Radiation-curable composition for use in a rapid prototyping process or a rapid manufacturing process

Abstract

The invention relates to a polymerisable, radiation-curable composition, in particular a UV / Vis-curable, UV-curable or Vis-curable composition comprising (i) monomers and (ii) at least one further component, wherein the (i) monomers comprise (a) at least one urethane (meth)acrylate that is at least difunctional, (b) at least one monofunctional acrylate having an alicyclic group and / or at least one monofunctional methacrylate having an alicyclic group, and (ii) the at least one further component comprises (c) at least one photoinitiator for the UV and / or visible range or a photoinitiator system for the UV and / or visible range. The composition according to the invention is suitable for producing dental prosthetic parts, orthopaedic instruments or dental pre-forms, which are characterised by a) a flexural strength of greater than or equal to 75 MPa, and / or b) a modulus of elasticity of greater than or equal to 2600 MPa, and / or c) a water absorption of less than 45 [μg / mm3], wherein these dental prosthetic parts, orthopaedic instruments or dental pre-forms can be produced using a rapid prototyping process or using a rapid manufacturing or rapid tooling process.

Description

[0001] Radiation-curable composition for use in rapid prototyping or rapid manufacturing processes

[0002] The invention relates to a polymerizable, radiation-curable, in particular UV / Vis, UV or Vis-curable composition, comprising (i) monomers and (ii) at least one further component, wherein the (i) monomers comprise (a) at least one at least difunctional urethane (meth)acrylate, (b) at least one monofunctional acrylate with an alicyclic group and / or at least one monofunctional methacrylate with an alicyclic group, and (ii) the at least one further component comprises (c) at least one photoinitiator for the UV and / or Vis range or a photoinitiator system for the UV and / or Vis range.The composition according to the invention is suitable for the production of blanks and three-dimensional molded bodies of dental prosthetic parts, orthopedic appliances, dental pre-forms, technical parts, tools, instruments, hoof repair parts or implants in medical prosthetics, which have a) a flexural strength of greater than or equal to 75 MPa and / or b) an E-modulus of greater than or equal to 2600 MPa, and / or c) a water absorption of less than 45 [ .g / mm. 3 ], which can be produced using a rapid prototyping or a rapid manufacturing or rapid tooling process.

[0003] In addition to manual manufacturing methods, digital manufacturing methods are becoming increasingly important in the dental field. Dental prostheses, such as crowns and bridges, have been manufactured subtractively using CAD / CAM technologies for several years. Since this milling technology utilizes only a small portion of the material, discarding the majority, and the tool can only work on one dental component at a time, significant cost advantages should be achieved with progressive processes involving the simultaneous production of many dental components and minimal or no waste.

[0004] Generative processes are already known in the dental field, for example in the form of laser sintering from CoCr, Ti or polymers for the production of crowns and bridges, implant components or models.

[0005] Compositions of acrylates or derivatives of acrylates for the production of dental prostheses with a corresponding property profile in relation to the mechanical requirements in the dental field according to DIN EN ISO 10477 are currently only available from a few manufacturers. Since only a few manufacturers can demonstrate approval according to MPG Class Ila for their printable plastics and resins, and most resins can currently only be printed unfilled, the mechanical properties of currently available materials are always poor. Therefore, these materials are not suitable for the production of definitive dental prostheses. A filled composition available on the market has the disadvantage of considerable sedimentation of the fillers and excessive water absorption according to ISO 10477:2020. If sedimentation is too severe, a homogeneous print result cannot be guaranteed given the long printing times.In addition, the user must first quantitatively homogenize the composition before use. Therefore, there is a need for compositions for the production of definitive prosthetic parts, orthopedic appliances, or dental preforms.

[0006] The object of the invention was to provide a mixture of monomers, which can optionally comprise fillers, which, after curing, in particular by means of radiation-curing processes, exhibits good properties with regard to the modulus of elasticity. In particular, a balance should be achieved between the necessary strength while avoiding brittleness and, at the same time, a balance between low viscosity as a requirement for printing and, at the same time, avoiding excessive sedimentation of the filler. In addition, the composition should be suitable for use in radiation-curing rapid manufacturing (RM) or rapid prototyping (RP) processes. A further object was to provide a composition which contains inorganic fillers and, in particular, as a polymerizable composition or as a polymerized composition, exhibits high transparency.Furthermore, the task was to specify a composition that has low water absorption, in particular according to ISO 10477:2020, and is therefore suitable for printing dental materials such as definitive dentures.

[0007] Dental products are understood here to mean, in particular, dental products that can be manufactured from polymerizable compositions, such as, but not limited to, complete dentures, temporary crowns and bridges, inlays, onlays, full crowns, bite splints, drilling templates for implantology, splints for orthodontic corrections (similar to Invisaligri), mouthguards, artificial teeth and brackets.

[0008] The invention relates to a polymerizable, radiation-curable composition comprising (i) monomers and (ii) at least one further component, wherein (i) the monomers comprise (a) at least one at least difunctional urethane (meth)acrylate,

[0009] (b) at least one monofunctional acrylate with an alicyclic group and / or at least one monofunctional methacrylate with an alicyclic group or mixtures thereof, in particular dicyclopentanyl methyl acrylate, and optionally

[0010] (d) at least one acrylic acid ester with an additional carboxy group, and (ii) which comprises at least one further component

[0011] (c) at least one photoinitiator for UV and / or Vis range or one photoinitiator system for UV and / or Vis range.

[0012] It is particularly preferred if (b) the at least one monofunctional acrylate with an alicyclic group and / or the at least one monofunctional methacrylate with an alicyclic group comprises at least one monofunctional acrylate with a dicyclopentane group and / or at least one monofunctional methacrylate with a dicyclopentane group, or mixtures containing these. The monofunctional acrylate with an alicyclic group preferably comprises at least one monofunctional acrylate with a dicyclopentane group and / or at least one monofunctional methacrylate with a dicyclopentane group, wherein the acrylate has from 14 to 25 carbon atoms, in particular 14 to 18 carbon atoms. Dicyclopentanyl methyl acrylate is particularly preferred.

[0013] In a particularly preferred embodiment, the composition (d) comprises at least one acrylic acid ester with an additional carboxy group.

[0014] An alternative subject matter of the invention is a polymerizable, radiation-curable composition comprising (i) monomers and (ii) at least one further component, wherein (i) the monomers comprise

[0015] (a) at least one at least difunctional urethane (meth)acrylate, and

[0016] (d) at least one acrylic acid ester with an additional carboxy group, and (ii) which comprises at least one further component

[0017] (c) at least one photoinitiator for UV and / or Vis range or one photoinitiator system for UV and / or Vis range.

[0018] The compositions according to the invention are suitable for use in a generative printing process with layer-by-layer jet-induced polymerization of the composition for producing three-dimensional molded articles. In particular, the composition has a viscosity of less than 7500 mPas, preferably less than 5000 mPas, in particular from 500 to less than 4000 mPas, preferably from 500 to 3000 mPas, particularly preferably from 1 to 1500 mPas. Further preferably, the composition has a viscosity of 100 to 1200 mPas.

[0019] The polymerization is preferably carried out by UV and / or Vis rays inducing a layer-by-layer polymerization of the composition to produce three-dimensional molded bodies.

[0020] The invention alternatively relates to a composition comprising (e) at least one disubstituted 4,4'-di(oxabenzene)dialkylmethane of the formula I with R 1, R 2 , R 5 and R 6 each independently selected from H or C1 to C4 alkyl, and with R 3 and R 4 each bivalent C1 to C4 alkylene, with n = 0 to 6 and m = 0 to 6, in particular n = 1 and m = 1 and / or n + m = 2.

