Photocurable compositions for use in rapid prototyping or rapid manufacturing processes - Patents.com

Abstract

The present invention relates to a polymerizable, photocurable, in particular UV / visible, UV or visible light curable composition comprising (i) a monomer and (ii) at least one further component, wherein the (i) monomer comprises (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 the (ii) at least one further component comprises (c) at least one photoinitiator for the UV and / or visible light range or a photoinitiator system for the UV and / or visible light range. The compositions according to the invention are suitable for producing dental prosthetic parts, orthodontic appliances or dental preforms, which have a) a flexural strength of 75 MPa or more, and / or b) a modulus of elasticity of 2600 MPa or more, and / or c) a modulus of elasticity of 45 [μg / mm 3 ], characterized in that they can be produced in rapid prototyping or in rapid manufacturing or rapid tooling processes.

Description

[Technical field]

[0001] The present invention relates to a polymerizable, photocurable, in particular UV / visible, UV or visible light curable composition comprising (i) a monomer and (ii) at least one further component, in which the (i) monomer comprises (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 the (ii) at least one further component comprises (c) at least one photoinitiator for the UV and / or visible light range or a photoinitiator system for the UV and / or visible light range. The composition according to the invention is suitable for producing semi-finished products and three-dimensional mouldings of dental prosthetic parts, orthodontic appliances, dental preforms, industrial parts, tools, instruments, hoof restoration parts or implants in medical prosthetics, which have a flexural strength of at least 75 MPa, and / or b) a modulus of elasticity of at least 2600 MPa, and / or c) a modulus of elasticity of at least 45 [μg / mm 3 ], where they can be produced in rapid prototyping or in rapid manufacturing or rapid tooling processes. [Background technology]

[0002] In addition to manual manufacturing methods, digital manufacturing methods are becoming more and more important in the dental field. Dentures, such as crowns and bridges, have been manufactured subtractively for several years now through CAD-CAM technology. Since in this milling technology, only a smaller portion of the raw material is utilized, and most of it is wasted, and the tool can only process one dental part at a time, the bottom-up method should be able to achieve significant cost advantages by simultaneously manufacturing multiple dental parts and with little or no waste.

[0003] Generative methods are already known in the dental field, for example in the form of laser sintering from CoCr, Ti or polymers for producing crowns and bridges, implant parts or models.

[0004] Compositions of acrylates or acrylate derivatives for the production of dentures with a corresponding property profile with respect 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 provide approval according to MPG class IIa for printable plastics and resins, and since currently most resins can only be printed unfilled, the mechanical properties of currently available materials are always low. These materials are therefore not suitable for the production of permanent dentures. Filling compositions available on the market have the disadvantage of significant settling of the filler as well as too high a water absorption rate according to ISO 10477:2020. In the case of too much settling, a homogeneous printing result is not ensured during long printing times. Furthermore, the user must first quantitatively homogenize the composition before use. Therefore, a composition for producing a final prosthetic part, an orthodontic device or a dental preform is needed. Summary of the Invention [Problem to be solved by the invention]

[0005] The object of the present invention is to provide a mixture of monomers, which may optionally contain fillers, which, especially after curing using a light curing method, has good properties in terms of elastic modulus, and in particular should achieve a balance between the necessary strength while avoiding brittleness and a low viscosity as a printing requirement while simultaneously avoiding significant settling of the filler. Furthermore, the composition should be usable for use in light curable rapid manufacturing (RM) or rapid prototyping (RP) methods. A further object was to provide a composition which contains inorganic fillers and has high transparency, especially as a polymerizable composition or as a polymerized composition. Furthermore, it was an object to indicate a composition which has low water absorption, especially according to ISO 10477:2020, and is therefore suitable for printing dental materials, for example permanent dentures. [Means for solving the problem]

[0006] In the present application, dental products are understood in particular to be dental products which can be produced from the polymerizable composition, such as, but not limited to, full prostheses, temporary crowns and bridges, inlays, onlays, full crowns, bite splints, drilling templates for implant technology, orthodontic splints (similar to Invisalign), mouth guards, artificial teeth and brackets.

[0007] The subject of the present invention is a polymerizable, radiation-curable composition comprising (i) a monomer and (ii) at least one further component, said monomer being (a) at least one at least difunctional urethane (meth)acrylate; (b) at least one monofunctional acrylate having an alicyclic group and / or at least one monofunctional methacrylate having an alicyclic group, or a mixture thereof, in particular dicyclopentanyl methyl acrylate, and optionally (d) at least one acrylic ester having an additional carboxy group; and (ii) at least one further component comprises (c) at least one photoinitiator for the ultraviolet and / or visible light range or a photoinitiator system for the ultraviolet and / or visible light range The composition comprises:

[0008] Here, it is particularly preferred if (b) 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 dicyclopentane group and / or at least one monofunctional methacrylate with a dicyclopentane group, or a mixture containing them. Preferably, the monofunctional acrylate 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, said acrylate having 14 to 25 C atoms, in particular 14 to 18 C atoms. Dicyclopentanyl methyl acrylate is particularly preferred.

