Radiation curable compositions for rapid prototyping or rapid manufacturing

Abstract

The present invention relates to a polymerizable, radiation-curable, in particular UV / Vis-, UV- or Vis-curable composition comprising (i) monomers, wherein the monomers comprise (a.1) at least one triacrylate derived from 1,3,5-tris(ω-hydroxyalkyl)isocyanurate, wherein the hydroxyalkyl group comprises 1 to 8 carbon atoms and may be linear, branched and / or cyclic, and (a.2) at least one difunctional monomer which is not a urethane (meth)acrylate, and (ii) at least one further component comprising at least one photoinitiator for the UV and / or Vis region or a photoinitiator system for the UV and / or Vis region. Furthermore, the present invention relates to a preform in the form of a three-dimensional molded body of the polymerized composition, in particular of the radiation-cured composition, for producing a dental restorative part, an orthopedic appliance or a dental preform, and to the use of the composition for producing a dental restorative part, an orthopedic appliance or a dental preform in a rapid prototyping process or in a rapid manufacturing or rapid tooling process.

Description

[0001] The present invention relates to a polymerizable, radiation-curable, in particular UV / Vis-, UV- or Vis-curable composition comprising

[0002] (i) a monomer, wherein the monomer comprises

[0003] (a.1) at least one triacrylate derived from 1,3,5-tris(ω-hydroxyalkyl)isocyanurate, in particular from 1,3,5-tris(2-hydroxyalkyl)isocyanurate, where the hydroxyalkyl group contains 1 to 8 C atoms and can be linear, branched and / or cyclic, and

[0004] (a.2) at least one difunctional monomer that is not a urethane (meth)acrylate, and

[0005] (ii) at least one other component comprising

[0006] At least one photoinitiator for the UV and / or Vis region or a photoinitiator system for the UV and / or Vis region and optionally at least one stabilizer. Furthermore, the present invention relates to a polymerized composition for producing dental restorative parts, orthopedic appliances or dental preforms, in particular blanks in the form of three-dimensional molded bodies of the radiation-cured composition, and to the use of such compositions for producing dental restorative parts, orthopedic appliances or dental preforms in rapid prototyping or rapid manufacturing or rapid tooling processes.

[0007] In addition to manual manufacturing methods, digital manufacturing methods, such as subtractive or additive methods (material buildup methods), are becoming increasingly important in dentistry. The advantages of additive methods are savings in expensive raw materials and faster production of objects. Generative methods are already known in dentistry, for example, in the form of laser sintering of CoCr, Ti, or polymers for producing crowns and bridges, implant components, or models.

[0008] To date, compositions of acrylates or acrylate derivatives for producing dental prostheses with a suitable profile of properties that meet the mechanical requirements in the dental field according to DIN EN ISO 207952 have not been available (see QuintessenzZahntech. 2017-43(10): p. 1325). Consequently, there is a fundamental need for the production of anatomical models, anatomical tabletop models, in particular for the production of anatomical models as an alternative to dental plaster models made from impressions of the patient's dental condition and gums or dentition, or for the production of prosthetic components or finished dental prostheses. Furthermore, there is a need for compositions for the production of finished prosthetic components, orthopedic appliances or dental preforms.

[0009] Impressions and models (also referred to as anatomical models or working models) form the basis for custom-made dental prostheses. Dentists and dental technicians only receive optimal individual care if they adhere to the material-specific requirements during impression taking and model production.

[0010] Dental technicians typically use plaster to produce models. Plaster is easy to work with and meets the requirements for precise, dimensionally stable, and smooth models. Requirements for dental anatomical plaster models include: volume stability, minimal expansion, no shrinkage, storage stability, compatibility with disinfectants, barrier agents, and waxes, a smooth, non-porous surface, adequate pressure resistance, high edge stability, good wear resistance, and high thermal loadability, particularly when used with or without wax extraction.

[0011] The object of the present invention is to provide a composition having good radiation-curing properties, in particular UV and / or Vis radiation curing properties, and a good polymerization depth during radiation curing. Furthermore, the radiation-cured composition should have good mechanical properties both at room temperature and at elevated temperatures so that it can be used to produce anatomical models. The composition should therefore meet the requirements for model materials used in the production of models for model casting, implantology, sawing and mastering, as well as precision underbite models. Therefore, the object of the present invention is to provide a photocurable composition for additive / generative processes that, in the cured state, as a printed molded body, meets the following requirements: retention of mechanical properties and dimensional stability at temperatures of 45°C to 55°C in a pressure vessel; dimensional stability during the drawing process and during cleaning, for example, using a steam jet; storage stability of the photocurable composition without significant viscosity changes during storage; sufficient reactivity when irradiated with a laser, LED, or DLP projector; the ability to print workpieces / molded bodies with sufficient geometric accuracy / resolution; color stability of the mixture; and minimal or no thixotropy. It was therefore an object of the present invention to provide radiation-curable compositions having a flexural strength of at least 40 MPa and a flexural modulus of at least 800 MPa when tested in water at 55° C. in the polymerized state.

[0012] The following is an overview of the further requirements placed on dental plaster models in the individual work steps: Models adapted to the influence of heat and water: Casting of the plastic saddle in the model casting (in a water bath at 55°C for 20 minutes), completion of the partial prosthesis / model casting (in a water bath at 55°C for 20-30 minutes), completion of the full prosthesis (injection technology Palajet / vessel technology - in a water bath at 55°C for 30 minutes), completion of the full prosthesis tamping-pressing technology (in a water bath at 100°C for 30-40 minutes), drawing tray (in a water bath at 55°C for 20-30 minutes), steam for cleaning (70°C - 110°C), extraction (in a water bath at 80°C - 100°C for 3-5 minutes), veneering with Pala Veneer (in a water bath at 55°C, 2 bar, for 20 minutes).