[0021] According to a particularly preferred alternative, the (d) at least one acrylic acid ester with additional carboxy group is selected from an acrylic acid ester with additional carboxy group of the formula II or III with R 7 each independently selected from divalent C, H, O and optionally N-containing groups having 1 to 25 C atoms, in particular divalent aromatic esters, aromatic urethanes, alkylene esters, alkyl urethanes, aromatic ethers, alkyl ethers, and R 8 is selected from H and 1 to 4 C-alkyl, preferably R 7 a divalent aromatic ester, with R 9independently selected from divalent benzoyl, salicyloyl and derivatives thereof or -C-, R 10 is bivalent -(OR 11 ) with R 11 is ethylene or propylene and where r is 0 to 10, in particular 1 to 6, preferably r = 1 or R 10 is independently selected from divalent alkylene and R 8 is selected from H and 1 to 4 C-alkyl, preferably R 8 is H, methyl, or ethyl. Preferably, (d) the at least one acrylic acid ester with an additional carboxyl group comprises phthalic acid mono-[2-(methacryloyloxy)ethyl ester] or 2-acryloyloxyethyl hydrogen phthalate, polyether-functionalized acrylic acid esters with a carboxyl group, and mixtures thereof.

[0022] In an alternative, (b) the at least one monofunctional acrylate with alicyclic group and / or at least one monofunctional methacrylate with alicyclic group may comprise at least one monofunctional acrylate with monovalent alicyclic group and / or at least one monofunctional methacrylate with monovalent alicyclic group, in particular dicyclopentanylalkylene acrylate and / or dicyclopentanylalkylene methacrylate, each independently with alkylene comprising C1 to C6 atoms or mixtures containing at least one of the monomers.

[0023] Particularly preferred difunctional urethane (meth)acrylates with a bivalent alicyclic group comprise or are selected from bis-(4',7'-dioxa-3',8'-dioxo-2'-aza-decyl-9'-ene)tetrahydrodicyclopentadiene, bis-(4',7'-dioxa-3',8'-dioxo-2'-aza-9'-methyl-decyl-9'-ene)tetrahydrodicyclopentadiene and / or mixtures thereof and optionally mixtures of the 3,8- / 3,9- / 4,8- / 3,10- / 4,1 O-isomers and / or the cis- and trans-isomers of the aforementioned compounds. Particularly preferably, the difunctional urethane acrylate having a bivalent alicyclic group is selected from bis-(4',7'-dioxa-3',8'-dioxo-2'-aza-decyl-9'-ene)tetrahydrodicyclopentadiene, bis-(4',7'-dioxa-3',8'-dioxo-2'-aza-9'-methyl-decyl-9'-ene)tetrahydrodicyclopentadiene and / or mixtures thereof and optionally mixtures of the 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers and / or the cis- and trans-isomers of the aforementioned compounds.

[0024] In a preferred embodiment, (a) the at least one difunctional urethane (meth)acrylate is selected from difunctional urethane (meth)acrylates having a divalent alkylene group.

[0025] The difunctional urethane (meth)acrylate with a bivalent alkylene group is preferably selected from linear or branched urethane dimethacrylates functionalized with a bivalent alkylene group, urethane dimethacrylate-functionalized polyethers with alkylene group(s), such as bis(methacryloxy-2-ethoxycarbonylamino)alkylene, bis(methacryloxy-2-ethoxycarbonylamino)-substituted polyalkylene ethers, preferably 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane, or IIDMA with the alternative designation HEMA-TDMI. Bis(methacryloxy-2-ethoxycarbonylamino)alkylene is preferred, where alkylene comprises linear or branched C3 to C20, preferably C3 to C6, particularly preferably a methyl-substituted alkylene, such as HEMA-TMDI. The divalent alkylene preferably comprises 2,2,4-trimethylhexamethylene and / or 2,4,4-trimethylhexamethylene.

[0026] Furthermore, the composition may comprise at least one further monomer (g) at least one di-, tri-, tetra-, or multi-functional monomer, which in particular is not a urethane (meth)acrylate and in particular does not correspond to formula I. Likewise, the composition may comprise a further mono-functional monomer (h).

[0027] In an alternative, (b) the at least one mono-functional acrylate with a monovalent alicyclic group and / or at least one mono-functional methacrylate with a monovalent alicyclic group can comprise tricyclodecanealkanol methacrylate and / or tricyclodecanealkanol acrylate with alkanol having 1 to 10 C atoms or mixtures containing at least one of these monomers, preference is given to tricyclodecanemethanol acrylate, tricyclodecanemethanol methacrylate, dicyclopentanyl acrylate, tricyclodecaneethanol acrylate, tricyclodecaneethanol methacrylate, isomers of the aforementioned monomers and / or mixtures thereof.

[0028] Likewise, a composition according to the invention preferably comprises as (e) at least one disubstituted 4,4'-di(oxabenzene)dialkylmethane of the formula I includes R 1 and R 2 each methyl-, and R 5 and R 6 equal and selected from H, methyl and ethyl, in particular with R 5 and R 6 equal and selected from H and methyl, and with R 3 and R 4 each independently bivalent ethylene or propylene with n = 1 to 6, preferably n = 2 to 4, and with m = 1 to 6, preferably m = 2 to 4, preferably with n = 2 and m = 2 or with n = 4 and m = 4 and mixtures thereof.

[0029] According to a further preferred alternative, the composition comprises as further components inorganic fillers selected from

[0030] (f) inorganic fillers comprising inorganic oxides or inorganic mixed oxides and / or dental glasses, in particular zirconium dioxide, mixed oxides of a metal oxide and silicon dioxide, silicon dioxide; preferred fillers comprise silicon dioxide and / or mixed oxides with silicon dioxide. The inorganic fillers are particularly preferably silanized, in particular silanized with acrylic-functional silanes, particularly preferably with (3-acryloyloxyalkyl)trimethoxysilanes with alkyl C1 to C6, preferably with (3-acryloyloxypropyl)trimethoxysilane.

[0031] A particularly preferred composition comprises

[0032] (a) 1 to 90 wt.% of at least one at least difunctional urethane (meth)acrylate, (b) 1 to 50 wt.% of at least one monofunctional acrylate with an alicyclic group and / or at least one monofunctional methacrylate with an alicyclic group, and

[0033] (c) 0.01 to 10 wt.% of at least one photoinitiator for UV and / or Vis range or a photoinitiator system for UV and / or Vis range,

[0034] (d) 1 to 50 wt.% of at least one acrylic acid ester with additional carboxy group

[0035] (e) 1 to 25 wt.% of at least one disubstituted 4,4'-di(oxabenzene)dialkylmethane of the formula I with R 1 , R 2 , R 5 and R 6 each independently selected from H or C1 to C4 alkyl, and with R 3 and R4 is each bivalent C1 to C4-alkylene, with n = 0 to 6 and m = 0 to 6, in particular n = 1 and m = 1 and / or n + m = 2,

[0036] (f) 0 to 35 wt.% inorganic fillers comprising inorganic oxides or inorganic mixed oxides and / or dental glasses, in particular silicon dioxide, zirconium dioxide, mixed oxides with silicon dioxide, preferred fillers comprise silicon dioxide and / or mixed oxides of a metal oxide and silicon dioxide,

[0037] (g) 0 to 10 wt.%, in particular 1 to 10 wt.% alkylene dimethacrylate and / or alkylene diacrylate, preferably with alkylene dimethacrylate, preferably each independently with alkylene C1 to C12-alkylene, preferably C1 to C4-alkylene, particularly preferably ethylene glycol dimethacrylate, and

[0038] (h) optionally 0.1 to 5 wt%, in particular 0.1 to 2 wt% of hydroxyethyl acrylate, the total composition being 100 wt%.

