to the following weight proportions (w1, w2, w3, w4, w5 and wn):

[0041] 1 / TG(total)=w1 / TG (1) +w2 / TG (2) +w3 / TG (3) +Optionally, w4 / TG (4) +Optionally, w5 / TG (5) +Optionally, wn / TG (n) where w1, w2, w3, w4, w5, and wn are the weight fractions of the first and second monomers and optionally the third monomer in 100 wt. % of the total composition, n=6 to 50, TG is 100°C or higher, and the polymerized composition a) has a flexural strength (according to DIN EN ISO 20795-2) of 40 MPa or higher, especially when measured in water at 55°C, and / or b) has a modulus of elasticity (according to DIN EN ISO 20795-2) of 800 MPa or higher, especially when measured in water at 55°C.

[0042] The glass transition temperature of the copolymer can be approximately expressed by the Fox equation (see above and Bulletin of the American Physical Society 1,3 Page 123 (1956)).

[0043] Semicrystalline plastics (most common plastics have a crystalline fraction of 10-80%) have both a glass transition temperature (below which the amorphous phase freezes out (with embrittlement)) and a melting temperature (at which the crystalline phase disappears). Because the glass transition is not a first-order phase transition, it is not associated with a precise temperature, as is the melting point for crystals. The detected values ​​vary systematically depending on the time and length scales or modes of motion of the molecular dynamics to which the measurement method used (see below) is sensitive. Whether a plastic can be used above or below its glass transition temperature depends on the type of plastic (it should be noted here that the glass transition temperature of a plastic increases with its crosslink density; i.e., the glass transition temperature of a thermoset plastic is significantly higher than that of a thermoplastic).

[0044] 1 / Tg=w1 / Tg (1) +w2 / Tg (2) , where w1 and w2 are the weight fractions of the respective comonomers, and Tg (1) and Tg (2)is the glass transition temperature of each of the homopolymers of monomers 1 and 2. In the case of additional comonomers, an additional term (wn / Tg(n)) is inserted into this equation. The disclosed glass transition temperatures can be taken from "polymer handbooks" known to those skilled in the art, or from data from the monomer manufacturer. If data on the glass transition temperature is not available, it can be determined by DSC, DMS (dynamic mechanical analysis), dielectric relaxation spectroscopy, or dilatometry. DSC measurement is the usual method for determining the glass transition temperature of a homopolymer. In this case, the homopolymer is dried, heated to 120°C, quenched to -100°C, and then heated at 20°C / min to 150°C or above, up to 300°C, and the glass transition temperature data is examined. The glass transition temperature is measured as an average value.

[0045] Preferred are compounds of formula I, wherein R 1 and R 2 are methyl, and R 5 and R 6 are identical and selected from H, methyl and ethyl, in particular R 5 and R 6 are the same and are selected from H and methyl; R 3 and R 4 are each independently a divalent ethylene or propylene, n=1 to 6, preferably n=2 to 4, m=1 to 6, preferably m=2 to 4, and preferably n=2 and m=2 or n=4 and m=4], and mixtures thereof.

[0046] Preferred at least difunctional monomers that are not urethane (meth)acrylates are selected from (b) difunctional acrylates having a divalent alicyclic group and difunctional methacrylates having a divalent alicyclic group. Particularly preferably, (b) they are selected from tricyclodecane dimethanol diacrylate (TCDDA), tricyclodecane dimethanol dimethacrylate, tricyclodecane diethanol diacrylate, tricyclodecane diethanol dimethacrylate, and / or mixtures thereof (partially synonymous with bis(methacryloyloxymethyl)tetrahydrodicyclopentadiene or bis(acryloyloxymethyl)tetrahydrodicyclopentadiene).

[0047] Advantageously, all monomers (a), (b), (c), (d), (e) and (f.1), (f.2) and / or (f.3) according to the invention have an average molecular weight (weight average) of less than 2000 g / mol, particularly preferably monomers (a), (b), (d), (e) and (f.1), (f.2) and / or (f.3) have an average molecular weight of less than 1000 g / mol.

[0048] When selecting a monomer, care should also be taken to ensure good bonding between the monomer and any fillers used. Typically, polyurethanes, acrylates, polyesters, and other monomers do not bond well with the fillers used. Therefore, the fillers are usually surface silanized or hydrophobized to improve bonding with the monomers.