[0013] Models with isolation and mechanical influences: bite-in, i.e. mechanical loading of the model in the articulator, isolation from prosthetic plastic, isolation from facing composite, isolation from wax, possibility of casting with UV plastic and / or wax, wax impregnation.

[0014] Models that are susceptible to heat and not compatible with water: Deep drawing (155 - 170°C / 1 to 2 minutes), hot glue gun to fix the model, wax to fix the model, casting with UV plastic and / or wax, wax impregnation, manual curing of drawing films and composite materials in HiLitePower / 3D (twice 90 seconds and once 180 seconds), curing of bite splints in HiLitePower / 3D (twice 5 minutes each), milling posts for milling technology (resistant to accumulated heat).

[0015] Behavior of the polymerized composition in other work steps: Dimensional stability and good cleaning properties in an ultrasonic bath containing isopropyl alcohol, discoloration and cleaning with occlusal films (Bausch, red, blue, black), discoloration and cleaning with occlusal spray (several manufacturers), wear resistance at the edges of workpieces (crowns, bridges, cast teeth), fracture / wear resistance (in articulators – plaster on plastic; plastic on plastic).

[0016] Scenario models and all working models are the foundation for all further dental work. To meet high aesthetic requirements, resin compositions used for final dental prostheses, such as working and orthodontic models, must be dimensionally and thermally stable. To reap the advantages of digital workflows by replacing plaster models with printed plastic models, these models must possess the same positive properties as plaster. However, due to various physical and chemical boundary conditions, plastics are subject to thermoplastic properties that must be kept within these limits through optimal monomer selection.

[0017] To date, no materials exist which possess all of the thermal stability properties mentioned, so that they can only be used in some dental technology applications.

[0018] Therefore, it is also an object of the present invention to provide a composition comprising monomers having particularly high thermal and dimensional stability in order to withstand elevated temperatures when using the polymerized composition as molded parts in a pressure tank and in the deep drawing of bite splints. During the production of orthodontic appliances, they must frequently be subjected to elevated temperatures.

[0019] The object of the invention is achieved by a composition according to claim 1 and a polymerized composition according to claim 11 as well as a blank according to claim 12 and a use according to claim 13. Preferred embodiments are disclosed in the dependent claims and in detail in the description.

[0020] The present invention relates to a polymerized composition, in particular a radiation-curable composition, preferably a composition polymerizable by means of UV / Vis, UV or Vis radiation, comprising

[0021] (i) Monomer and

[0022] (ii) at least one other component, wherein the monomers described in (i) comprise

[0023] (a.1) at least one triacrylate derived from 1,3,5-tris(ω-hydroxyalkyl)isocyanurate, wherein the hydroxyalkyl groups each independently contain 1 to 8 C atoms, in particular linear, branched and / or cyclic hydroxyalkyl groups having 3 to 8 C atoms, preferably 1 to 6 C atoms, particularly preferably 1 to 4 C atoms, preferably 1 to 3 C atoms, particularly preferably hydroxyethyl groups, and

[0024] (a.2) at least one difunctional monomer which is not a urethane acrylate or urethane methacrylate, and (ii) the at least one further component comprises at least one photoinitiator for the UV and / or Vis region or a photoinitiator system for the UV and / or Vis region, and optionally at least one stabilizer, and optionally further customary additives, optionally pigment(s) or dye(s).

[0025] Particularly preferred compositions have a viscosity at room temperature (approximately 20° C. to 23° C.) of less than or equal to 5000 m·Pas, preferably less than or equal to 3000 m·Pas, particularly preferably 500 to less than 2500 m·Pas.

[0026] According to one embodiment, the monomers preferably comprise (a.1) at least one triacrylate derived from 1,3,5-tris(ω-hydroxyalkyl)isocyanurate, particularly preferably 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 containing at least two of these monomers.

[0027] Other preferred (i) monomers are selected from: (a.2) at least one difunctional monomer which is not a urethane (meth)acrylate and which comprises (b) and / or (c), wherein

[0028] (b) a difunctional acrylate having a divalent alicyclic group and a difunctional methacrylate having a divalent alicyclic group, and optionally

[0029] (c) at least one disubstituted 4,4'-bis(oxyphenyl)dialkylmethane of formula I

[0030]

[0031] where R 1 、R 2 、R 5 and R 6 are each independently selected from H or C1 to C4-alkyl, and wherein R 3 and R 4 each a divalent C1 to C4-alkylene group, where n = 0 to 6 and m = 0 to 6, and optionally

[0032] (i) Monomers contain

[0033] (d) at least one at least difunctional urethane (meth)acrylate,

[0034] (e) at least one monofunctional acrylate having an alicyclic group and / or monofunctional methacrylate having an alicyclic group.

[0035] Preferred are disubstituted 4,4'-bis(oxyphenyl)dialkylmethanes of formula I and mixtures thereof, wherein R 1 and R 2 Each is methyl and R 5 and R 6 are identical 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 4Each is independently a divalent ethylene or propylene group, n = 1 to 6, preferably n = 2 to 4, and m = 1 to 6, preferably m = 2 to 4, preferably n = 2 and m = 2 or n = 4 and m = 4.

[0036] In a preferred alternative, R in Formula I 1 and R 2 can each be methyl, and R 5 and R 6 can be the same and selected from H, methyl and ethyl, preferably R 5 and R 6 are the same and are selected from H and methyl, and R 3 and R 4 Each independently represents a divalent ethylene or propylene radical, n = 1 to 6, preferably n = 2 to 4 and m = 1 to 6, particularly preferably n = 2 to 4 and m = 2 to 4, more preferably n = 2 and m = 2 or n = 4 and m = 4, and mixtures thereof. Particularly preferred are mixtures of 4,4'-bis(oxyphenyl)dialkylmethanes of formula I: which are mixtures of a) and b): a) wherein R 1 and R 2 Each is a methyl group, and R 5 and R 6 Equal to H, and R 3 and R 4 are each independently a divalent ethylene group, n = 1 to 6, preferably n = 2 to 4, and m = 1 to 6, preferably m = 2 to 4, preferably n = 4 and m = 4, and mixtures thereof, b) wherein R 1 and R 2 Each is a methyl group, and R 5 and R 6 Equal to methyl, and R 3 and R 4 Each is independently a divalent ethylene group, n = 1 to 6, preferably n = 2 to 4, and m = 1 to 6, preferably m = 2 to 4, preferably n = 2 and m = 2, and mixtures thereof.