[0009] In a particularly preferred embodiment, the composition comprises (d) at least one acrylic acid ester having an additional carboxy group.

[0010] An optional subject of the present invention is a polymerizable, photocurable composition comprising (i) a monomer and (ii) at least one further component, said monomer being (a) at least one at least difunctional urethane (meth)acrylate, and (d) at least one acrylic ester having an additional carboxy group; and (ii) at least one further component comprises (c) at least one photoinitiator for the ultraviolet and / or visible light range or a photoinitiator system for the ultraviolet and / or visible light range The composition comprises:

[0011] The compositions according to the invention are suitable for use in generative printing processes with layer-by-layer light-induced polymerization of the composition for producing three-dimensional bodies, in particular the compositions have a viscosity of less than 7500 mPa·s, preferably less than 5000 mPa·s, in particular from 500 to less than 4000 mPa·s, preferably from 500 to 3000 mPa·s, particularly preferably from 1 to 1500 mPa·s.More preferably, the compositions have a viscosity of 100 to 1200 mPa·s.

[0012] The polymerization is advantageously carried out by induced UV and / or visible light polymerization of said composition layer by layer to produce three-dimensional bodies.

[0013] The subject of the present invention is, in one alternative, (e) Formula I [ka] [In the formula, R 1 , R 2 , R 5 and R 6 are each independently H or C 1 ~C 4 -alkyl, and R 3 and R 4 are divalent C 1 ~C 4 -alkylene, where n=0-6 and m=0-6, in particular where n=1 and m=1, and / or n+m=2. and wherein the disubstituted 4,4'-di(oxabenzene)dialkylmethane is selected from the group consisting of 4,4'-di(oxabenzene)dialkylmethane and 4,4'-di(oxabenzene)dialkylmethane.

[0014] According to a particularly preferred option, (d) the at least one acrylic ester having an additional carboxy group has the formula II or III [ka] [In the formula, R 7are each independently selected from divalent radicals containing C, H, O and optionally N and 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 1-4C-alkyl, preferably R 7 is a divalent aromatic ester], [ka] [In the formula, R 9 is independently selected from divalent benzoyl, salicyloyl and derivatives thereof, or -C-; R 10 is a divalent -(OR 11 ) r - and R 11 is ethylene or propylene and r is 0 to 10, in particular 1 to 6, preferably r=1, or R 10 are independently selected from divalent alkylenes, and R 8 is selected from H and 1-4C-alkyl, preferably R 8 is H, methyl or ethyl] Preferably, the (d) at least one acrylic ester having an additional carboxy group comprises phthalic acid mono-[2-(methacryloyloxy)-ethyl ester] or hydrogen 2-acryloyloxyethyl phthalate, polyether-functionalized acrylic esters having a carboxy group, and mixtures thereof.

[0015] In one alternative, (b) the at least one monofunctional acrylate having an alicyclic group and / or the at least one monofunctional methacrylate having an alicyclic group is at least one monofunctional acrylate having a monovalent alicyclic group and / or at least one monofunctional methacrylate having a monovalent alicyclic group, in particular dicyclopentanyl alkylene acrylate and / or dicyclopentanyl alkylene methacrylate, wherein each alkylene is independently selected from the group consisting of C 1 ~C 6- contains an atom, or a mixture containing at least one of the monomers.

[0016] Particularly preferred difunctional urethane (meth)acrylates having a divalent alicyclic group are 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, as well as any mixture of 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers, and / or cis and trans isomers of the above compounds, or are selected from these. Difunctional urethane acrylates having a divalent alicyclic group 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, as well as any mixture of 3,8- / 3,9- / 4,8- / 3,10- / 4,10-isomers, and / or cis and trans isomers of the above compounds are particularly preferred.

[0017]

Chemical formula

[0018] In a preferred embodiment, (a) at least one difunctional urethane (meth)acrylate is selected from difunctional urethane (meth)acrylates having a divalent alkylene group.

[0019] Difunctional urethane (meth)acrylates having divalent alkylene groups are preferably linear or branched, divalent alkylene functionalized urethane dimethacrylates, alkylene functionalized polyethers, such as bis(methacryloxy-2-ethoxycarbonylamino)alkylenes, bis(methacryloxy-2-ethoxycarbonylamino)-substituted polyalkylene ethers, preferably 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane, UDMA (also known as HEMA-TDMI). Bis(methacryloxy-2-ethoxycarbonylamino)alkylenes are preferred, where alkylene is C 3 ~C 20 , advantageously C 3 ~C 6 and methyl-substituted alkylenes, such as HEMA-TMDI, are particularly preferred. The divalent alkylenes advantageously include 2,2,4-trimethylhexamethylene and / or 2,4,4-trimethylhexamethylene.