[0039] Further preferred is a composition comprising

[0040] (a) 30 to 70 wt.% of at least one at least difunctional urethane (meth)acrylate,

[0041] (b) 10 to 40 wt.% of at least one monofunctional acrylate with an alicyclic group and / or at least one monofunctional methacrylate with an alicyclic group,

[0042] (c) 0.01 to 10 wt.% of at least one photoinitiator for UV and / or Vis range or a photoinitiator system for UV and / or Vis range,

[0043] (d) 5 to 40% by weight, in particular 5 to 25% by weight, of at least one acrylic acid ester with an additional carboxy group,

[0044] (e) 1 to 15% by weight, in particular 2 to 5% by weight, of at least one disubstituted 4,4'-di(oxabenzene)dialkylmethane of the formula I with R 1 , R 2 , R 5 and R 6 each independently selected from H or C1 to C4 alkyl, and with R 3 and R 4 each bivalent C1 to C4-alkylene, with n = 0 to 6 and m = 0 to 6, in particular n = 1 and m = 1 and / or n + m = 2,

[0045] (f) 0 to 35 wt.% inorganic fillers comprising inorganic oxides or inorganic mixed oxides and / or dental glasses, in particular silicon dioxide, zirconium dioxide, mixed oxides with silicon dioxide and another metal oxide, preferred fillers comprise silicon dioxide and / or mixed oxides with silicon dioxide and another metal oxide,

[0046] (g) 0 to 10 wt.%, in particular 1 to 10 wt.% of alkylene dimethacrylate and / or alkylene diacrylate, preferably with alkylene dimethacrylate, preferably each independently with alkylene C1 to C12-alkylene, preferably C1 to C4-alkylene, particularly preferably ethylene glycol dimethacrylate,

[0047] (h) optionally 0.1 to 5 wt%, in particular 0.1 to 2 wt% of hydroxyethyl acrylate, the total composition being 100 wt%.

[0048] Further preferred is a composition comprising

[0049] (a) 40 to 60 wt.% of at least one at least difunctional urethane (meth)acrylate,

[0050] (b) 15 to 30 wt.% of at least one monofunctional acrylate with an alicyclic group and / or at least one monofunctional methacrylate with an alicyclic group,

[0051] (c) 0.01 to 10 wt.% of at least one photoinitiator for UV and / or Vis range or a photoinitiator system for UV and / or Vis range,

[0052] (d) 5 to 30% by weight, in particular 5 to 25% by weight, of at least one acrylic acid ester with an additional carboxy group,

[0053] (e) 1 to 15% by weight, in particular 2 to 5% by weight, of at least one disubstituted 4,4'-di(oxabenzene)dialkylmethane of the formula I, with R 1 , R 2 , R 5 and R 6 each independently selected from H or C1 to C4 alkyl, and with R 3 and R 4 each bivalent C1 to C4 alkylene, with n = 0 to 6 and m = 0 to 6, in particular n = 1 and m = 1 and / or n + m = 2,

[0054] (f) 0 to 35 wt.% inorganic fillers comprising inorganic oxides or inorganic mixed oxides and / or dental glasses, in particular silicon dioxide, zirconium dioxide, mixed oxides with silicon dioxide, preferred fillers comprise silicon dioxide and / or mixed oxides with silicon dioxide and another metal oxide,

[0055] (g) 0 to 10 wt.%, in particular 1 to 10 wt.% of alkylene dimethacrylate and / or alkylene diacrylate, preferably with alkylene dimethacrylate, preferably each independently with alkylene C1 to C12-alkylene, preferably C1 to C4-alkylene, particularly preferably ethylene glycol dimethacrylate, the total composition being 100 wt.%. Optionally, additionally

[0056] (h) 0.1 to 5 wt.%, in particular 0.1 to 2 wt.% of hydroxyethyl acrylate may be present in the composition. A particularly preferred composition comprises

[0057] (a) 1 to 90 wt.% of at least one at least difunctional urethane (meth)acrylate,

[0058] (b) 1 to 50% by weight, in particular 20 to 35% by weight, of at least one monofunctional acrylate with an alicyclic group and / or at least one monofunctional methacrylate with an alicyclic group, and

[0059] (c) 0.01 to 10 wt.% of at least one photoinitiator for UV and / or Vis range or a photoinitiator system for UV and / or Vis range,

[0060] (d) optionally 1 to 10 wt.%, in particular 1 to 9 wt.%, preferably 1 to 7 wt.%, of at least one acrylic acid ester with an additional carboxy group,

[0061] (e) 1 to 25% by weight, in particular 2 to 5% by weight, of at least one disubstituted 4,4'-di(oxabenzene)dialkylmethane of the formula I, with R 1 , R 2 , R 5 and R 6 each independently selected from H or C1 to C4 alkyl, and with R 3 and R 4 each bivalent C1 to C4 alkylene, with n = 0 to 6 and m = 0 to 6,

[0062] (f) 0 to 35 wt.% of inorganic fillers comprising inorganic oxides or inorganic mixed oxides and / or dental glasses, in particular zirconium dioxide, mixed oxides of silicon dioxide, silicon dioxide, preferred fillers comprise silicon dioxide and / or mixed oxides with silicon dioxide and a metal oxide, the total composition being 100 wt.%. Optionally,

[0063] (g) 0 to 10 wt.%, in particular 1 to 10 wt.% of alkylene dimethacrylate and / or alkylene diacrylate, preferably with alkylene dimethacrylate, preferably each independently with alkylene C1 to C12 alkylene, preferably C1 to C4 alkylene, particularly preferably ethylene glycol dimethacrylate, and / or optionally (h) 0.1 to 5 wt.%, in particular 0.1 to 2 wt.% of hydroxyethyl acrylate may be present in the composition.

[0064] Further preferred is a composition which comprises

[0065] (a) 30 to 70% by weight, in particular 40 to 60% by weight, of at least one at least difunctional urethane (meth)acrylate,

[0066] (b) 10 to 40% by weight, in particular 15 to 35% by weight, of at least one monofunctional acrylate with an alicyclic group and / or at least one monofunctional methacrylate with an alicyclic group,

[0067] (c) 0.01 to 10 wt.% of at least one photoinitiator for UV and / or Vis range or a photoinitiator system for UV and / or Vis range,

[0068] (d) optionally 1 to 9 wt.%, in particular 1 to 7 wt.%, of at least one acrylic acid ester with an additional carboxy group (e) 1 to 15 wt.%, in particular 2 to 5 wt.%, of at least one disubstituted 4,4'-di(oxabenzene)dialkylmethane of the formula I, with R 1 , R 2 , R 5 and R 6 each independently selected from H or C1 to C4 alkyl, and with R 3 and R 4each bivalent C1 to C4 alkylene, with n = 0 to 6 and m = 0 to 6,

[0069] (f) 0 to 35 wt.% of inorganic fillers comprising inorganic oxides or inorganic mixed oxides and / or dental glasses, in particular silicon dioxide, zirconium dioxide and / or mixed oxides with silicon dioxide and another metal oxide, and

[0070] (g) 0 to 10 wt.%, in particular 1 to 10 wt.% of alkylene dimethacrylate and / or alkylene diacrylate, preferably with alkylene dimethacrylate, preferably each independently with alkylene C1 to C12-alkylene, preferably C1 to C4-alkylene, particularly preferably ethylene glycol dimethacrylate,

[0071] (h) optionally 0.1 to 5 wt%, in particular 0.1 to 2 wt% of hydroxyethyl acrylate, the total composition being 100 wt%.