[0037] Preferred at least bifunctional monomers other than urethane (meth)acrylates are selected from (b) bifunctional acrylates having a divalent alicyclic group and bifunctional methacrylates having a divalent alicyclic group. Particularly preferably, (b) is 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).

[0038] Preferably, all monomers (a), (b), (c), (d), (e) and (f) 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) have an average molecular weight of less than 1000 g / mol.

[0039] Semi-crystalline plastics (many common plastics have a crystalline fraction of 10 to 80%) have both a glass transition temperature (below which the amorphous phase freezes (and thereby becomes brittle)) and a melting temperature (at which the crystalline phase dissipates). The glass transition is not a first-order phase transition and, therefore, is not associated with a specific temperature, such as the melting point, in the case of crystals. The measured values ​​vary systematically depending on which time and length scales of molecular dynamics, or which modes of motion, the measurement method used (see below) is sensitive to. Whether a plastic can be used above or below its glass transition temperature depends on the type of plastic (it should be noted that the glass transition temperature of a plastic increases with its crosslinking density, i.e., the glass transition temperature of thermosets is significantly higher than that of thermoplastics).

[0040] When selecting monomers, it should also be ensured that they bind well to the fillers that may be used. Polyurethanes, acrylates, polyesters, and other monomers generally do not bind well to the fillers used. Therefore, fillers are often surface-silanized or hydrophobized to improve bonding with the monomers.

[0041] If inorganic fillers cannot be used in the polymerizable composition due to a particular dental application, for example due to the target viscosity of the composition, it is possible to use dyes or pigments in the composition for the purpose of reflecting radiation, in particular diffusely reflecting or scattering incident radiation. Dyes are understood to be compounds that are soluble in the polymerizable composition and preferably form clear solutions.

[0042] The radiation curable composition according to the invention can preferably be irradiated using radiation sources that emit light in the Vis region, particularly preferably radiation sources that emit radiation in the range of 360 to 750 nm, in particular about 385 nm, particularly preferably about 405 nm. The composition according to the invention can particularly preferably be irradiated in the Vis region of 380 to 660 nm using polychromatic radiation sources such as DLP projectors or preferably monochromatic radiation sources such as laser projectors.

[0043] When the pigments and / or dyes are added, the photoinitiator content in the composition can be reduced. Too high a photoinitiator content can lead to so-called "overcuring", inaccuracies and / or geometric changes in the irradiated composition, so that the corresponding manufactured dental component is unusable.

[0044] The use of optional inorganic fillers, pigments, or dyes according to the invention results in uniform scattering of radiation, particularly UV and Vis radiation, within the monomer matrix of the composition, which is why the composition is considered to cure uniformly. As a result, the polymerized composition has a higher value for the achieved work of fracture.

[0045] The composition according to the invention, after irradiation with a radiation source in the Vis region, in particular in the range 385 to 405 nm, preferably by stereolithography and preferably in the form of a blank, a 3D molded part, a dental restoration part, an anatomical model, an anatomical tabletop model, a dental working model, a full dental model, a dental root model, an anatomical or dental sawn model, in particular a situational model, a crossbite model, a functional model, a precursor model, a restoration model, a precision model, a master model and a precision crossbite model, an anatomical model of a dental plaster model for replacing the dentition, a prosthetic component, an orthopedic appliance or a dental preform, to obtain the polymerized composition, and after optional post-tempering of the polymerized composition with a radiation source, has the following properties: a) a flexural strength of greater than or equal to 40 MPa, in particular greater than or equal to 75 MPa, and / or b) an E modulus of greater than or equal to 800 MPa, in particular greater than 1500 MPa, in particular greater than or equal to 2000 MPa, according to DIN EN ISO 20795-2, in particular typically at room temperature, preferably 23° C. + / - 2°C, preferably between room temperature and 55°C (in water). The radiation-cured composition, in particular as a molded body or blank, preferably has the following flexural strength and E modulus. For the definition of the aforementioned dental models, see Lehrbuch der Zahntechnik, Volume 3, Quintessenz Verlag, A. Hohmann, W. Hielscher, 5th edition, 2012. Post-curing or post-tempering, respectively, can preferably be carried out, for example, using laboratory lighting (HiLitePower 3D) or in a light oven with a spectrum preferably between 390 and 540 nm.

[0046] Optionally, the composition may further contain 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 these monomers, as (a.2) at least one difunctional monomer other than a urethane acrylate or urethane methacrylate. Preferred polyether diacrylates may be selected from triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and / or tetraethylene glycol dimethacrylate. Alternatively or additionally, the composition may contain a diacrylate selected from decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, hexyldecanediol di(meth)acrylate, butanediol di(meth)acrylate, or a mixture containing at least one of these acrylates.

[0047] The bracketed designation in the term (meth)acrylate or (alkyl)acrylate means that the acrylate can be present as acrylate or methacrylate and alternatively as alkylacrylate.

[0048] Likewise, preferred monomers as the at least one other monomer in the composition may be selected from:

[0049] (d) at least one at least difunctional urethane (meth)acrylate, and / or

[0050] (f) at least one monofunctional, trifunctional, tetrafunctional or polyfunctional monomer, which in particular is not a urethane (meth)acrylate.

[0051] Hydroxyethyl acrylate can be used as monofunctional monomer. Likewise, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and / or hydroxyethyl acrylate can be used, optionally as a mixture of at least two of the monomers.