[0020] Furthermore, the composition may comprise at least one further monomer (g), in particular at least one di-, tri-, tetra- or polyfunctional monomer which is not a urethane (meth)acrylate and in particular does not correspond to formula I. Likewise, the composition may comprise a further monofunctional monomer (h).

[0021] In one alternative, (b) the at least one monofunctional acrylate having a monovalent alicyclic group and / or the at least one monofunctional methacrylate having a monovalent alicyclic group comprises a tricyclodecane alkanol methacrylate and / or a tricyclodecane alkanol acrylate, said alkanol having 1 to 10 C atoms, or a mixture containing at least one of these monomers, with tricyclodecane methanol acrylate, tricyclodecane methanol methacrylate, dicyclopentanyl acrylate, tricyclodecane ethanol acrylate, tricyclodecane ethanol methacrylate, isomers of the above monomers and / or mixtures thereof being preferred.

[0022] Similarly, the composition according to the invention preferably comprises as (e) a compound of formula I [ka] [In the formula, R 1 and R 2 are each methyl, and R 5 and R 6 are identical and selected from H, methyl and ethyl, in particular R 5 and R 6 are the same and selected from H and methyl, and R 3 and R 4 are each independently a divalent ethylene or propylene, n=1 to 6, preferably n=2 to 4, and m=1 to 6, preferably m=2 to 4, preferably n=2 and m=2, or n=4 and m=4; and mixtures thereof.

[0023] According to a further preferred option, the composition comprises as a further component an inorganic filler, said inorganic filler being (f) inorganic fillers selected from inorganic oxides or inorganic mixed oxides and / or dental glasses, in particular zirconium dioxide, mixed oxides of metal oxides and silicon dioxide, silicon dioxide-containing inorganic fillers, preferred fillers include silicon dioxide and / or mixed oxides with silicon dioxide. Particularly preferably, the inorganic fillers are silanized, in particular with acryl-functional silanes, particularly preferably with (3-acryloyloxyalkyl)trimethoxysilanes, where the alkyl is C 1 ~C 6 and preferably with (3-acryloyloxypropyl)trimethoxysilane.

[0024] Particularly preferred compositions are (a) 1 to 90% by weight of at least one at least difunctional urethane (meth)acrylate; (b) 1 to 50% by mass of at least one monofunctional acrylate having an alicyclic group and / or at least one monofunctional methacrylate having an alicyclic group, and (c) 0.01 to 10% by weight of at least one photoinitiator for the ultraviolet and / or visible light range or a photoinitiator system for the ultraviolet and / or visible light range; (d) 1 to 50% by weight of at least one acrylic acid ester having an additional carboxy group; (e) 1 to 25 mass % of a compound of formula I [wherein R 1 , R 2 , R 5 and R 6 are each independently H or C 1 ~C 4 -alkyl, and R 3 and R 4 are divalent C 1 ~C 4 -alkylene, n=0-6 and m=0-6, in particular n=1 and m=1 and / or n+m=2; (f) 0 to 35% by weight of inorganic oxides or inorganic mixed oxides and / or dental glass, in particular inorganic fillers containing silicon dioxide, zirconium dioxide, mixed oxides with silicon dioxide, preferably silicon dioxide and / or mixed oxides of metal oxides and silicon dioxide, (g) 0 to 10% by weight, in particular 1 to 10% by weight, of alkylene dimethacrylates and / or alkylene diacrylates, preferably alkylene dimethacrylates, wherein the alkylenes are preferably each independently selected from C 1 ~C 12 -Alkylene, preferably C 1 ~C 4 -alkylene], particularly preferably ethylene glycol dimethacrylate, and (h) optionally 0.1 to 5% by weight, in particular 0.1 to 2% by weight, of hydroxyethyl acrylate where the overall composition is 100% by weight.