[0049] If inorganic fillers cannot be used in the polymerizable composition based on the particular dental application, for example due to the desired viscosity of the composition, a method for reflecting radiation, and in particular for diffusely reflecting or scattering incident radiation, is to use dyes or pigments in the composition. A dye is considered to be a compound that is soluble in the polymerizable composition and that advantageously forms a clear solution.

[0050] The radiation-curable compositions according to the invention can be irradiated advantageously with a radiation source emitting light in the Vis spectral region, particularly preferred are radiation sources emitting radiation at 360 to 750 nm, in particular at about 385 nm, particularly preferably at about 405 nm. Particularly preferably, the compositions according to the invention can be irradiated in the Vis spectral region of 380 to 660 nm using a polychromatic radiation source, such as, for example, a DLP projector, or advantageously using a monochromatic radiation source, such as, for example, a laser projector.

[0051] When such pigments and / or dyes are added, the photoinitiator content of the composition can be reduced, since too high a photoinitiator content can lead to so-called "overcuring," imprecision, and / or shape changes of the irradiated composition, making the correspondingly manufactured dental part unusable.

[0052] The optional use of inorganic fillers, pigments or dyes according to the invention leads to a uniform scattering of the radiation source, in particular the UV and Vis radiation source, in the monomer matrix of the composition, which results in a uniform curing of the composition, which in turn leads to higher fracture energy values ​​being achieved in the polymerized composition.

[0053] The compositions according to the invention can be irradiated using a radiation source in the Vis spectral range, in particular from 385 to 405 nm, preferably in a stereolithography process to obtain polymeric compositions advantageously in the form of blanks, 3D moulded parts, dental prosthetic parts, anatomical models, anatomical table models, dental working models, dental complete models, dental die models, anatomical or dental saw-cut models, in particular situation models, crossbite models, functional models, pre-models, restorative models, precision models, master models and precision crossbite models, anatomical models for replacing dental plaster models, prosthetic parts, orthopedic appliances or dental preforms, which polymeric compositions, optionally after a post-heat treatment with a radiation source, have the following properties: 20795-2, particularly at ambient room temperature, advantageously 23°C ± 2°C, preferably between ambient room temperature and 55°C (in water), a) a flexural strength of 40 MPa or more, especially 75 MPa or more, and / or b) a modulus of elasticity of 800 MPa or more, especially more than 1500 MPa, especially 2000 MPa or more. Advantageously, the radiation-curable composition, especially as a molding or blank, has the flexural strength and modulus specified below. For the definition of the dental model, see the teachings of Zahntechnik, Band 3, Quintessenz Verlag, A- Hohmann, W. Hielscher, 5 August 2012. Post-curing or post-heat treatment can advantageously be carried out, for example, using a laboratory lighting device (HiLite Power 3D) or in a light oven, advantageously with a light spectrum of 390 to 540 nm.

[0054] Optionally, the composition may further comprise, as (f.2), at least one difunctional monomer that is not a urethane acrylate or urethane methacrylate, at least one polyether diacrylate, such as poly(ethylene glycol) diacrylate, poly(ethylene glycol) di(alkyl)acrylate, poly(propylene glycol) diacrylate, poly(propylene glycol) di(alkyl)acrylate, or a mixture of at least two of the foregoing monomers. Preferred polyether diacrylates may be selected from triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and / or tetraethylene glycol dimethacrylate. Alternatively or additionally, the composition may comprise a diacrylate selected from decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, hexyldecanediol di(meth)acrylate, and butanediol di(meth)acrylate, or a mixture comprising at least one acrylate.

[0055] The notation in parentheses with the term (methyl)acrylate or (alkyl)acrylate means that the acrylate can be present as the acrylate or methylacrylate, or as the alkylacrylate.

[0056] As a monofunctional monomer, hydroxyethyl acrylate can be used, as can hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and / or hydroxyethyl acrylate, optionally as a mixture of at least two of the aforementioned monomers.

[0057] Furthermore, the composition may contain (d) at least one at least difunctional urethane (meth)acrylate selected from difunctional urethane (meth)acrylates having divalent alkylene groups (difunctional urethane acrylates and / or difunctional urethane methacrylates). The content may be 0 to 40% by weight in the total composition, where the content is advantageously 1 to 35% by weight, preferably 5 to 35% by weight, and advantageously the proportion of the first monomer component is 70 to 99.99% by weight.