[0072] Further preferred is a composition comprising

[0073] (a) 30 to 70 wt.%, in particular 40 to 60 wt.% of at least one at least difunctional urethane (meth)acrylate,

[0074] (b) optionally 10 to 40 wt.%, in particular 15 to 30 wt.%, of at least one monofunctional acrylate with an alicyclic group and / or at least one monofunctional methacrylate with an alicyclic group,

[0075] (c) 0.01 to 10 wt.% of at least one photoinitiator for UV and / or Vis range or a photoinitiator system for UV and / or Vis range,

[0076] (d) 1 to 60 wt.%, preferably from 5 to 60 wt.%, particularly preferably from 10 to 50 wt.%, in particular 10 to 40 wt.% of at least one acrylic acid ester with an additional carboxy group

[0077] (e) optionally 5 to 30 wt.%, in particular 5 to 15 wt.% of at least one disubstituted 4,4'-di(oxabenzene)dialkylmethane of the formula I with R 1 , R 2 , R 5 and R 6each independently selected from H or C1 to C4 alkyl, and with R 3 and R 4 each bivalent C1 to C4 alkylene, with n = 0 to 6 and m = 0 to 6,

[0078] (f) 0 to 35 wt.%, in particular 1 to 25 wt.%, of inorganic fillers comprising inorganic oxides or inorganic mixed oxides and / or dental glasses, in particular zirconium dioxide, mixed oxides with silicon dioxide, silicon dioxide, preferred fillers comprise silicon dioxide and / or mixed oxides with silicon dioxide and another metal oxide, (g) 0 to 10 wt.%, in particular 1 to 7 wt.% of alkylene dimethacrylate and / or alkylene diacrylate, preferably with alkylene dimethacrylate, preferably each independently with alkylene C1 to C12-alkylene, preferably C1 to C4-alkylene, particularly preferably ethylene glycol dimethacrylate,

[0079] (h) optionally 0.1 to 5 wt%, in particular 0.1 to 2 wt% of hydroxyethyl acrylate, the total composition being 100 wt%.

[0080] When selecting the monomers, it is also important to ensure that they bond well with the optional filler. Polyurethanes, acrylates, polyesters, and other monomers generally do not bond well with the fillers used. Therefore, the fillers are usually silanized or hydrophobized on their surfaces to improve their bonding with the monomers. The fillers according to the invention are preferably silanized on their surfaces with silanes containing acrylate groups.

[0081] Surprisingly, it was found that even acidic monomers adhere well to the filler particles. The invention therefore provides a composition comprising a polymerizable monomer with a free carboxyl group and / or an anhydride group, wherein the composition additionally comprises a difunctional acrylate or methacrylate with an alicyclic group and at least one photoinitiator.

[0082] If inorganic fillers cannot be used in the polymerizable composition due to the specific dental application, e.g., due to the desired viscosity of the composition, it is possible to incorporate dyes or pigments into the composition to reflect radiation, particularly diffuse reflection or scattering of the incident radiation. Dyes are considered compounds that are soluble in the polymerizable composition and preferably form a clear solution.

[0083] The radiation-curable compositions according to the invention can preferably be irradiated with a radiation source that emits light in the visible range; particular preference is given to radiation sources that emit radiation from 360 to 750 nm, in particular at approximately 385 nm, and particularly preferably at approximately 405 nm. The composition according to the invention can particularly preferably be irradiated with a polychromatic radiation source, such as a DLP projector, or preferably with a monochromatic radiation source, such as a laser projector, in the visible range from 380 to 660 nm. By adding these pigments and / or dyes, the photoinitiator content in the composition can be reduced. An excessively high photoinitiator content can lead to so-called "overcuring" of the irradiated composition, i.e., embrittlement, so that the correspondingly produced dental parts are unusable.

[0084] The use of the inorganic fillers, pigments, or dyes according to the invention leads to a uniform dispersion of the radiation sources, especially the UV and visible radiation sources, in the monomer matrix of the composition, so that a more uniform curing of the composition is assumed. As a result, the polymerized compositions exhibit increased values ​​for the achieved fracture energy.

[0085] The composition according to the invention has the following properties after exposure to a radiation source in the visible range, in particular from 385 to 405 nm, preferably after exposure in a stereolithography process and obtaining a polymerized composition preferably in the form of a blank, dental prosthetic part, orthopedic appliance or dental pre-form, as well as optional post-treatment of the polymerized composition with a radiation source: a) a flexural strength of greater than or equal to 75 MPa and / or b) an E-modulus of greater than or equal to 2600 MPa, in particular greater than or equal to 2700 MPa, in each case determined according to DIN EN ISO 10477: 2020.

[0086] The post-curing or post-annealing can preferably be carried out using a laboratory light unit (HiLite Power 3D) or in a light oven, preferably with a light spectrum of 390 - 540 nm.

[0087] The invention relates to a polymerizable, radiation-curable composition, in particular polymerizable by means of UV / VIS, UV or VIS radiation, comprising (i) monomers, preferably a mixture of monomers, and (ii) at least one further component, wherein the (i) monomers comprise

[0088] (a) at least one at least difunctional urethane (meth)acrylate,

[0089] (b) at least one monofunctional acrylate with an alicyclic group and / or at least one monofunctional methacrylate with an alicyclic group, and / or

[0090] (d) at least one acrylic acid ester with an additional carboxy group, and / or

[0091] (e) optionally at least one disubstituted 4,4'-di(oxabenzene)dialkylmethane of formula I with R 1 , R 2 , R 5 and R 6 each independently selected from H or C1 to C4 alkyl, in particular with R 1 and R 2is C1 to C4-alkyl, preferably methyl, and with R 5 and R 6 the same and selected from H, methyl or ethyl, in particular with R 5 and R 6 equal and selected from H or methyl, and with R 3 and R 4 each bivalent C1 to C4-alkylene, with n = 2 to 6 and m = 2 to 6, and (ii) the at least one further component,

[0092] (c) comprises at least one photoinitiator for UV and / or Vis range or a photoinitiator system.

[0093] In preferred alternatives, the formula IR 1 and R 2 each methyl-, and R 5 and R 6 be the same and selected from H, methyl and ethyl, preferably R 5 and R 6 equal and selected from H and methyl, and with R 3 and R 4each independently bivalently ethylene or propylene with n = 1 to 6, preferably n = 2 to 4, and with m = 1 to 6, particularly preferably n = 2 to 4 and m = 2 to 4, further preferably with n = 2 and m = 2 or with n = 4 and m = 4, and mixtures thereof. Particular preference is given to a mixture of 4,4'-di(oxabenzene)dialkylmethane of the formula I a) with R 1 and R 2 each methyl-, and R 5 and R 6 equal to H and with R 3 and R 4 each independently bivalent ethylene with n = 1 to 6, preferably n = 2 to 4, and with m = 1 to 6, preferably m = 2 to 4, preferably with n = 4 and m = 4 and mixtures thereof in mixtures with b) with R 1 and R 2 each methyl-, and R 5 and R 6 equal to methyl and with R 3 and R 4 each independently bivalent ethylene with n = 1 to 6, preferably n = 1 to 4 and m = 1 to 4, preferably with n = 1 and m = 1 and mixtures thereof.