[0025] More preferably, (a) 30 to 70% by weight of at least one at least difunctional urethane (meth)acrylate; (b) 10 to 40 mass % of at least one monofunctional acrylate having an alicyclic group and / or at least one monofunctional methacrylate having an alicyclic group; (c) 0.01 to 10% by weight of at least one photoinitiator for the ultraviolet and / or visible light range or a photoinitiator system for the ultraviolet and / or visible light range; (d) from 5 to 40% by weight, in particular from 5 to 25% by weight, of at least one acrylic ester having additional carboxy groups, (e) 1 to 15% by weight, in particular 2 to 5% by weight, of formula I, 1 , R 2 , R 5 and R 6 are each independently H or C 1 ~C 4 -alkyl, and R 3 and R 4 are divalent C 1 ~C 4-alkylene, n=0-6 and m=0-6, in particular n=1 and m=1 and / or n+m=2; (f) 0 to 35% by weight of inorganic oxides or inorganic mixed oxides and / or dental glass, in particular inorganic fillers comprising silicon dioxide, zirconium dioxide, mixed oxides of silicon dioxide and further metal oxides, preferably fillers comprising silicon dioxide and / or mixed oxides of silicon dioxide and further metal oxides, (g) 0 to 10% by weight, in particular 1 to 10% by weight, of alkylene dimethacrylates and / or alkylene diacrylates, preferably alkylene dimethacrylates, wherein the alkylenes are preferably each independently selected from C 1 ~C 12 -Alkylene, preferably C 1 ~C 4 -alkylene], particularly preferably ethylene glycol dimethacrylate, (h) optionally 0.1 to 5% by weight, in particular 0.1 to 2% by weight, of hydroxyethyl acrylate wherein the total composition is 100% by weight.

[0026] More preferably, (a) 40 to 60% by weight of at least one at least difunctional urethane (meth)acrylate; (b) 15 to 30 mass % of at least one monofunctional acrylate having an alicyclic group and / or at least one monofunctional methacrylate having an alicyclic group; (c) 0.01 to 10% by weight of at least one photoinitiator for the ultraviolet and / or visible light range or a photoinitiator system for the ultraviolet and / or visible light range; (d) at least one acrylic ester having from 5 to 30% by weight, in particular from 5 to 25% by weight, of additional carboxy groups (e) 1 to 15% by weight, in particular 2 to 5% by weight, of formula I, 1 , R 2 , R 5 and R 6are each independently H or C 1 ~C 4 -alkyl, and R 3 and R 4 are divalent C 1 ~C 4 -alkylene, n=0-6 and m=0-6, in particular n=1 and m=1 and / or n+m=2; (f) 0 to 35% by weight of inorganic oxides or inorganic mixed oxides and / or dental glass, in particular inorganic fillers containing silicon dioxide, zirconium dioxide, mixed oxides with silicon dioxide, preferably fillers containing silicon dioxide and / or mixed oxides of silicon dioxide and further metal oxides; (g) 0 to 10% by weight, in particular 1 to 10% by weight, of alkylene dimethacrylates and / or alkylene diacrylates, preferably alkylene dimethacrylates, wherein the alkylenes are preferably each independently selected from C 1 ~C 12 -Alkylene, preferably C 1 ~C 4 -alkylene], particularly preferably ethylene glycol dimethacrylate, wherein the total composition is 100% by weight. Optionally, additionally (h) 0.1 to 5% by weight, especially 0.1 to 2% by weight, of hydroxyethyl acrylate may be included in the composition.

[0027] Particularly preferred compositions are (a) 1 to 90% by weight of at least one at least difunctional urethane (meth)acrylate; (b) 1 to 50% by weight, in particular 20 to 35% by weight, of at least one monofunctional acrylate having an alicyclic group and / or at least one monofunctional methacrylate having an alicyclic group, and (c) 0.01 to 10% by weight of at least one photoinitiator for the ultraviolet and / or visible light range or a photoinitiator system for the ultraviolet and / or visible light range; (d) optionally 1 to 10% by weight, in particular 1 to 9% by weight, preferably 1 to 7% by weight, of at least one acrylic acid ester having additional carboxy groups, (e) 1 to 25% by weight, in particular 2 to 5% by weight, of formula I, 1 , R 2 , R 5 and R 6 are each independently H or C 1 ~C 4 -alkyl, and R 3 and R 4 are divalent C 1 ~C 4 -alkylene, n=0-6 and m=0-6; (f) 0 to 35% by weight of inorganic oxides or inorganic mixed oxides and / or dental glass, in particular zirconium dioxide, mixed oxides with silicon dioxide, inorganic fillers containing silicon dioxide, preferably silicon dioxide and / or mixed oxides of silicon dioxide and metal oxides. wherein the overall composition is 100% by weight. (g) 0 to 10% by weight, in particular 1 to 10% by weight, of alkylene dimethacrylates and / or alkylene diacrylates, preferably alkylene dimethacrylates, wherein the alkylenes are preferably each independently selected from C 1 ~C 12 -Alkylene, preferably C 1 ~C 4 -alkylene], particularly preferably ethylene glycol dimethacrylate, and / or optionally (h) 0.1 to 5% by weight, in particular 0.1 to 2% by weight, of hydroxyethyl acrylate. may be included in the composition.