[0058] The difunctional urethane (meth)acrylate having a divalent alkylene group is advantageously selected from linear or branched urethane dimethacrylates functionalized with divalent alkylene groups, functionalized polyethers having alkylene groups, such as bis(methacryloxy-2-ethoxycarbonylamino)alkylene, bis(methacryloxy-2-ethoxycarbonylamino)-substituted polyalkylene ethers, advantageously 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane, UDMA or HEMA-TDMI. Preferred is bis(methacryloxy-2-ethoxycarbonylamino)alkylene, where alkylene is a linear or branched C3-C 20 , advantageously C3-C6, for example, alkylene, particularly preferably substituted with methyl groups, such as HEMA-TMDI. Divalent alkylene advantageously includes 2,2,4-trimethylhexamethylene and / or 2,4,4-trimethylhexamethylene.

[0059] Optionally, the composition may contain one or more fillers, such as doped silicon dioxide fillers, especially mixed oxides of zirconium dioxide and silicon dioxide. Particularly preferred are particularly aggregated mixed oxides containing 75 to 99% by weight of silicon dioxide and 1 to 25% by weight of silicon dioxide, based on the total composition of the mixed oxide. In particular, the mixed oxide contains 85 to 90% by weight of silicon dioxide and 10 to 15% by weight of zirconium dioxide, wherein the primary particles of the aggregated oxide particles contain microcrystalline domains of 4 to 7 nm, advantageously with a crystallinity index of 0.6 to 0.7 as measured by the method of Windisch et al. (WO 01 / 30306), and further preferably the aggregated oxide particles are surface-modified with at least one organofunctional silane reactive with at least one monomer and / or polymer component. The agglomerated oxide particles treated according to the present invention have excellent properties in terms of gloss level in abrasion measurements, excellent transparency, and very good values ​​in reflectance and roughness measurements after toothbrush testing.

[0060] The particle size of the dental glass containing inorganic fillers, for example at least one inorganic oxide, mixed oxide, or for example barium aluminum oxide, is in this application on average less than 10 μm in average particle size d 50 Particularly preferably, the filler has a particle size of about 3 to 70 nm, in particular 10 to 50 nm (nanometers), optionally the particles can be aggregated or agglomerated into particles up to 10 μm. The primary particle size of the inorganic filler, which can optionally be present as aggregated and / or aggregated primary particles, is on average about 3 to 70 nm, in particular 10 to 50 nm. Preferably, the mixed oxide of zirconium dioxide and silicon dioxide has a primary particle size of 3 to 70 nm. The advantage of very small particle sizes, which can optionally be aggregated and / or agglomerated, is that light is substantially diffusely scattered by these particles during radiation curing, thus resulting in better curing in stereolithography or DLP processes.

[0061] Furthermore, it is preferred that the composition be non-thixotropic. Additionally, it is particularly preferred that the composition have a viscosity of less than 3000 mPas, in particular less than 500-2500 mPas, preferably 500-2000 mPas, and particularly preferably 500-1600 mPas. The viscosity is advantageously measured using a rheometer (Anton Par, Physiker NCR 301, viscosity range 200-3000 mPas, 100 / s at 23°C) according to DIN 1342-2;2003-11 (Newtonian liquids) or DIN 1342-3;2003-11 (non-Newtonian liquids). The composition according to the present invention exhibits no thixotropy, or advantageously only very little thixotropy. The produced composition is structurally viscous, and it is preferred that the composition be structurally viscous regardless of whether it contains a filler. According to a further embodiment, it is preferred that little change in viscosity occurs over a relatively long storage period. Furthermore, the composition exhibits very good reactivity when irradiated using a laser or DLP projector.

[0062] Particularly preferred photoinitiators include α-hydroxyphenyl ketones, 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 photoinitiators, combinations of phenylphosphine oxides, bisacylphosphine oxides (BAPO).

[0063] 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).

[0064] According to a further preferred embodiment, the composition comprises: (ii) 0.01 to 2% by weight of a photoinitiator or photoinitiator system in the UV and / or Vis region of the spectrum, and 0.01 to 2% by weight of a stabilizer, and optionally (g) inorganic fillers including inorganic oxides or inorganic mixed oxides and / or dental glass, in particular zirconium dioxide, mixed oxides of zirconium oxide and silicon dioxide, 0 to 10% by weight, in particular 0.01 to 7.5% by weight of silicon dioxide; where the total composition is 100% by weight.