[0052] Furthermore, the composition may contain (d) at least one at least difunctional urethane (meth)acrylate selected from difunctional urethane (meth)acrylates having a divalent alkylene group (difunctional urethane acrylate and / or difunctional urethane methacrylate).

[0053] The difunctional urethane (meth)acrylate having a divalent alkylene group is preferably selected from linear or branched urethane dimethacrylates functionalized with a divalent alkylene group, functionalized polyethers having one or more alkylene groups, such as bis(methacryloyloxy-2-ethoxycarbonylamino)alkylene, bis(methacryloyloxy-2-ethoxycarbonylamino)-substituted polyalkylene ethers, preferably 1,6-bis(methacryloyloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane, UDMA, or HEMA-TDMI. Bis(methacryloyloxy-2-ethoxycarbonylamino)alkylene is preferred, where the alkylene group comprises a linear or branched C3 to C20, preferably C3 to C6, alkylene groups substituted with methyl groups, such as HEMA-TMDI. The divalent alkylene group preferably comprises 2,2,4-trimethylhexamethylene and / or 2,4,4-trimethylhexamethylene.

[0054] (f) Trifunctional, tetrafunctional or polyfunctional monomers may be selected from:

[0055] Particularly preferred are pentaerythritol tetraacrylate (TG 105°C) and ditrimethylolpropane tetraacrylate (TG 100°C). 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). Furthermore, trifunctional monomers can be selected from (wherein they are preferably used in only 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) glycerol triacrylate (TG 20°C), ethoxylated (15) trimethylolpropane triacrylate (TG -30°C).

[0056] TG is preferably determined by means of DSC. The published glass transition temperatures can be obtained from the "Polymer Handbooks" known to those skilled in the art, from information from monomer manufacturers. If no information on the glass transition temperature is provided, it can be determined by means of DSC, DMS (dynamic mechanical analysis), dielectric relaxation spectroscopy or dilatometry. A common method is DSC measurement for determining the glass transition temperature of homopolymers. For this purpose, the homopolymer is dried, heated to 120°C, rapidly cooled to -100°C and subsequently heated at 20°C / min to 150°C or higher up to 300°C and the data for the glass transition temperature are determined. The glass transition temperature is measured as an average value. 1 / Tg = w1 / Tg(1) + w2 / Tg(2), where w1 and w2 are the mass ratios of the respective comonomers, and Tg(1) and Tg(2) are the glass transition temperatures of the homopolymers of monomers 1 and 2, respectively. In the case of further comonomers, a further term (wn / Tg(n)) is incorporated into the equation. The glass transition temperature of copolymers can be approximated by the Fox equation, see above and [Bulletin of the American Physical Society 1, 3 p. 123 (1956)]. TG(total) can be calculated from 1 / TG(total) according to the following formula, where the monomers are present in the total composition of the polymer according to the following weight proportions (w1, w2, w3, w4, w5, and wn). 1 / TG(total) = w1 / TG (1) + w2 / TG (2) + w3 / TG (3) + Choose w4 / TG (4) +Optional w5 / TG (5) + Choose wn / TG (n) , wherein w1, w2, w3, w4, w5 and wn are each the weight proportions of the monomers in the total composition.

[0057] Optionally, the composition may contain one or more fillers, such as doped silica fillers, in particular mixed oxides of zirconium dioxide and silicon dioxide. Particularly preferred are agglomerated mixed oxides comprising 75 to 99% by weight of silicon dioxide and 1 to 25% by weight of zirconium dioxide, based on the total composition of the mixed oxide. In particular, the mixed oxide comprises 85 to 90% by weight of silicon dioxide and 10 to 15% by weight of zirconium dioxide. Furthermore, it is preferred that the primary particles of the agglomerated oxide particles comprise crystallite regions of 4 to 7 nm and a crystallinity index advantageously of 0.6 to 0.7, as determined according to the method of Windisch et al. (WO 01 / 30306 A), and that the agglomerated oxide particles are surface-modified with at least one organofunctional silane reactive with at least one monomeric and / or polymeric component. The agglomerated oxide particles treated according to the invention exhibit excellent properties with respect to gloss values ​​in abrasion measurements, excellent transparency, and very good values ​​in reflection and roughness measurements after the toothbrush test.

[0058] The particle size of the inorganic filler, such as the at least one inorganic oxide, mixed oxide or dental glass (for example comprising barium aluminum oxide) has an average d of less than 10 μm for this application. 50 The filler particularly preferably has an average particle size of approximately 3 to 70 nm, in particular 10 to 50 nm (nanometers). The particles may optionally be present in aggregated or agglomerated form as particles up to 10 µm. The primary particle size of the inorganic filler, which may optionally be present as agglomerated and / or aggregated primary particles, has an average particle size of approximately 3 to 70 nm, in particular 10 to 50 nm. The mixed oxide of zirconium dioxide and silicon dioxide preferably has a primary particle size of 3 to 70 nm. The advantage of very small particle sizes, which may optionally be present in aggregated and / or agglomerated form, is that during radiation curing, light is scattered essentially diffusely on these particles, thus resulting in better curing in stereolithography or DLP processes.

[0059] Furthermore, the composition is preferably non-thixotropic. Furthermore, the composition particularly preferably has a viscosity of less than 3000 m·Pas, in particular from 500 to less than 2500 m·Pas, preferably from 500 to 2000 m·Pas, and particularly preferably from 500 to 1600 m·Pas. The viscosity is preferably measured according to DIN 1342-2; 2003-11 Newtonian liquids or DIN 1342-3; 2003-11 Non-Newtonian liquids using a rheometer (Anton Par, Physica MCR 301, viscosity range 200-3000 m·Pas at 100 / s at 23°C). The composition according to the present invention has no thixotropy or preferably only low thixotropy. The resulting composition is structurally viscous, preferably both with and without fillers. According to another embodiment, the viscosity preferably shows little change over a prolonged storage period. Furthermore, the composition exhibits excellent reactivity when irradiated with a laser or DLP projector.