[0028] More preferably, (a) from 30 to 70% by weight, in particular from 40 to 60% by weight, of at least one at least difunctional urethane (meth)acrylate, (b) 10 to 40% by weight, in particular 15 to 35% by weight, of at least one monofunctional acrylate having an alicyclic group and / or at least one monofunctional methacrylate having an alicyclic group, (c) 0.01 to 10% by weight of at least one photoinitiator for the ultraviolet and / or visible light range or a photoinitiator system for the ultraviolet and / or visible light range; (d) optionally from 1 to 9% by weight, in particular from 1 to 7% by weight, of at least one acrylic acid ester having additional carboxy groups, (e) 1 to 15% by weight, in particular 2 to 5% by weight, of formula I, 1 , R 2 , R 5 and R 6 are each independently H or C 1 ~C 4 -alkyl, and R 3 and R 4 are divalent C 1 ~C 4 -alkylene, n=0-6 and m=0-6; (f) 0 to 35% by weight of inorganic oxides or inorganic mixed oxides and / or dental glass, in particular inorganic fillers comprising silicon dioxide, zirconium dioxide and / or mixed oxides of silicon dioxide and further metal oxides, and (g) 0 to 10% by weight, in particular 1 to 10% by weight, of alkylene dimethacrylates and / or alkylene diacrylates, preferably alkylene dimethacrylates, wherein the alkylenes are preferably each independently selected from C 1 ~C 12 -Alkylene, preferably C 1 ~C 4 -alkylene], particularly preferably ethylene glycol dimethacrylate, (h) optionally 0.1 to 5% by weight, in particular 0.1 to 2% by weight, of hydroxyethyl acrylate wherein the total composition is 100% by weight.

[0029] More preferably, (a) from 30 to 70% by weight, in particular from 40 to 60% by weight, of at least one at least difunctional urethane (meth)acrylate, (b) optionally from 10 to 40% by weight, in particular from 15 to 30% by weight, of at least one monofunctional acrylate having an alicyclic group and / or at least one monofunctional methacrylate having an alicyclic group, (c) 0.01 to 10% by weight of at least one photoinitiator for the ultraviolet and / or visible light range or a photoinitiator system for the ultraviolet and / or visible light range; (d) from 1 to 60% by weight, preferably from 5 to 60% by weight, particularly preferably from 10 to 50% by weight and in particular from 10 to 40% by weight of at least one acrylic ester having additional carboxy groups, (e) optionally from 5 to 30% by weight, in particular from 5 to 15% by weight, of formula I, 1 , R 2 , R 5 and R 6 are each independently H or C 1 ~C 4 -alkyl, and R 3 and R 4 are divalent C 1 ~C 4 -alkylene, n=0-6 and m=0-6; (f) 0 to 35% by weight, in particular 1 to 25% by weight, of inorganic oxides or inorganic mixed oxides and / or dental glass, in particular zirconium dioxide, mixed oxides with silicon dioxide, inorganic fillers containing silicon dioxide, preferably fillers containing silicon dioxide and / or mixed oxides of silicon dioxide and further metal oxides, (g) 0 to 10% by weight, in particular 1 to 7% by weight, of alkylene dimethacrylates and / or alkylene diacrylates, preferably alkylene dimethacrylates, wherein the alkylenes are preferably each independently selected from C 1 ~C 12 -Alkylene, preferably C 1 ~C 4-alkylene], particularly preferably ethylene glycol dimethacrylate, (h) optionally 0.1 to 5% by weight, in particular 0.1 to 2% by weight, of hydroxyethyl acrylate wherein the total composition is 100% by weight.

[0030] When selecting monomers, attention should also be paid to ensure that they bond well with any fillers used. Usually, polyurethanes, acrylates, polyesters and other monomers do not bond well with the fillers used. Therefore, usually, fillers are surface-silanized or hydrophobized to improve the bond with monomers. The fillers according to the present invention are preferably surface-silanized with silanes having acrylate groups.

[0031] Surprisingly, it has been found that acidic monomers also adhere well to the filler particles.According to the present invention, therefore, there is provided a composition having a polymerizable monomer having a free carboxy group and / or an anhydride group, said composition further comprising a difunctional acrylate or methacrylate having an alicyclic group and at least one photoinitiator.

[0032] If inorganic fillers cannot be used in the polymerizable composition based on a specific dental application, for example based on the target viscosity of the composition, a dye or pigment may be placed in the composition for the reflection of light, especially for the diffuse reflection or scattering of incident light.As a dye, a compound that is soluble in the polymerizable composition and preferably forms a transparent solution is suitable.

[0033] The photocurable compositions according to the invention can be irradiated with a light source which advantageously emits light in the visible light range, with particular preference being given to light sources which emit light from 360 to 750 nm, in particular about 385 nm, particularly preferably about 405 nm. Particularly preferably, the compositions according to the invention can be irradiated in the visible light range from 380 to 660 nm using a polychromatic light source, for example a DLP projector, or advantageously a monochromatic light source, for example a laser projector.