[0065] The subject of the present invention is also a composition optionally containing a filler, the inorganic filler being optionally present as aggregated and / or coagulated primary particles, the primary particle size of which is on average about 3 to 70 nm, in particular 10 to 50 nm. Alternatively or additionally, conventional fillers having a particle size of 0.4 to 10 μm can be used in the composition.

[0066] The subject of the present invention is further a polymeric composition, as well as the corresponding 3D mouldings, and dental models, splints, orthodontic appliances and prosthetic mouldings or blanks as described below, in which the polymeric composition alternatively or cumulatively i) a) has a flexural strength (according to DIN EN ISO 20795-2) of 75 MPa or more, in particular 80 MPa or more, preferably measured (according to DIN EN ISO 139), preferably 90 MPa or more, and / or b) has an elastic modulus (according to DIN EN ISO 20795-2) of 2000 MPa or more, and / or ii) a) have a flexural strength (according to DIN EN ISO 20795-2) of 70 MPa or more, in particular when measured in water at 37°C, and / or b) have a modulus of elasticity (according to DIN EN ISO 20795-2) of 2000 MPa or more, in particular when measured in water at 37°C, and / or iii) a) have a flexural strength (according to DIN EN ISO 20795-2) of 50 MPa or more, in particular when measured in water at 45°C, and / or b) have a modulus of elasticity (according to DIN EN ISO 20795-2) of 1500 MPa or more, in particular when measured in water at 45°C, and / or iv) a) have a flexural strength (according to DIN EN ISO 20795-2) of 40 MPa or more, in particular when measured in water at 55°C, and / or b) have an elastic modulus (according to DIN EN ISO 20795-2) of 900 MPa or more, in particular when measured in water at 55°C, and are in particular obtainable by irradiation of the polymerizable composition.

[0067] It is particularly preferred here that the polymeric composition has a shrinkage of less than 7%, advantageously less than or equal to 6.8%, preferably less than or equal to 6.5% and particularly preferably less than or equal to 6.0% (measured according to Watts, Dent. Mater 7: 281-286, October 1991, also called the bonded disk method, ambient room temperature, Translux Energy, 60 seconds of irradiation).

[0068] The subject of the present invention is also a blank in the form of a three-dimensional molding of a polymeric composition suitable for producing dental prosthetic parts, orthopedic appliances or dental preforms, the blank having a.1) a bending strength (according to DIN EN ISO 20795-2) of 75 MPa or more and / or b.1) a modulus of elasticity (according to DIN EN ISO 20795-2) of 2000 MPa or more and optionally a.2) a bending strength (according to DIN EN ISO 20795-2) of 50 MPa or more, in particular when measured in water at 45 ° C, and / or b.2) a modulus of elasticity (according to DIN EN ISO 20795-2) of 1500 MPa or more, in particular when measured in water at 45 ° C, and optionally iv) a) have a flexural strength (according to DIN EN ISO 20795-2) of 40 MPa or more, in particular when measured in water at 55°C, and / or b) have a modulus of elasticity (according to DIN EN ISO 20795-2) of 900 MPa or more, in particular when measured in water at 55°C.

[0069] The subject of the present invention is also the use of the composition according to the invention for producing anatomical models, anatomical table models, anatomical models for replacing dental stone models, prosthetic parts, dental prosthetic parts, orthopedic appliances, aligners, dental splints or dental preforms, as well as in rapid prototyping or rapid manufacturing or rapid tooling processes. Preference is given to radiation curing of the composition by means of a laser beam, an LED light source or a DLP projector.

[0070] Furthermore, the subject of the present invention is the use of the composition for producing dental prosthetic parts, including prosthetic bases or parts thereof, artificial teeth, dentitions with at least 2 to 16 artificial teeth with integral interdental connections, crowns, provisional crowns, full prostheses, full crowns, splints for orthodontic correction (similar to Invisalign), dental bridges, abutments, suprastructures, dental bars, inlays, onlays, orthopedic appliances such as occlusal splints, dental preforms for artificial teeth, surgical guides for implant dentistry, mouthguards and / or implants.