[0060] The preferred composition may further comprise the following components as monomers:

[0061] (d) at least one difunctional urethane acrylate or urethane methacrylate selected from difunctional urethane acrylates having a divalent alkylene group and urethane methacrylates having a divalent alkylene group, and / or

[0062] (e) at least one monofunctional acrylate having an alicyclic group and / or monofunctional methacrylate having an alicyclic group selected from (octahydro-4,7-methylene-1H-indenyl)methanol acrylate (synonymous with (octahydro-4,7-methylene-1H-indenyl)methyl acrylate), (octahydro-4,7-methylene-1H-indenyl)methanol methacrylate (TCDA), (octahydro-4,7-methylene-1H-indenyl)ethanol acrylate and (octahydro-4,7-methylene-1H-indenyl)ethanol methacrylate, and optionally

[0063] (f) at least one monofunctional, trifunctional, tetrafunctional or polyfunctional monomer, which is in particular not a urethane (meth)acrylate. Alternatively, the monomer (i) may further comprise polyether acrylates and / or methacrylates selected from polyether dimethacrylates, polyether tri-, tetra- or polyfunctional methacrylates, polyether diacrylates, polyether tri-, tetra- and / or polyfunctional acrylates.

[0064] A preferred combination of the above monomers is a combination of a monomer selected from (d) and a monomer selected from (e) and optionally (f). The above acrylic acid ester of (octahydro-4,7-methylene-1H-indenyl)alkanol may exist as isomers, and therefore various isomers may be used alone or in combination.

[0065] Particularly preferred compositions comprise as (i) monomers

[0066] a) 5 to 45% by weight of at least one triacrylate derived from 1,3,5-tris(ω-hydroxyalkyl)isocyanurate, where the hydroxyalkyl group contains 1 to 8 C atoms, particularly preferably a hydroxyethyl group, and

[0067] (b) 5 to 45% by weight of at least one difunctional acrylate having a divalent alicyclic group and / or difunctional methacrylate having a divalent alicyclic group, and

[0068] (c) 0 to 60% by weight of at least one disubstituted 4,4'-bis(oxyphenyl)dialkylmethane of formula I, in which R 1 、R 2 、R 5 and R 6 are each independently selected from H or C1 to C4-alkyl, and wherein R 3 and R 4 each a divalent C1 to C4-alkylene group, where n = 0 to 6 and m = 0 to 6, and optionally

[0069] (d) 0 to 60% by weight of at least one at least difunctional urethane acrylate and / or difunctional urethane methacrylate,

[0070] (e) 0 to 20% by weight of at least one monofunctional acrylate having an alicyclic group and / or a monofunctional methacrylate having an alicyclic group, and

[0071] (ii) 0.01 to 5 wt. % of at least one other component comprising

[0072] at least one photoinitiator for the UV and / or Vis region or a photoinitiator system for the UV and / or Vis region, and optionally at least one stabilizer for the UV and / or Vis region, and optionally at least one pigment and / or dye, and further customary additives, where the total composition adds up to 100% by weight.

[0073] According to another embodiment, the following composition is preferred, which comprises

[0074] (i) a monomer comprising

[0075] (a) 5 to 35% by weight of at least one triacrylate derived from 1,3,5-tris(ω-hydroxyalkyl)isocyanurate, where the hydroxyalkyl group contains 1 to 8 C atoms and can be linear, branched and / or cyclic, in particular 1 to 6 C atoms, preferably 1 to 4 C atoms, preferably 1 to 3 C atoms, particularly preferably hydroxyethyl, and

[0076] (b) 5 to 35% by weight of at least one difunctional acrylate having a divalent alicyclic group and / or difunctional methacrylate having a divalent alicyclic group, and

[0077] (c) 20 to 50% by weight, in particular 30 to 50% by weight, of at least one disubstituted 4,4′-bis(oxyphenyl)dialkylmethane of the formula I, in which R 1 、R 2 、R 5 and R 6 are each independently selected from H or C1 to C4-alkyl, and wherein R 3 and R 4 each a divalent C1 to C4-alkylene group, where n = 0 to 6 and m = 0 to 6, and optionally

[0078] (d) 20 to 40% by weight of at least one at least difunctional urethane acrylate and / or difunctional urethane methacrylate,

[0079] (e) 5 to 20% by weight, in particular 5 to 15% by weight, of at least one monofunctional acrylate having a cycloaliphatic group and / or monofunctional methacrylate having a cycloaliphatic group, and optionally

[0080] (f) 1 to 20% by weight of at least one monofunctional, trifunctional, tetrafunctional or polyfunctional monomer, in particular polyether acrylates and / or methacrylates selected from polyether dimethacrylates, polyether tri-, tetra- or polyfunctional methacrylates, polyether diacrylates, polyether tri-, tetra- and / or polyfunctional acrylates,

[0081] (ii) 0.01 to 5% by weight of at least one further component comprising at least one photoinitiator for the UV and / or Vis region or a photoinitiator system for the UV and / or Vis region, and optionally at least one stabilizer for the UV and / or Vis region, and optionally at least one pigment and / or dye, and further customary additives,

[0082] Wherein the total composition adds up to 100 wt%.

[0083] Particularly preferred photoinitiators include α-hydroxyphenyl ketone, benzil dimethyl ketal or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, and mixtures of at least two of the photoinitiators, phenylphosphine oxide combinations, and bisacylphosphine oxide (BAPO).

[0084] 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 hydroxyphenyl triazine (HPT).

[0085] According to another preferred embodiment, the composition may comprise:

[0086] (ii) 0.01 to 2% by weight of a photoinitiator for the UV and / or Vis region or a photoinitiator system for the UV and / or Vis region, and 0.01 to 2% by weight of a stabilizer, and optionally

[0087] (g) 0 to 10% by weight, in particular 0.01 to 7.5% by weight, of inorganic fillers comprising inorganic oxides or inorganic mixed oxides and / or dental glass, in particular zirconium dioxide, mixed oxides of zirconium oxide and silicon dioxide, silicon dioxide, the total composition adding up to 100% by weight.