[0094] Optionally, the composition may have a content of alkylene dimethacrylate and / or alkylene diacrylate, preferably each independently with alkylene C1 to C12 alkylene, of 0 to 10 wt.%, in particular 0 to 5 wt.%, preferably 0.001 to 5 wt.%, the total content of the composition being 100 wt.%.

[0095] Optionally, the composition may additionally comprise 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 with alkyl having 1 to 10 C atoms, preferably 1 to 4 C atoms, or a mixture containing at least two of the monomers mentioned, in particular each independently containing at least 2 ethylene glycol or propylene glycol units, preferably 3 to 15. 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 diacrylates selected from decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, hexyldecanediol di(meth)acrylate, butanediol di(meth)acrylate or mixtures containing at least one of the acrylates.

[0096] The designation in brackets in the terms (methyl)acrylate or (alkyl)acrylate means that the acrylates can be present as acrylate or methyl acrylate or alternatively as alkyl acrylate.

[0097] Furthermore, it is preferred if the composition contains as (d) the at least one acrylic acid ester with an additional carboxy group, acrylic acid ester with at least one additional anhydride group of carboxy groups and / or the at least one derivative of the aforementioned acrylic acid esters, in particular (alkyl)acrylic acid esters with alkyl C1 to C4-alkyl groups, preferably with alkyl being methyl or ethyl, selected from an acrylic acid ester with an additional carboxy group of the formula II or III, with R 7each independently selected from divalent C, H, O-containing groups having 1 to 50 C atoms, in particular having 1 to 25 C atoms, preferably 8 to 25 C atoms, in particular divalent aromatic esters, alkylene esters, aromatic ethers, alkyl ethers, and R 8 is selected from H and 1 to 4 C-alkyl, preferably R 7 a divalent aromatic ester, preferably an ester of a phthalate and R 8 is H, methyl or ethyl, where R 9 can be independently selected from divalent benzoyl, salicyloyl or -C-, R 10 can be a bivalent -(OR 11 ), with R 11 is ethylene or propylene and where r = 0 to 8, in particular where r = 1 to 4, preferably r = 1, particularly preferably -(OR 11 )- a bivalent group derived from poly(alkylene glycol), in particular poly(propylene glycol) or poly(ethylene glycol) with 1 to 6 propylene glycol or ethylene glycol units, or R 10can be independently selected from divalent alkylene and R 8 can be selected from H and 1 to 4 C-alkyl, preferably R 8 H, methyl or ethyl.

[0098] The invention also relates to a composition which can comprise as (d) at least one acrylic acid ester with an additional carboxy group, acrylic acid ester with at least one additional anhydride group of carboxy groups and / or derivatives of the aforementioned acrylic acid esters, in particular phthalic acid mono-[2-(methacryloyloxy)ethyl ester] or 2-acryloyloxyethyl hydrogen phthalate, 2-(acryloyloxy)ethyl 2-hydroxyethyl phthalate, polyether-functionalized acrylic acid esters with a carboxy group, preferably the composition comprises polyether-functionalized acrylic acid esters with a carboxy group on acrylic, polyether-functionalized acrylic acid esters with a carboxy group on alkyl, wherein in particular the polyethers are based on poly(propylene glycol) and poly(ethylene glycol) with 1 to 6 glycol units.

[0099] According to the invention, the composition comprises 2-acryloyloxyethyl hydrogen phthalate of formula III with R 9 Benzoyl, R 10 is bivalent -(OR 11) r -, with r = 1 and R 8 is H or methyl, preferably H optionally in a mixture with 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate or hydroxypropyl (meth)acrylate.

[0100] Likewise preferred monomers as at least one further monomer in the composition can be selected from: (g) at least one di-, tri-, tetra- or multi-functional monomer, which in particular is not a urethane (meth)acrylate.

[0101] Hydroxyethyl acrylate is preferably used as the monofunctional monomer. Hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and / or hydroxyethyl acrylate can also be used, optionally as a mixture of at least two of the aforementioned monomers. Preferably, the at least one acrylic acid ester with an additional carboxyl group is present in a mixture with hydroxyethyl acrylate, with the acrylic acid ester with an additional carboxyl group being present in a concentration of 95 to 99 wt.% and the hydroxyethyl acrylate in a concentration of 1 to 5 wt.%, and the mixture having a total content of 100 wt.%.

[0102] According to an alternative, compositions are preferred which comprise, as a further component, inorganic fillers selected from, (f) inorganic fillers, inorganic oxides or inorganic mixed oxides, in particular oxides of zirconium and / or silicon and / or dental glasses, preference being given to silicon dioxide, zirconium dioxide or mixed oxides with silicon dioxide and a metal oxide, in particular metal dioxide and silicon dioxide. In the present case, metal oxides or metal dioxides are those which do not correspond to silicon dioxide, which has already been mentioned as a specific metal oxide. Particular preference is given to mixed oxides with silicon dioxide and another metal oxide having primary particle sizes in the range of less than 100 nm, which are optionally present as agglomerates with 2 to 5 pm. These oxides or mixed oxides are preferably essentially X-ray amorphous.Aluminosilicate glasses, fluoroaluminosilicate glasses, and / or barium aluminum silicate can be used as dental glasses. The oxides can be selected from the aforementioned as well as from amorphous spherical fillers based on oxides or mixed oxides. Primary particles are considered to be the smallest oxide particles, which may be present as agglomerates.

[0103] The particle sizes of the inorganic fillers, such as the at least one inorganic oxide, mixed oxide or dental glass, for example comprising barium aluminum oxide, have on average a mean particle diameter of d50 less than 10 pm for the present applications. The fillers particularly preferably have a particle diameter of approximately 3 to 70 nm, in particular from 10 to 50 nm (nanometers). Optionally, the particles can be aggregated or agglomerated as particles with a size of up to 10 pm. The primary particle sizes of the inorganic fillers, which can optionally be agglomerated and / or aggregated primary particles, have on average a particle diameter of approximately 3 to 70 nm, in particular from 10 to 50 nm. The inorganic oxides, such as silicon dioxide, preferably have a primary particle size of 3 to 70 nm.Particle size can be determined in a dispersion in water by determining the particle size distribution by volume weight (Malvern, using laser diffraction, ISO 13320: 2009). Additionally or alternatively, the particle size can be determined using SEM (scanning electron microscope). The advantage of the very small particle diameters, which may be aggregated and / or agglomerated, is that the light from these particles is essentially diffusely scattered during radiation curing, thus leading to improved curing in the stereolithography or DLP process.

[0104] The invention relates to a composition comprising monomers and optionally pre-polymers (oligomers) and / or polymers comprising at least one difunctional urethane (meth)acrylate, at least one monofunctional acrylate with dipentanyl group and / or methacrylate with dipentanyl group, at least one acrylic acid ester with additional carboxy group, acrylic acid ester with at least one additional anhydride group of carboxy groups and / or derivative of the aforementioned acrylic acid esters and optionally at least one inorganic filler.

[0105] To meet high aesthetic demands, dental materials used for the fabrication of definitive dentures, such as working models, orthodontic models, surgical guides, temporary restorations, and splints, must exhibit high transparency. This transparency is generally achieved by optimally matching the refractive indices of the fillers and the polymer matrix. However, due to various physical and chemical constraints, very strict limits are placed on the selection of both fillers and monomers.