[0071] Dental products are understood in the present invention to mean in particular dental products that can be produced from the polymerizable composition, such as, but not limited to, full prostheses, provisional crowns and bridges, inlays, onlays, full crowns, occlusal splints, surgical guides for implant dentistry, orthodontic correction splints (similar to Invisalign), mouthguards, artificial teeth.

[0072] In order to meet high aesthetic requirements, compositions that can be used in dentistry for producing final dentures, such as working models, orthodontic models, surgical guides, prostheses, and splints, must have high transparency. This transparency is usually achieved by optimally adjusting the refractive index of the filler and the refractive index of the polymer matrix. However, various physical and chemical boundary conditions impose very narrow limits on the selection of both fillers and monomers.

[0073] According to yet another embodiment, the resulting polymeric composition or blank, in particular a radiation-cured composition, in particular a UV-Vis-cured composition, which has advantageously also been radiation-cured on the entire surface, has the above-mentioned properties with respect to its flexural strength and / or modulus of elasticity according to DIN EN ISO 20795-2. Further radiation-curing on the entire surface is understood to mean a subsequent heat treatment, for example in a 3D light oven.

[0074] The following methods are referred to here: rapid prototyping or rapid manufacturing processes, processes for manufacturing workpieces such as dental prosthetic parts, rapid tooling processes, and processes for manufacturing appliances, respectively, including stereolithography and DLP processes. Optionally, after curing the polymerizable composition in the aforementioned processes, a post-heat treatment using UV, Vis, or UV / Vis light may be performed. Advantageously, the post-heat treatment of the polymerizable composition or dental prosthetic part, orthopedic appliance, or dental preform or blank is performed simultaneously from at least three sides, preferably five to six sides, as is possible in a light oven. Alternatively, or additionally, the polymerizable composition may be heat-treated.

[0075] Furthermore, color pigments can be added to the composition to adjust the color. In addition, red fibers can be added to the composition to mimic the blood vessels of the gums. Suitable color pigments include, for example, PV Echtrot (CAS 4948-15-6), Indischblau 220943 (CAS 68186-87-8), Echtschwarz 100 (CAS 68186-91-4), Kronos 2220 (CAS 13463-67-7), and Lichtgelb 3R (CAS 68186-90-3).

[0076] For the polymeric composition, layer thicknesses of 5 μm, in particular in the range of 25 μm to 250 μm per cured layer can be achieved, with print layers having thicknesses of 30 μm, 50 μm, 70 μm, 100 μm, 120 μm and 170 μm being particularly preferred.

[0077] High transparency can be achieved by optimally selecting the formulation components with respect to their refractive index.

[0078] Examples of photoinitiators include benzoin alkyl ethers or benzoin alkyl esters, benzil monoketals, acylphosphine oxides, or aliphatic and aromatic 1,2-diketo compounds such as 2,2-diethoxyacetophenone, 9,10-phenanthrenequinone, diacetyl, furyl, anisyl, 4,4'-dichlorobenzyl, and 4,4'-dialkoxybenzyl, or camphorquinone. The photoinitiator is preferably used together with a reducing agent. Examples of reducing agents include amines, such as aliphatic or aromatic tertiary amines, such as N,N-dimethyl-p-toluidine or triethanolamine, cyanoethylmethylaniline, triethylamine, N,N-dimethylaniline, N-methyldiphenylamine, N,N-dimethyl-sym.-xylidine, N,N-3,5-tetramethylaniline, and 4-dimethylaminobenzoic acid ethyl ester, or organic phosphites. A common photoinitiator system is, for example, camphorquinone plus ethyl-4-(N,N-dimethylamino)benzoate, 2-(ethylhexyl)-4-(N,N-dimethylamino)benzoate, or N,N-dimethylaminoethyl methacrylate.

[0079] In particular, 2,4,6-trimethylbenzoyldiphenylphosphine oxide is suitable as an initiator for UV light-initiated polymerization. UV photoinitiators can be used alone or in combination with visible light initiators.

[0080] Particularly preferred photoinitiators and / or initiator systems include a) at least one radical photoinitiator, 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, or α-hydroxyketones, camphorquinone, acylphosphine oxides, optionally with the addition of a stabilizer, and optionally b) at least one co-initiator, for example, an amine, typically a tert-amine, 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.

[0081] Particularly preferred photoinitiators include α-hydroxyphenyl ketones, 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 photoinitiators, combinations of phenylphosphine oxides, bisacylphosphine oxides (BAPO).