[0034] When adding these pigments and / or dyes, the photoinitiator content in the composition can be reduced: too high a photoinitiator content can lead to so-called "overhardening" of the irradiated composition, embrittlement, so that the dental parts produced accordingly become unusable.

[0035] The use of inorganic fillers, pigments or dyes according to the present invention results in a homogeneous scattering of the light source, especially the UV and visible light sources, in the monomer matrix of the composition, so that a homogeneous curing of the composition is envisaged, as a result of which the polymerized composition has an increased value in terms of the achieved fracture work.

[0036] The compositions according to the invention, after exposure to a light source in the visible light range, in particular from 385 to 405 nm, preferably in a stereolithography process, and the polymerized compositions advantageously obtained in the form of semi-finished products, dental prosthetic parts, orthodontic appliances or dental preforms, as well as after any post-treatment of the light source-polymerized compositions, have the following properties a) a bending strength of 75 MPa or more, and / or b) a modulus of elasticity of 2600 MPa or more, in particular 2700 MPa or more (specified in accordance with DIN EN ISO 10477:2020 in each case). Post-curing or post-treatment can advantageously be carried out, for example, using a laboratory lighting device (HiLite Power 3D) or in a light oven, advantageously using a light spectrum of 390 to 540 nm.

[0037] The subject of the present invention is a polymerizable, photocurable, in particular UV / visible, UV or visible photopolymerizable composition comprising (i) a monomer, preferably a mixture of monomers, and (ii) at least one further component, wherein said (i) monomer is (a) at least one at least difunctional urethane (meth)acrylate; (b) at least one monofunctional acrylate having an alicyclic group and / or at least one monofunctional methacrylate having an alicyclic group, and / or (d) at least one acrylic acid ester having an additional carboxy group; and / or (e) optionally comprising a compound of formula I, 1 , R 2 , R 5 and R 6 are each independently H or C 1 ~C 4 -alkyl, in particular R 1 and R 2 is C 1 ~C 4 - alkyl, preferably methyl, and R 5 and R 6 are identical and selected from H, methyl or ethyl, in particular R 5 and R 6 are the same and selected from H or methyl, and R 3 and R 4 are divalent C 1 ~C 4 -alkylene, n=2 to 6 and m=2 to 6], and (ii) at least one further component is (c) at least one photoinitiator or photoinitiator system for the ultraviolet and / or visible light range; The composition comprises:

[0038] In a preferred embodiment, in formula I, R 1 and R 2 are each methyl, and R 5 and R 6 are the same and selected from H, methyl and ethyl, preferably R 5 and R 6 are the same and selected from H and methyl, and R 3 and R 4 are each independently a divalent ethylene or propylene, n=1 to 6, preferably n=2 to 4 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. 1 and R 2 are each methyl, and R5 and R 6 is H and R 3 and R 4 each independently represents a divalent ethylene, n=1 to 6, preferably n=2 to 4, and m=1 to 6, preferably m=2 to 4, and preferably n=4 and m=4], and mixtures of these with b) 4,4'-di(oxabenzene)dialkylmethanes of the formula 1 and R 2 are each methyl, and R 5 and R 6 is methyl and R 3 and R 4 are each independently a divalent ethylene, and n=1 to 6, preferably n=1 to 4 and m=1 to 4, preferably n=1 and m=1; and mixtures thereof are particularly preferred.

[0039] Optionally, the composition comprises an alkylene dimethacrylate and / or an alkylene diacrylate, each of which is preferably independently selected from the group consisting of C 1 ~C 12 -alkylene] content may be from 0 to 10% by weight, in particular from 0 to 5% by weight, preferably from 0.001 to 5% by weight, where the total content of the composition is 100% by weight.

[0040] 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, said alkyl having 1 to 10 C atoms, preferably 1 to 4 C atoms, or a mixture of at least two of said monomers, in particular those each independently containing at least two, preferably 3 to 15, ethylene glycol or propylene glycol units. Preferred polyether diacrylates may be selected from triethylene glycol dimethacrylate, diethylene glycol dimethacrylate and / or tetraethylene glycol dimethacrylate. Alternatively or additionally, the composition may comprise a diacrylate selected from decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, hexyldecanediol di(meth)acrylate, butanediol di(meth)acrylate, or a mixture containing at least one of said acrylates.

[0041] The parenthetical designation in the terms (methyl)acrylate or (alkyl)acrylate means that the acrylates can be present as the acrylate or methylacrylate as well as, alternatively, as the alkylacrylate.