[0106] A preferred filler content can be from 0 to 35 wt.% based on the total composition. Preferred fillers include silicon dioxide, zirconium dioxide, mixed oxides with silicon dioxide, and / or at least one mixed oxide of zirconium oxide and silicon dioxide, as well as mixtures comprising at least one of the inorganic oxides. The filler content can preferably be from 0.01 to 10 wt.% of a mixed oxide and optionally additionally 0 to 25 wt.% of silicon dioxide. A mixture with a content of 1 to 10 wt.% of the mixed oxide and 9 to 25 wt.% of silicon dioxide is preferred, particularly with a filler content of 10 to 35 wt.% based on the total composition.

[0107] Furthermore, it is preferred if the composition is not thixotropic. Furthermore, it is particularly preferred if the composition has a viscosity of less than 7500 mPas, in particular from 500 to 7000 mPas, preferably from 500 to less than 4000 mPas, preferably from 500 to 3000 mPas, particularly preferably from 500 to 1500 mPas. The viscosity is preferably measured according to DIN 1342-2; 2003-11 Newtonian fluids or DIN 1342-3; 2003-11 non-Newtonian fluids using a rheometer (Anton Par, Physiker MCR 301, at a shear rate d(gamma) / dt = 100 / s at 23°C). The compositions according to the invention have no or preferably only a slight thixotropy. According to a further embodiment, it is preferred that these exhibit virtually no viscosity changes over a prolonged storage period. Furthermore, the compositions exhibit very good reactivity upon exposure to a laser or DLP projector.With the composition according to the invention, workpieces or three-dimensional molded bodies can be printed with very good geometric precision / resolution. Furthermore, good color stability of the workpieces is observed.

[0108] The invention relates to a polymerized composition, preferably as a three-dimensional molded body, in particular as a dental prosthetic part, orthopedic appliance, or dental preform, obtainable by irradiation of a polymerizable composition. Additional all-round radiation curing is understood, for example, to mean post-curing in a 3D light oven.

[0109] Preferably, the polymerized compositions have a ratio of elastic modulus / flexural strength of greater than or equal to 25, preferably greater than or equal to 26, and in particular in combination with water absorption of less than or equal to 45 [ .g / mm 3 ] according to ISO 10477.

[0110] The invention also relates to a blank in the form of a three-dimensional shaped body of a polymerized composition, which has preferably been additionally radiation-cured on all sides, which is suitable for the production of dental prosthetic parts, orthopedic appliances, dental pre-forms, technical parts, tools, instruments, hoof repair parts or implants in medical prosthetics, wherein the blank has a) a flexural strength of greater than or equal to 75 MPa, and / or b) an E-modulus of greater than or equal to 2600 MPa and / or c) a water absorption of less than 45 [ .g / mm 3 ] The blank may preferably be in the form of an artificial tooth or a bridge, or as part of a bridge which, for final individual adaptation to the patient, only requires polishing or minor reworking of the occlusal surface.

[0111] Furthermore, the invention relates to an article in the form of a three-dimensional shaped body of a polymerized composition in the form of dental prosthetic parts, orthopedic appliances, dental preforms, technical parts, tools, instruments, hoof repair parts or implants in medical prosthetics, characterized in that the blank a) has a flexural strength of greater than or equal to 75 MPa according to DIN EN ISO 10477: 2020 and / or b) a modulus of elasticity of greater than or equal to 2600 MPa according to DIN EN ISO 10477: 2020 and / or c) a water absorption of less than 45 [|ig / mm 3] The invention further relates to the use of a composition for producing dental prosthetic parts, orthopedic appliances, dental preforms or technical parts, tools, instruments, hoof repair parts or implants in medical prosthetics, in rapid prototyping or rapid manufacturing, i.e. the production of dental prosthetic parts or rapid tooling processes. Suitable technical parts include all parts subject to mechanical stress, such as, in particular, parts in the automotive sector, parts of machines, parts of engines, parts of fittings, parts of furniture, parts of consumer articles or parts of kitchen utensils.

[0112] The following processes – rapid prototyping or rapid manufacturing, a process for producing workpieces such as a dental prosthetic part, or rapid tooling, a process for producing tools – each include stereolithography and DLP processes. Optionally, after curing of the polymerizable composition in the aforementioned processes, a post-treatment with UV, Vis, or UV / Vis light can be performed. Preferably, post-treatment of the polymerized composition or the dental prosthetic parts, orthopedic appliances, or dental preforms or blanks is performed simultaneously from at least three sides, preferably from five to six sides, as is possible in a light oven.

[0113] The dental prosthetic parts include a denture base or parts thereof, e.g. as a replica of a gingiva or part thereof, artificial teeth, dental arches with at least two to 16 interdentally material-connected artificial teeth, crowns, temporary crowns, full dentures, full crowns, splints for orthodontic corrections (similar to Invisaligri), dental bridges, abutments, superstructures, dental bars, inlays, veneers, onlays, orthopedic appliances such as occlusal splints, dental pre-forms of artificial teeth, drilling templates for implantology, mouthguards, and / or implants.

[0114] The invention also relates to its use as bone cement for cementing artificial joint prostheses, crowns, telescopes, veneers, dental bridges, denture teeth, implants, implant components, abutments, superstructures, and orthodontic appliances. In addition to dental prosthetic components, medical implants or use in the veterinary field, particularly as a hoof repair material, are also preferred. Color pigments can be added to the composition to adjust the color. Furthermore, red fibers can be added to the composition to imitate gingival veins. In the polymerized composition, layer thicknesses in the range of 5 μm to 250 μm per cured layer can be achieved.

[0115] In an alternative, the mono-functional monomer can contain at least one of the monomers mentioned: methyl methacrylate and optionally additionally ethyl methacrylate, propyl methacrylate, butyl methacrylate, n-hexyl methacrylate, 2-phenoxyethyl methacrylate, isobornyl methacrylate, isodecyl methacrylate, polypropylene glycol monomethacrylate, tetrahydrofuryl methacrylate, polypropylene glycol monomethacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, n-hexyl acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate, isodecyl acrylate, polypropylene glycol monoacrylate, tetrahydrofuryl acrylate, polypropylene glycol monoacrylate, benzyl, furfuryl or phenyl (meth)acrylate a mixture containing at least one of these (meth)acrylates and / or copolymers comprising one or at least two of the aforementioned monomers.

[0116] Furthermore, the composition may comprise monomers selected from tri-, tetra- or multi-functional monomers other than urethane (meth)acrylate, such as pentaerythritol tetraacrylate, trimethylolpropane tri(meth)acrylate and / or pentaerythritol tetra(meth)acrylate.

[0117] Suitable photoinitiators include, for example, benzoin alkyl ethers or esters, benzil monoketals, acylphosphine oxides, or aliphatic and aromatic 1,2-diketo compounds, such as 2,2-diethoxyacetophenone, 9,10-phenanthrenequinone, diacetyl, furil, anisile, 4,4'-dichlorobenzil, and 4,4'-dialkoxybenzil, or camphorquinone. The photoinitiators are preferably used together with a reducing agent. Examples of reducing agents are amines such as aliphatic or aromatic tertiary amines, for example 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 ethyl 4-dimethylaminobenzoate, or organic phosphites. Common photoinitiator systems include camphorquinone plus ethyl 4-(N,N-dimethylamino)benzoate, 2-(ethylhexyl)-4-(N,N-dimethylamino)benzoate, or N,N-dimethylaminoethyl methacrylate.