[0082] 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).

[0083] The present invention will be explained in more detail by the following examples, without being limited to these exemplary embodiments.

[0084] The compositions according to the invention can be used to print workpieces, blanks or three-dimensional objects with very good geometric accuracy / resolution. The objects according to the invention exhibit very good mechanical properties even at high temperatures. Furthermore, good color stability can be observed in the workpieces.

[0085] Illustrative Embodiments : General preparation example: The initiator is pre-dissolved in (octahydro-4,7-methano-1H-indenyl)methyl acrylate or tricyclodecane dimethanol diacrylate. The other monomers are then added and the mixture is homogenized. A pigment concentrate or pigment can be added. The composition is then advantageously homogenized. The prepared composition can be processed in a 3D printer. It should be noted that photosensitive initiators can react with ambient light, resulting in undesired polymerization (the composition is advantageously transferred to a printing bath under appropriate measures). Post-curing or post-heat treatment is carried out by irradiation at 385-405 nm, for example using a laboratory lighting device, HiLite Power3D.

[0086] Using the prepared mixture, test specimens are printed in accordance with ISO 20795-2 (50 μm) for the following tests using a 3D precision printer (Cara Print 4.0) at a wavelength of 405 nm. After the printing process, the test specimens are rinsed with isopropanol and subjected to a post-heat treatment process. This is carried out by irradiating each side for 3-5 minutes or according to the manufacturer's specifications with a laboratory lighting lamp HiLite Power 3D, 200 W (Kulzer GmbH). Properties of the inventive mixture of model material tested according to DIN EN ISO 20795-2 or in accordance with this standard: [Table 1]

[0087] Comparative Examples 1 and 2 show that a high proportion of quadruple crosslinker alone does not guarantee good mechanical properties, since these comparative examples do not exhibit acceptable mechanical properties even at ambient room temperature. Although the comparative compositions do have viscosities that are suitable for 3D printing applications, they do not meet the mechanical property requirements according to ISO-20795.

[0088] [Table 2]

[0089] [Table 3]

[0090] [Table 4]

[0091] [Table 5]

[0092] [Table 6]

[0093] [Table 7]

Claims

1. (i) a monomer; (ii) at least one further component; 1. A polymerizable radiation curable composition for use in a rapid prototyping process, or a rapid manufacturing process, or a rapid tooling process, comprising: In the composition (i) (a) a mixture of first monomers, wherein the mixture of first monomers has a TG (glass transition temperature) of 120°C or higher when the corresponding homopolymer of each first monomer is present in an amount of 40 to 99.99% by weight, and the mixture of first monomers comprises at least one triacrylate derived from 1,3,5-tris(hydroxyalkyl)isocyanurate, at least one difunctional urethane(meth)acrylate selected from difunctional urethane(meth)acrylates having divalent alkylene groups, and at least one diacrylate ester based on tricyclodecane dialkanol, the alkanol containing 1 to 6 C atoms, wherein the hydroxyalkyl groups each independently contain 1 to 8 C atoms; and (b) 0 to 60 wt. % of at least one second monomer or mixture of second monomers, the TG (glass transition temperature) of each corresponding homopolymer of the second monomer being 100° C. or less; and (ii) the at least one further component comprising at least one photoinitiator in the UV and / or Vis region of the spectrum or a photoinitiator system in the UV and / or Vis region of the spectrum, and optionally at least one stabilizer in the UV and / or Vis region of the spectrum, and optionally at least one pigment and / or dye, and further conventional additives, is present in an amount of 0.01 to 5 wt. %; wherein the total composition is 100% by weight and the viscosity of said composition at ambient room temperature (about 20°C to 23°C) is 3000 mPas or less; composition.

2. 10. The composition of claim 1, wherein the viscosity of the composition at ambient room temperature (about 20°C to 23°C) is from 500 to less than 2500 mPas.

3. A composition described in claim 1 or 2, characterized in that the second monomer or mixture of second monomers contains at least one monofunctional acrylate having an alicyclic group and / or a monofunctional methacrylate having an alicyclic group.

4. The composition described in claim 3, characterized in that the second monomer or mixture of second monomers contains at least one monofunctional acrylate ester based on a tricyclodecane alkanol, the alkanol containing 1 to 6 C atoms, or a mixture thereof.