[0042] The composition comprises as (d) at least one acrylic acid ester having an additional carboxy group, an acrylic acid ester having at least one additional anhydride group of the carboxy group, and / or at least one derivative of said acrylic acid ester, in particular an (alkyl)acrylic acid ester, the alkyl being C 1 ~C 4 -alkyl group, advantageously said alkyl being methyl or ethyl, of formula II or formula III [ka] [In the formula, R 7are each independently selected from divalent radicals containing C, H, O and having 1 to 50 C atoms, in particular 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 1-4C-alkyl, preferably R 7 is a divalent aromatic ester, preferably a phthalate ester, and R 8 is H, methyl or ethyl], [ka] [In the formula, R 9 may be independently selected from divalent benzoyl, salicyloyl, or -C-; R 10 is a divalent -(OR 11 ) r - can be R 11 is ethylene or propylene, and r=0 to 8, in particular r=1 to 4, preferably r=1, and particularly preferably -(OR 11 )- can be a divalent radical derived from a poly(alkylene glycol), especially a poly(propylene glycol) or poly(ethylene glycol) having 1 to 6 propylene glycol or ethylene glycol units, or R 10 can be independently selected from divalent alkylene, and R 8 can be selected from H and 1-4C-alkyl, preferably R 8 is H, methyl or ethyl] It is preferred that the acrylic acid ester contains an acrylic acid ester having an additional carboxy group of the formula:

[0043] The subject of the present invention is also compositions which may contain as (d) at least one acrylic acid ester having an additional carboxy group, at least one acrylic acid ester having an anhydride group for the carboxy group, and / or derivatives of the abovementioned 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 having carboxy groups, preferably said compositions comprising polyether-functionalized acrylic acid esters having carboxy groups on the acrylic, polyether-functionalized acrylic acid esters having carboxy groups on the alkyl, in particular said polyethers based on poly(propylene glycol) and poly(ethylene glycol) having 1 to 6 glycol units.

[0044] According to the invention, the composition comprises a compound of formula III, 9 is benzoyl, and R 10 is a divalent -(OR 11 ) r -, r=1, and R 8 is H or methyl, preferably H], optionally in admixture with 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate or hydroxypropyl (meth)acrylate.

[0045] Monomers which are likewise preferred as the at least one further monomer in the composition may be selected from at least one difunctional, trifunctional, tetrafunctional or polyfunctional monomer, in particular one which is not a urethane (meth)acrylate.

[0046] As monofunctional monomer, hydroxyethyl acrylate is preferably used. Similarly, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and / or hydroxyethyl acrylate can be used, optionally as a mixture of at least two of the above monomers. Advantageously, at least one acrylic acid ester having an additional carboxy group is present in a mixture with hydroxyethyl acrylate, where the acrylic acid ester having an additional carboxy group is present in an amount of 95-99% by weight and hydroxyethyl acrylate is present in an amount of 1-5% by weight, the mixture having an overall content of 100% by weight.

[0047] According to one option, compositions are preferred which contain an inorganic filler as a further component, said inorganic filler being selected from (f) inorganic fillers, inorganic oxides or inorganic mixed oxides, in particular zirconium and / or silicon oxides, and / or dental glasses, preferably silicon dioxide, zirconium dioxide, or mixed oxides of silicon dioxide and metal oxides, in particular mixed oxides of metal dioxide and silicon dioxide. As metal oxides or metal dioxides, those which do not correspond to the silicon dioxide already mentioned as specific metal oxides are considered in the present application. As metal oxides, mixed oxides of silicon dioxide and further metal oxides are particularly preferred, which have a primary particle size in the range of less than 100 nm and are optionally present as secondary agglomerates of 2 to 5 μm. These oxides or mixed oxides are advantageously essentially present in X-ray amorphous form. As dental glasses, aluminosilicate glasses, fluoroaluminosilicate glasses, and / or barium aluminum silicates can be used. The oxides can be selected from those mentioned above as well as from amorphous spherical fillers based on oxides or mixed oxides. As primary particles, the smallest particles of the oxides are considered, which can be present as secondary agglomerates.

[0048] The particle size of the inorganic filler, e.g. at least one inorganic oxide, mixed oxide, or dental glass, e.g. containing barium aluminum oxide, is, for the purposes of the present application, on average, an average particle diameter d 50 Particularly preferably, the fillers have a particle diameter of about 3 to 70 nm, in particular 10 to 50 nm (nanometers), optionally the particles may be present as primary or secondary aggregates, particles up to 10 μm. The primary particle size of the inorganic fillers, which may optionally be present as secondary aggregates and / or primary aggregates, has a particle diameter of about 3 to 70 nm, in particular 10 to 50 nm. Preferably, inorganic oxides, such as silicon dioxide, have a primary particle size of 3 to 70 nm. The determination of the particle size can be carried out by determining the particle size distribution by volume mass in a dispersion in water (Malvern, by laser diffraction, ISO 13320: 2009). Additionally or alternatively, the particle size can be determined using SEM (scanning electron microscope). The advantage of very small particle diameters, which may optionally exist as primary and / or secondary aggregates, is that upon curing with light, light is essentially diffusely scattered on these particles, resulting in improved curing in stereolithography or DLP processes.