[0118] Particularly suitable as initiator for UV-initiated polymerization is 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (bis-trimethylbenzoyl)-phenylphosphine oxide,

[0119] Ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L), benzil dimethyl ketal, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 4-benzoyl-4'methyldiphenyl sulfide, benzophenone, 1-hydroxycyclohexylphenyl ketone, camphorquinone, 2,2 Diethoxyacetophenone, 2,4 diethylthioxanthone, dimethylhydroxyacetophenone, 4,4-bis(diethylamino)benzophenone, 1-(9,9-dibutyl-9H-fluoren-2-yl)-2-methyl-2-morpholin-4-yl-propan-1-one, isopropylthioxanthone, 1-hydroxycyclohexylphenyl ketone and benzophenone, 4-methylbenzophenone and benzophenone, 2,4,6 Trimethylbenzoyldiphenylphosphine oxide, dimethylhydroxyacetophenone, methyl o-benzoyl benzoate, methyl benzoyl formate, 4-phenylbenzophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinepropan-1-one, and / or ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, as well as mixtures comprising at least two of the photoinitiators. UV photoinitiators can be used alone or in combination with a visible-light initiator.

[0120] Suitable optional photoinitiators and / or initiator systems can comprise 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 an alpha-hydroxyketone, camphorquinone, or acylphosphine oxide. Stabilizers can optionally also be added, and optionally b) at least one co-initiator, such as an amine, usually a tert-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.

[0121] Typical stabilizers include 2,6-di-tert-butyl-4-methylphenol (BHT), 2-hydroxy-4-methoxybenzophene and / or hydroquinone monomethyl ether (MEHQ).

[0122] The invention is explained in more detail by the following examples, without limiting the invention to these embodiments.

[0123] The post-hardening / post-tempering was carried out using a Hi Lite Power 3D laboratory light unit

[0124] Method description:

[0125] The specimens were printed with the Cara Print 4.0 (wavelengths: 385 nm and 405 nm) at a layer thickness of 50 pm using a suitable print dataset according to the manufacturer's instructions and then post-cured for 2 x 5 minutes with HiLite Power 3D. Methods:

[0126] The measurements in Table 3 were carried out according to DIN EN ISO 10477:2020 (23 ± 2 °C, at least 30% relative humidity unless otherwise stated). Reference is made to DIN EN ISO 10477:2020 in full, i.e. the disclosure content is disclosed. The test specimens were manufactured from the printed test specimens or flat bars, which were post-cured.

[0127] The flexural strength is determined according to DIN EN ISO 10477: 2020, chapters 5.4 and 7.5, see Fig. 2 ISO 10477. Flexural strength test specimen with a height hf = 2 ± 0.1 mm and width bf = 2.0 ± 0.1 mm, length l f = 25 ± 2 mm are printed and exposed as described above. The specimens are tested after 24 hours of water immersion at 37 °C. The test is carried out using a Zwick universal testing machine with a preload of 0.4 N and a test speed of 0.75 mm / min. From the measured flexural strength (grade 7.5, ISO 10477), the corresponding Young's modulus (calculated as a secant) is determined from the curve slope (between 1 N and 7 N).

[0128] The three-media abrasion measurements are carried out according to the ACTA method (ISO / TS 14569-2, 2001, Dental materials - Guidance on testing of wear, Part 2, Chapter 5). The test specimens measuring 10 x 12 mm are printed, post-exposed (as described above), and appropriately fixed in the test wheel. After grinding (= creation of a uniform surface using diamond grinding wheels), abrasion takes place in the same device (DMA three-media abrasion machine, SD Mechatronik) in a mixture of water and poppy seeds (110 g dried blue poppy seeds : 205 g water) over 300,000 cycles. The antagonist and test wheel rotate in opposite directions (contact pressure 20 N, antagonist wheel at 240 rpm, test wheel at 180 rpm). After 150,000 cycles, the poppy-water mixture is renewed.

[0129] Since the sample wheel is wider than the antagonist wheel, a non-abraded area remains on each test specimen; this area serves as the reference height for evaluation. The evaluation (average depth in pm and volume loss in mm 3) is carried out using a non-contact surface laser scanner (OPM GmbH, resolution 100 p / mm, z-axis resolution 0.1 pm) on an area of ​​2 x 8 mm (of which approx. 1 mm of non-abraded area on both sides serves as a reference height). Water absorption and solubility are determined according to DIN EN ISO 10477: 2020, chapters 5.6, 5.7 and 7.7. Round test specimens with a diameter of 15 + / - 1 mm and a thickness of 1 + / - 0.1 mm are printed, post-exposed (printing method as described above), polished to a high gloss according to an application situation, and the diameter and thickness are individually measured to determine the volume (V). 5 test specimens are conditioned in a desiccator over silica gel at 37 °C until constant weight (m1). This is followed by storage in water at 37 °C for 7 days. The weight after water storage is determined 1 minute after removal and blotting with cellulose (m2). Re-drying is carried out in a desiccator at 37 °C until constant weight (m3).

[0130] Water absorption is calculated as (m2 - m3) / V. Solubility is calculated as (m1 - m3) / V. The maximum limit for water absorption according to the standard is < 40 g / m 3 and the limit for water solubility is < 7.5 g / m 3 .

[0131] Examples of implementation:

[0132] The prepared mixture is used to print test specimens for subsequent testing on a 3D precision printer with a wavelength of 405 nm (Cara Print 4.0). After the printing process, the test specimens are rinsed with isopropanol and subjected to a post-treatment process. This is done by exposing both sides to light for 5 minutes each or, according to the manufacturer's instructions, in a 200 W Hi Lite Power 3D laboratory light lamp (Külzer GmbH).

[0133] The properties of the mixture according to the invention as printed materials, in particular printed dental materials, are tested according to ISO 10477 (in water 37 °C) and according to the poppy abrasion described above.

[0134] It is assumed that competitor Nextdent avoids the brittleness in its C&B MFH product by using a high proportion of HEMA (according to the MSDS: 15-25%). The resulting printed blanks exhibit excessive water absorption, and pronounced sedimentation was observed. The composition of Nextdent is listed in the MSDS as follows: urethane dimethacrylate 50 to 75 wt.%, 2-hydroxymethacrylate <25 wt.%, ethylene glycol dimethacrylate <10 wt.%, ethoxylated bisphenol A dimethacrylate <10 wt.%, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide 1 to 5 wt.%. Table 1: Examples

[0135] Table 2: Examples

[0136] Table 3: Chemical-physical and mechanical properties

[0137] (for averaged results, the standard deviation is in parentheses)

[0138] The monofunctional dicyclopentanyl methylacrylate serves as a thinner and is believed to counteract the shrinkage of the radiation-cured composition. Compositions containing dicyclopentanyl methacrylate also exhibit very low water absorption, good elastic moduli, and high flexural strength values. The acrylic acid ester with an additional carboxyl group is used as a monofunctional monomer and as a plasticizer and exhibits a higher viscosity (typically > 4000 m-Pas) compared to HEMA. The use of the acrylic acid ester counteracts sedimentation and has a positive effect on the shrinkage of the composition, which is less pronounced than the effect of HEMA.The composition of Example 2, with the combination of IIDMA and acrylic acid ester with an additional carboxyl group, exhibits the highest flexural strength without water storage and a high Young's modulus. Example 3, comprising the combination of IIDMA, dicyclopentanyl methyl acrylate, and acrylic acid ester with an additional carboxyl group, exhibits the highest Young's modulus without water storage and the lowest water solubility. Both Examples 1 and 3 exhibit the lowest water absorption and the lowest water solubility.