5. 5. The composition according to claim 4, characterized in that (i) in the composition, (b) at least one second monomer or mixture of second monomers is present in an amount of 15 to 25% by weight, comprising a monofunctional acrylate ester based on a tricyclodecane alkanol, the alkanol containing 1 to 6 C atoms, and wherein the total composition is 100% by weight.

6. A composition according to claim 4, characterized in that the composition contains 15 to 45% by weight of monofunctional acrylate esters based on tricyclodecane alkanols, the alkanols of which contain 1 to 6 C atoms, and diacrylate esters based on tricyclodecane dialkanols, the alkanols of which contain 1 to 6 C atoms, and wherein the total composition is 100% by weight.

7. The composition according to claim 1, characterized in that in the composition there is present 5 to 15 wt. % of diacrylate esters based on tricyclodecane dialkanols, the alkanols of which contain 1 to 6 C atoms, and 15 to 25 wt. % of monofunctional acrylate esters based on tricyclodecane alkanols, the alkanols of which contain 1 to 6 C atoms, wherein the total composition is 100 wt. %.

8. 8. Composition according to any one of claims 1 to 7, characterized in that (a) the at least one diacrylate ester based on a tricyclodecane dialkanol, the alkanol of which contains 1 to 6 C atoms, is selected from tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, tricyclodecane diethanol diacrylate, tricyclodecane diethanol dimethacrylate and / or mixtures thereof.

9. (i) The composition according to claim 3, characterized in that the mixture of second monomers, each of which has a corresponding homopolymer having a TG (glass transition temperature) of 100°C or less, contains at least one monofunctional acrylate having an alicyclic group and / or a monofunctional methacrylate having an alicyclic group, selected from (octahydro-4,7-methano-1H-indenyl)methanol acrylate, (octahydro-4,7-methano-1H-indenyl)methanol methacrylate, (octahydro-4,7-methano-1H-indenyl)ethanol acrylate and (octahydro-4,7-methano-1H-indenyl)ethanol methacrylate.

10. In the composition: (i) (a) 70 to 99.99% by weight of a mixture of first monomers, the TG (glass transition temperature) of each homopolymer of the corresponding first monomer being 120° C. or higher; (b) 0-30% by weight of at least one second monomer or mixture of second monomers, the TG (glass transition temperature) of the corresponding respective homopolymer of the second monomer being 100° C. or less, and the second monomer or mixture of second monomers comprising at least one monomer or mixture of second monomers, the TG of the respective homopolymer of which is 30° C. or more; - 0.01 to 5% by weight of said at least one further component comprising at least one photoinitiator in the UV and / or Vis spectral region or a photoinitiator system in the UV and / or Vis spectral region, and optionally at least one stabilizer in the UV and / or Vis spectral region, and optionally at least one pigment and / or dye, and further customary additives; 10. The composition of claim 1, wherein the total composition is 100% by weight.

11. In the composition: (i) (a) 75 to 99.99% by weight of a mixture of first monomers, the TG (glass transition temperature) of each homopolymer of the corresponding first monomer being 120° C. or higher; (b) 0-25% by weight of at least one second monomer or a mixture of second monomers, the TG (glass transition temperature) of each homopolymer of the corresponding second monomer being 100° C. or less, said second monomer or mixture of second monomers comprising at least one monofunctional acrylate having an alicyclic group and / or a monofunctional methacrylate having an alicyclic group; - 0.01 to 5% by weight of said at least one further component comprising at least one photoinitiator in the UV and / or Vis spectral region or a photoinitiator system in the UV and / or Vis spectral region, and optionally at least one stabilizer in the UV and / or Vis spectral region, and optionally at least one pigment and / or dye, and further customary additives; and wherein there is present a monomer comprising 11. The composition according to any one of claims 1 to 10, wherein the total composition is 100% by weight and the viscosity of said composition at ambient room temperature (about 20°C to 23°C) is less than or equal to 3000 mPas.

12. The (i) mixture of first monomers and the (ii) at least one additional component are represented by the following formula: 1 / TG (total) = w1 / TG （１） +w2 / TG （２） +w3 / TG （３） + optionally w4 / TG （４） + optionally w5 / TG （５） + optionally, wn / TG （ｎ） is present in said composition according to w1, w2, w3, w4, w5, and wn are each a weight percentage of said monomer in 100% by weight of the total mixture of said first monomer and said second monomer and optionally a third monomer, n=6 to 50, and TG is 100° C. or higher; A composition according to any one of claims 1 to 11, characterized in that the viscosity of said composition at ambient room temperature (approximately 20°C to 23°C) is less than or equal to 3000 mPas.