[0088] Likewise, the present invention relates to a composition comprising a filler having an average primary particle size of an inorganic filler (optionally present as agglomerated and / or aggregated primary particles) having a particle size of approximately 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 this composition.

[0089] The present invention further provides polymerized compositions and corresponding 3D molded bodies, as well as the dental models, splints, orthodontic appliances and prosthetic molded parts or blanks mentioned below, wherein the polymerized compositions alternatively or cumulatively have i) a) a flexural strength greater than or equal to 75 MPa (according to DIN EN ISO 20795-2), and / or b) an E modulus greater than or equal to 2000 MPa (according to DIN EN ISO 20795-2), and / or

[0090] ii) a) a flexural strength greater than or equal to 70 MPa (according to DIN EN ISO 20795-2), in particular measured in water at 37°C, and / or b) an E modulus greater than or equal to 2000 MPa (according to DIN EN ISO 20795-2), in particular measured in water at 37°C, and / or

[0091] iii) a) a flexural strength greater than or equal to 50 MPa (according to DIN EN ISO 20795-2), in particular measured in water at 45°C, and / or b) an E modulus greater than or equal to 1500 MPa (according to DIN EN ISO 20795-2), in particular measured in water at 45°C, and / or

[0092] iv) a) a flexural strength of greater than or equal to 40 MPa (according to DIN EN ISO 20795-2), in particular measured in water at 55° C., and / or b) an E modulus of greater than or equal to 900 MPa (according to DIN EN ISO 20795-2), in particular measured in water at 55° C., obtainable in particular by irradiating the polymerizable composition.

[0093] It is particularly preferred that the polymerized composition has a shrinkage of less than 7%, preferably less than or equal to 6.8%, preferably less than or equal to 6.5%, particularly preferably less than or equal to 6.0% (determined according to Watts, Dent. Mater 7:281-286, October 1991 (also known as the Bonded Disc method), at room temperature, Translux Energy, 60 s irradiation).

[0094] Furthermore, the present invention provides a blank in the form of a three-dimensional molded body of the polymerized composition suitable for producing dental restorative parts, orthopedic appliances or dental preforms, characterized in that the blank has a.1) a flexural strength greater than or equal to 75 MPa (according to DIN EN ISO 20795-2), and / or b.1) an E modulus greater than or equal to 2000 MPa (according to DIN EN ISO 20795-2), and optionally

[0095] a.2) a flexural strength greater than or equal to 50 MPa (according to DIN EN ISO 20795-2), in particular measured in water at 45°C, and / or b.2) an E modulus greater than or equal to 1500 MPa (according to DIN EN ISO 20795-2), in particular measured in water at 45°C, and optionally

[0096] iv) a) a flexural strength greater than or equal to 40 MPa (according to DIN EN ISO 20795-2), in particular measured in water at 55°C, and / or b) an E modulus greater than or equal to 900 MPa (according to DIN EN ISO 20795-2), in particular measured in water at 55°C.

[0097] The present invention also relates to the use of the composition for producing anatomical models, anatomical tabletop models, anatomical models for dental plaster models of replacement dentition, prosthetic parts, dental restorative parts, orthopedic appliances, braces, dental splints or dental preforms, as well as the use of the composition according to the invention in rapid prototyping processes or in rapid manufacturing or rapid tooling processes. The composition is preferably radiation-cured by means of a laser beam, an LED light source or a DLP projector.

[0098] Furthermore, the present invention provides for the use of the composition for producing dental restoration parts, including prosthetic bases or parts thereof, dentures, dental arches with at least 2 to 16 prosthetic teeth connected interproximally in a materially integral manner, crowns, temporary crowns, complete prostheses, full crowns, splints for orthodontic correction (similar to Invisalign), dental bridges, abutments, superficial structures, dental connecting strips, inlays, onlays, orthopedic appliances such as bite splints, dental preforms for dentures, drill templates for implantology, mouth guards and / or implants.

[0099] Currently, dental products are particularly understood to mean dental products producible from polymerizable compositions, such as, but not limited to, complete prostheses, temporary crowns and bridges, inlays, onlays, full crowns, bite splints, drill templates for implantology, splints for orthodontic correction (similar to Invisalign), mouth guards, dentures.

[0100] To meet high aesthetic demands, compositions used in the dental field for producing final dental prostheses, such as working models, orthodontic models, jigs, temporary prostheses, and splints, must exhibit high transparency. This transparency is typically achieved by optimally matching the refractive indices of the filler and the polymer matrix. However, various physical and chemical boundary conditions place extremely narrow limits on the selection of fillers and monomers.

[0101] According to another alternative embodiment, polymerized compositions or blanks having the properties described below with respect to their flexural strength and / or E modulus according to DIN EN USO 20795-2 can be obtained, in particular radiation-cured compositions, in particular UV / Vis-cured compositions, which are preferably also radiation-cured from all sides. Radiation curing also from all sides is understood to mean, for example, post-tempering in a 3D light oven.

[0102] Here, the following methods—rapid prototyping or rapid manufacturing (methods for producing workpieces, such as dental restorations) or rapid tooling (methods for producing tools)—each include stereolithography and DLP methods. Optionally, in these methods, after curing the polymerizable composition, post-tempering with UV, Vis, or UV / Vis light can be performed. Preferably, post-tempering of the polymerized composition or dental restoration, orthopedic appliance, or dental preform or blank is performed simultaneously from at least three sides, preferably from five to six sides, as is possible in a laser furnace. Alternatively, the polymerized composition can be annealed in addition or as an alternative.

[0103] Colored pigments can also be added to the composition to adjust the color. Furthermore, red fibers can be added to simulate the blood vessels of the gums. Suitable colored pigments include, for example, PV True Red (CAS 4948-15-6), Indian Blue 220943 (CAS 68186-87-8), True Black 100 (CAS 68186-91-4), Kronos 2220 (CAS 13463-67-7), and Brilliant Yellow 3R (CAS 68186-90-3).