Claims

Polymerizable, radiation-curable composition comprising (i) Monomers and (ii) at least one further component, characterized in that (i) the monomers comprise (a) at least one difunctional urethane(meth)acrylate, (b) at least one monofunctional acrylate with an alicyclic group and / or at least one monofunctional methacrylate with an alicyclic group, and (ii) comprising at least one further component (c) at least one photoinitiator for the UV and / or Vis range or a photoinitiator system for the UV and / or Vis range. Composition according to claim 1, characterized in that it comprises (d) at least one acrylic acid ester with an additional carboxyl group. Composition according to claim 1 or 2, characterized in that it comprises (e) at least one disubstituted 4,4'-di(oxabenzene)dialkylmethane of Formula 1 with R 1 , R 2 , R 5 and R 6 each independently selected from H or C1 to C4 alkyl, and with R 3 and R 4 each bivalent C1 to C4 alkylene, with n = 0 to 6 and m = 0 to 6.

4. Composition according to any one of claims 1 to 3, wherein the composition is suitable for use in an additive manufacturing process with layer-by-layer beam-induced polymerization of the composition for the production of three-dimensional molded bodies.

5. Composition according to any one of claims 1 to 4, characterized in that the (d) at least one acrylic acid ester with an additional carboxy group is selected from an acrylic acid ester with an additional carboxy group of formula II or III with R 7each independently selected from bivalent C, H, O and optionally N containing groups with 1 to 25 C atoms, in particular bivalent aromatic esters, aromatic urethanes, alkyl esters, alkylurethanes, aromatic ethers, alkyl ethers, and R 8 selected from H and 1 to 4 C-alkyl, preferably R 7 a bivalent aromatic ester, with R 9 independently selected from bivalent benzoyl, salicyloyl and derivatives thereof or -C-, R 10 is bivalent -(OR) 11 ) r - with R 11 equal to ethylene or propylene and with r equal to 0 to 10, in particular 1 to 6, preferably r = 1 or R 10 is independently selected from bivalent alkylene and / or R 8 is selected from H and 1 to 4 C-alkyl, preferably R 8 is H, Methyl or Ethyl.

6. Composition according to any one of claims 1 to 5, characterized in that (b) the at least one monofunctional acrylate with an alicyclic group and / or at least one monofunctional methacrylate with an alicyclic group comprises at least one monofunctional acrylate with a dicyclopentanyl group and / or at least one monofunctional methacrylate with a dicyclopentanyl group or mixtures containing these.

7. Composition according to any one of claims 1 to 6, characterized in that (b) the at least one monofunctional acrylate with an alicyclic group and / or at least one monofunctional methacrylate with an alicyclic group comprises at least one monofunctional acrylate with a monovalent alicyclic group and / or at least one monofunctional methacrylate with a monovalent alicyclic group.

8. Composition according to any one of claims 2 to 7, characterized in that (d) the at least one acrylic acid ester with an additional carboxy group comprises phthalic acid mono-[2-(methacryloyloxy)ethyl ester], 2-acryloyloxyethyl hydrogen phthalate, polyether-functionalized acrylic acid esters with a carboxy group and mixtures thereof.

9. Composition according to one of claims 1 to 7, characterized in that (a) that at least one difunctional urethane(meth)acrylate is selected from difunctional urethane(meth)acrylates having a bivalent alkylene group.

10. Composition according to one of claims 7 to 9, characterized in that (b) comprising at least one mono-functional acrylate with a mono-valent alicyclic group and / or at least one mono-functional methacrylate with a mono-valent alicyclic group, tricyclodecanalkanol methacrylate, tricyclodecanalkanol acrylate with alkanol having 1 to 10 carbon atoms or mixtures containing at least one of these monomers.

11. Composition according to any one of claims 1 to 10, characterized in that (e) at least one disubstituted 4,4'-di(oxabenzene)dialkylmethane of formula I includes R 1 and R 2 each methyl and R 5 and R 6 equal and selected from H, Methyl and Ethyl, in particular with R 5 and R 6 equal and selected from H and Methyl, and with R 3 and R 4each independently bivalent ethylene or propylene with n = 1 to 6, preferably n = 2 to 4, and with m = 1 to 6, preferably m = 2 to 4, preferably with n = 2 and m = 2 or with n = 4 and m = 4 as well as mixtures thereof.

12. Composition according to any one of claims 1 to 11, characterized in that the composition further comprises inorganic fillers selected from, (f) inorganic fillers comprising inorganic oxides or inorganic mixed oxides and / or dental glasses, in particular silicon dioxide, zirconium dioxide, mixed oxides of a metal oxide with silicon dioxide and / or a mixed oxide of silicon dioxide and zirconium dioxide, as well as mixtures comprising any of the aforementioned inorganic oxides; preferred fillers comprising silicon dioxide and / or mixed oxides of metal dioxide with silicon dioxide.

13. Composition according to any one of claims 1 to 12, characterized in that the composition comprises (a) 1 to 90 wt% of at least one difunctional urethane(meth)acrylate, (b) 1 to 50 wt.% of at least one monofunctional acrylate with an alicyclic group and / or at least one monofunctional methacrylate with an alicyclic group, (c) 0.01 to 10 wt.% of at least one photoinitiator for the UV and / or Vis range or a photoinitiator system for the UV and / or Vis range, (d) 1 to 50 wt.% at least one acrylic acid ester with an additional carboxy group (e) 1 to 25 wt% at least one disubstituted 4,4'-di(oxabenzene)dialkylmethane of formula I with R 1 , R 2 , R 5 and R 6 each independently selected from H or C1 to C4 alkyl, and with R 3 and R 4 each bivalent C1 to C4 alkylene, with n = 0 to 6 and m = 0 to 6. (f) 0 to 35 wt.% inorganic fillers comprising inorganic oxides or inorganic mixed oxides and / or dental glasses, in particular silicon dioxide, zirconium dioxide, mixed oxides of a metal oxide and silicon dioxide, preferred fillers comprising silicon dioxide and / or mixed oxides of a metal dioxide and silicon dioxide, wherein the total composition is 100 wt.%. Composition according to any one of claims 1 to 13, characterized in that the composition has a viscosity of less than 7500 mPas, in particular of 500 to less than 4000 mPas, preferably of 500 to 3000 mPas.Three-dimensional molded body of a polymerized composition according to one of claims 1 to 14 in the form of dental prosthetic parts, orthopedic appliances, dental pre-forms, technical parts, tools, instruments, hoof repair parts or implant in medical prosthetics, characterized in that the molded body a) has a flexural strength of greater than or equal to 75 MPa according to DIN EN ISO 10477. : 2020 and / or b) has a modulus of elasticity greater than or equal to 2600 MPa according to DIN EN ISO 10477 : 2020 and / or c) has a water absorption of less than 45 [ .g / mm ] 3 ].

16. Blank in the form of a three-dimensional molded body of a polymerized composition according to any one of claims 1 to 14 for the manufacture of dental prosthetic parts, orthopedic appliances, dental pre-forms, technical parts, tools, instruments, hoof repair parts or implants in medical prosthetics, characterized in that the blank a) has a flexural strength of greater than or equal to 75 MPa according to DIN EN 10477:2020 and / or b) has a modulus of elasticity of greater than or equal to 2600 MPa according to DIN EN ISO 10477:2020 and / or c) has a water absorption of less than 45 g / mm². 3 ] exhibits.

17. Use of a composition according to any one of claims 1 to 11 for the manufacture of dental prosthetic parts, orthopedic appliances, dental pre-forms, technical parts, tools, instruments, hoof repair parts, implants in medical prosthetics, in particular a composition according to any one of claims 1 to 14, in a rapid prototyping or in a rapid manufacturing or rapid tooling process, or as bone cement for cementing artificial joint prostheses, crowns, telescopes, veneers, dental bridges, denture teeth, implants, implant parts, abutments, superstructures, orthodontic appliances.

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