13. The (i) first monomer mixture is a monomer represented by the following formula: 1 / TG (total) = w1 / TG （１） +w2 / TG （２） +w3 / TG （３） + optionally w4 / TG （４） + optionally w5 / TG （５） + optionally, wn / TG （ｎ） is present in said composition according to 13. A polymerized composition obtainable by polymerizing the polymerizable composition according to any one of claims 1 to 12, characterized in that w1, w2, w3, w4, w5, and wn are each the weight fraction of said monomer in 100 wt.% of the total mixture of the mixture of the first monomer and the second and optionally the third monomer, n=6 to 50, TG is 100°C or higher, and the polymerized composition has a flexural strength (according to DIN EN ISO 20795-2) of 40 MPa or higher, measured in water at 55°C, and / or a modulus (according to DIN EN ISO 20795-2) of 800 MPa or higher, measured in water at 55°C.

14. the polymeric composition alternatively or cumulatively comprising: i) a) has a flexural strength (according to DIN EN ISO 20795-2) of 75 MPa or more, and / or b) has an elastic modulus (according to DIN EN ISO 20795-2) of 2000 MPa or more, and / or ii) a) have a flexural strength (according to DIN EN ISO 20795-2) of 70 MPa or more when measured in water at 37°C, and / or b) have a modulus of elasticity (according to DIN EN ISO 20795-2) of 2000 MPa or more when measured in water at 37°C, and / or iii) a) have a flexural strength (according to DIN EN ISO 20795-2) of 50 MPa or more when measured in water at 45°C, and / or b) have a modulus of elasticity (according to DIN EN ISO 20795-2) of 1500 MPa or more when measured in water at 45°C, and / or iv) A polymeric composition obtainable by polymerizing the polymerizable composition according to any one of claims 1 to 12, or the polymeric composition according to claim 13, characterized in that a) it has a flexural strength (according to DIN EN ISO 20795-2) of at least 40 MPa, measured in water at 55°C, and / or b) it has a modulus of elasticity (according to DIN EN ISO 20795-2) of at least 900 MPa, measured in water at 55°C.

15. 14. A blank in the form of a three-dimensional shaped body of a polymerized composition obtainable by polymerizing the polymerizable composition of any one of claims 1 to 12 or the polymerized composition of claim 13 for producing a dental prosthetic part, an orthopedic appliance or a dental preform, characterized in that the blank has a. 1) a flexural strength (according to DIN EN ISO 20795-2) of 75 MPa or more, and / or b. 1) a modulus of elasticity (according to DIN EN ISO 20795-2) of 2000 MPa or more, and optionally a. 2) a flexural strength (according to DIN EN ISO 20795-2) of 50 MPa or more, measured in water at 45°C, and / or b. 2) a modulus of elasticity (according to DIN EN ISO 20795-2) of 1500 MPa or more, measured in water at 45°C.

16. 13. Use of a composition according to any one of claims 1 to 12 for producing an anatomical model, an anatomical table model, a dental working model, a dental complete model, a dental die model, an anatomical or dental saw-cut model, a situation model, an crossbite model, a functional model, a pre-model, a restorative model, a precision model, an anatomical model for replacing a dental plaster model, an aligner, a dental splint, a prosthetic part, a dental prosthetic part, an orthopedic appliance or a dental preform.

17. 13. Use of a composition according to any one of claims 1 to 12 in a rapid prototyping process, or a rapid manufacturing process or a rapid tooling process.

18. 18. Use according to claim 16 or 17, characterized in that the dental prosthetic part comprises a prosthetic base or parts thereof, artificial teeth, a dentition with at least 2 to 16 artificial teeth with integral interdental connections, a crown, a provisional crown, a complete prosthesis, a complete crown, a splint for orthodontic correction, a dental bridge, an abutment, a suprastructure, a dental bar, an inlay, an onlay, an orthopedic appliance such as an occlusal splint, a dental preform for an artificial tooth, a surgical guide for implant dentistry, a mouthguard and / or an implant.

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