[0104] In the polymerized composition, layer thicknesses of 5 µm, in particular 25 µm to 250 µm, per cured layer can be achieved. Printed layers of 30 µm, 50 µm, 70 µm, 100 µm, 120 µm and 170 µm are particularly preferred.

[0105] High transparency can be achieved by optimally selecting the formulation components according to their refractive index.

[0106] Benzoin alkyl ethers or esters, benzil monoketals, acylphosphine oxides, or aliphatic and aromatic 1,2-diketone compounds, such as 2,2-diethoxyacetophenone, 9,10-phenanthrenequinone, diacetyl, furil, anisil, 4,4'-dichlorobenzil and 4,4'-dialkoxybenzil or camphorquinone, for example, can be considered as photoinitiators. 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-3,5-dimethylaniline, N,N-3,5-tetramethylaniline and ethyl 4-dimethylaminobenzoate or organic phosphites. Common photoinitiator systems are, for example, camphorquinone+ethyl 4-(N,N-dimethylamino)benzoate, 2-(ethylhexyl) 4-(N,N-dimethylamino)benzoate or N,N-dimethylaminoethyl methacrylate.

[0107] 2,4,6-Trimethylbenzoyldiphenylphosphine oxide is particularly suitable as an initiator for polymerization initiated by UV light. UV photoinitiators can be used alone or in combination with visible light initiators.

[0108] Particularly preferred photoinitiators and / or initiator systems comprise a) at least one free-radical photoinitiator, in particular at least one peroxide and / or azo compound, in particular LPO (dilauroyl peroxide), BPO (dibenzoyl peroxide), t-BPEH (tert-butyl peroxy-2-ethylhexanoate), AIBN (2,2'-azobis-(isobutyronitrile), DTBP (di-tert-butyl peroxide), or α-hydroxyketones, camphorquinone, or acylphosphine oxides. Optionally, stabilizers and optionally b) at least one coinitiator, such as an amine, typically a tertiary amine, in particular at least one aromatic amine, such as N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidine, and / or diethyl p-dibenzylaminobenzoate, may also be added.

[0109] Particularly preferred photoinitiators include α-hydroxyphenyl ketone, benzil dimethyl ketal or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, and mixtures of at least two of the photoinitiators, phenylphosphine oxide combinations, and bisacylphosphine oxide (BAPO).

[0110] 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 hydroxyphenyl triazine (HPT).

[0111] The present invention is explained in more detail by the following examples without limiting the present invention to these examples.

[0112] The compositions according to the invention can be used to print workpieces, blanks, or three-dimensional molded bodies with excellent geometric accuracy / resolution. The molded bodies according to the invention have excellent mechanical properties even at elevated temperatures. Furthermore, good color stability can be observed in the workpieces.

[0113] Example:

[0114] General production example: The initiator is pre-dissolved in TCD acrylate or TCD diacrylate. The other monomers are then added and the mixture is homogenized. A pigment concentrate or pigment may be added, and the composition is preferably homogenized. The resulting composition can be processed using a 3D printer. It should be noted that the photoinitiator may react with ambient light and produce undesirable polymerization (the composition is preferably transferred to a pressure bath under appropriate measures). Irradiation is performed at 385-405 nm and post-curing or post-tempering is performed, for example, using a HiLite Power 3D laboratory lighting system.

[0115] The prepared mixture was used to print specimens according to ISO 20795-2 (50 µm) for the following tests on a 3D precision printer (Cara Print 4.0) with a wavelength of 405 nm. After the printing process, the specimens were rinsed with isopropyl alcohol and subjected to a post-tempering process. This was done by irradiating both sides with a HiLite Power 3D, 200 W laboratory lamp (Kulzer GmbH) for 3 to 5 minutes or as specified by the manufacturer. The properties of the mixture according to the invention for model materials were tested according to DIN EN ISO 20795-2 or in accordance with these standards.

[0116]

[0117]

[0118]

[0119]

Claims

1. A polymerizable radiation curable composition comprising (i) Monomer and (ii) at least one other component, It is characterized by (i) the monomer comprises (a.1) 5 to 45% by weight of at least one triacrylate derived from 1,3,5-tris(ω-hydroxyalkyl)isocyanurate, wherein the hydroxyalkyl groups each independently contain 1 to 8 C atoms, and (a.2) at least one difunctional monomer which is not a urethane acrylate or a urethane methacrylate, comprising (b) 5 to 45% by weight of at least one difunctional acrylate having a divalent alicyclic group and / or difunctional methacrylate having a divalent alicyclic group selected from tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, tricyclodecane diethanol diacrylate, tricyclodecane diethanol dimethacrylate and / or mixtures thereof, and (c) up to 60% by weight of at least one disubstituted 4,4'-bis(oxyphenyl)dialkylmethane of the formula I where R 1 、R 2 、R 5 and R 6 are each independently selected from H or C1 to C4-alkyl, and wherein R 3 and R 4 each independently a divalent C1 to C4-alkylene group, wherein n=0 to 6 and m=0 to 6, and (d) up to 60% by weight of at least one at least difunctional urethane (meth)acrylate, (e) up to 20% by weight of at least one monofunctional acrylate having a cycloaliphatic group and / or monofunctional methacrylate having a cycloaliphatic group, selected from (octahydro-4,7-methylene-1H-indenyl)methanol acrylate, (octahydro-4,7-methylene-1H-indenyl)methanol methacrylate, (octahydro-4,7-methylene-1H-indenyl)ethanol acrylate and (octahydro-4,7-methylene-1H-indenyl)ethanol methacrylate and mixtures thereof, (ii) 0.01 wt% to 5 wt% of the at least one other component comprising at least one photoinitiator for the UV and / or Vis region or a photoinitiator system for the UV and / or Vis region, and optionally a stabilizer, Wherein the total composition adds up to 100 wt%.

2. The composition according to claim 1, characterized in that The viscosity of the composition at room temperature of 20° C. to 23° C. is less than or equal to 3000 m·Pas.

3. The composition according to claim 1, characterized in that (a.1) The at least one triacrylate derived from 1,3,5-tris(ω-hydroxyalkyl)isocyanurate comprises 1,3,5-tris(2-hydroxyethyl)isocyanurate triacrylate, 1,3,5-tris(hydroxymethyl)isocyanurate triacrylate, 1,3,5-tris(2-hydroxyethyl)isocyanurate trimethacrylate, 1,3,5-tris(hydroxymethyl)isocyanurate trimethacrylate or a mixture containing at least two of these monomers.

4. The composition according to any one of claims 1 to 3, characterized in that (a.2) at least one difunctional monomer other than a urethane (meth)acrylate comprising (c) at least one disubstituted 4,4'-bis(oxyphenyl)dialkylmethane of formula I and mixtures thereof, where R 1 and R 2 Each is a methyl group, and R 5 and R 6 are the same and are selected from H, methyl and ethyl, and R 3 and R 4 Each is independently a divalent ethylene group or a propylene group, and n=1 to 6.

5. The composition according to claim 1, characterized in that (d) At least one difunctional urethane acrylate or urethane methacrylate is selected from difunctional urethane acrylates having a divalent alkylene group and urethane methacrylates having a divalent alkylene group.

6. The composition according to claim 1, characterized in that It contains (i) a monomer comprising (a) 5 to 35% by weight of at least one triacrylate derived from 1,3,5-tris(ω-hydroxyalkyl)isocyanurate, where the hydroxyalkyl group contains 1 to 8 C atoms and can be linear, branched and / or cyclic, and (b) 5 to 35% by weight of at least one difunctional acrylate having a divalent alicyclic group and / or difunctional methacrylate having a divalent alicyclic group selected from tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, tricyclodecane diethanol diacrylate, tricyclodecane diethanol dimethacrylate and / or mixtures thereof, and (c) 20 to 50% by weight of at least one disubstituted 4,4'-bis(oxyphenyl)dialkylmethane of formula I where R 1 、R 2 、R 5 and R 6 are each independently selected from H or C1 to C4-alkyl, And R 3 and R 4 each a divalent C1 to C4-alkylene group, where n=0 to 6 and m=0 to 6, and optionally (d) 20 to 40% by weight of at least one at least difunctional urethane acrylate and / or difunctional urethane methacrylate, (e) 5 to 20% by weight of at least one monofunctional acrylate having an alicyclic group and / or a monofunctional methacrylate having an alicyclic group, (ii) 0.01 to 5 wt. % of at least one other component comprising at least one photoinitiator for the UV and / or Vis region or a photoinitiator system for the UV and / or Vis region, and optionally at least one stabilizer for the UV and / or Vis region, and optionally at least one pigment and / or dye and other customary additives, Wherein the total composition adds up to 100 wt%.

7. The composition according to any one of claims 1 to 3 and 5 to 6, characterized in that Dental products can be produced from the composition.

8. The polymerized composition according to any one of claims 1 to 3 and 5 to 6, characterized in that The polymerized composition alternatively or cumulatively has i) a) a flexural strength according to DIN EN ISO 20795-2 of greater than or equal to 75 MPa, and / or b) an E modulus according to DIN EN ISO 20795-2 of greater than or equal to 2000 MPa, and / or ii) a) a flexural strength according to DIN EN ISO 20795-2 of greater than or equal to 70 MPa, measured in water at 37°C, and / or b) an E modulus according to DIN EN ISO 20795-2 of greater than or equal to 2000 MPa, measured in water at 37°C, and / or iii) a) a flexural strength according to DIN EN ISO 20795-2 of greater than or equal to 50 MPa, measured in water at 45°C, and / or b) an E modulus according to DIN EN ISO 20795-2 of greater than or equal to 1500 MPa, measured in water at 45°C, and / or iv) a) a flexural strength according to DIN EN ISO 20795-2 of greater than or equal to 40 MPa, measured in water at 55° C., and / or b) an E modulus according to DIN EN ISO 20795-2 of greater than or equal to 900 MPa, measured in water at 55° C.

9. A blank in the form of a three-dimensional molded body of the polymerized composition according to any one of claims 1 to 3 and 5 to 6 for producing a dental restorative 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 greater than or equal to 75 MPa, and / or b.1) an E modulus according to DIN EN ISO 20795-2 of greater than or equal to 2000 MPa, and optionally a.2) a flexural strength according to DIN EN ISO 20795-2 of greater than or equal to 50 MPa, measured in water at 45° C., and / or b.2) an E modulus according to DIN EN ISO 20795-2 of greater than or equal to 1500 MPa, measured in water at 45° C.

10. Use of the polymerized composition according to any one of claims 1 to 3 and 5 to 6 for producing anatomical models, appliances, dental splints, prosthetic parts, dental restoration parts, orthopedic appliances or dental preforms, in a rapid prototyping process or in a rapid manufacturing process or rapid tooling process.

11. Use according to claim 10, characterized in that Anatomical models include anatomical tabletop models, dental working models, dental full models, dental root models, anatomical saw cut or dental saw cut models, crossbite models, precursor models, precision models, and / or anatomical models of dental plaster models for replacement dentition.

12. Use according to claim 10, characterized in that The dental restoration components include prosthetic bases or parts thereof, dentures, dental arches with at least 2 to 16 dentures connected interproximally in a materially integral manner, crowns, temporary crowns, complete prostheses, full crowns, splints for orthodontic correction, dental bridges, abutments, shallow structures, dental connecting strips, inlays, onlays, orthopedic appliances, dental preforms for dentures, drill templates for implantology, mouth guards and / or implants.

13. Use according to claim 12, characterized in that The orthopedic appliance comprises a bite splint.

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