[0049] The subject of the present invention is a composition comprising monomers and optionally prepolymers (oligomers) and / or polymers comprising at least one difunctional urethane (meth)acrylate, at least one monofunctional acrylate having a dipentanyl group, and / or a methacrylate having a dipentanyl group, at least one acrylic acid ester having an additional carboxy group, at least one acrylic acid ester having an anhydride group of the additional carboxy group, and / or derivatives of the abovementioned acrylic acid esters, and optionally at least one inorganic filler.

[0050] In order to meet high aesthetic demands, compositions that can be used in the dental field to manufacture permanent dentures, such as working models, KFO models, drilling templates, temporary restorations, and splints, must have high transparency. This transparency can usually be achieved by optimal matching of the refractive index of the filler and the polymer matrix. However, due to various physical and chemical constraints, there are very narrow limitations on the choice of fillers and monomers.

[0051] The preferred filler content is 0-35% by weight, 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 containing at least one of the aforementioned inorganic oxides. Advantageously, the filler content can be 0.01-10% by weight of mixed oxides and, optionally, additionally, 0-25% by weight of silicon dioxide. In particular, mixtures having a content of 1-10% by weight of mixed oxides and a content of 9-25% by weight of silicon dioxide with a filler content of 10-35% by weight, based on the total composition, are preferred.

[0052] It is furthermore preferred if the composition is not thixotropic. It is furthermore particularly preferred if the composition has a viscosity of less than 7500 mPa·s, in particular between 500 and 7000 mPa·s, advantageously between 500 and 4000 mPa·s, preferably between 500 and 3000 mPa·s, particularly preferably between 500 and 1500 mPa·s. The viscosity is advantageously measured using a rheometer according to DIN 1342-2; 2003-11 Newtonian fluids or DIN 1342-3; 2003-11 non-Newtonian fluids (Anton Par, Physiker MCR 301, shear rate d(gamma) / dt=100 / s 23° C.). The composition according to the invention is not thixotropic or advantageously only slightly so. According to a further embodiment, it is preferred that little change in viscosity occurs over long storage periods. Furthermore, the composition has very good reactivity upon exposure to a laser or DLP projector.

[0053] Using the compositions according to the invention, workpieces or three-dimensional bodies can be printed with very good geometric accuracy / resolution. Furthermore, good color stability is observed in the case of the workpieces.

[0054] The subject of the present invention is a polymerized composition, preferably as a three-dimensional molded body, in particular as a dental prosthesis part, an orthodontic appliance or a dental preform, which is obtained by irradiating a polymerizable composition. By additional full-surface light curing is meant, for example, post-treatment in a 3D light oven.

[0055] Advantageously, the polymerized composition has a modulus / flexural strength ratio of 25 or more, advantageously 26 or more, and in particular a modulus / flexural strength ratio of 45 [μg / mm 3 ] and has a water absorption rate of less than 100%.

[0056] The subject of the invention is also a semi-finished product in the form of a three-dimensional moulding of the polymerised composition, which is advantageously additionally light-cured all over and is suitable as a dental prosthesis part, an orthodontic appliance, a dental preform, an industrial part, a tool, an instrument, a hoof restoration part or an implant in medical prostheses, said semi-finished product having a) a bending strength of 75 MPa or more, and / or b) an elastic modulus of 2600 MPa or more, and / or c) a modulus of elasticity of 45 [μg / mm 3 The blanks can advantageously be in the form of artificial teeth or bridges or parts of bridges, which only need to be ground or slightly reworked on the occlusal surface for a final individual adaptation to the patient.

[0057] The present invention further relates to an article in the form of a three-dimensional molding of the polymerized composition in the form of a dental prosthetic part, an orthodontic device, a dental preform, an industrial part, a tool, an instrument, a hoof restoration part or an implant in medical prosthetics, the semi-finished product of which has a) a bending strength of 75 MPa or more in accordance with DIN EN ISO 10477:2020 and / or b) a modulus of elasticity of 2600 MPa or more in accordance with DIN EN ISO 10477:2020 and / or c) a modulus of elasticity of 45 [μg / mm 3 ].

[0058] The present invention also relates to the use of the composition for producing dental prosthetic parts, orthodontic appliances, dental preforms, or industrial parts, tools, instruments, hoof repair parts, or implants in medical prosthetics in rapid prototyping or in rapid manufacturing, i.e. for producing dental prosthetic parts or for rapid tooling methods.As industrial parts, all parts that are subject to mechanical stress, such as parts in the automotive field, machine parts, engine parts, instrument parts, furniture parts, consumer goods parts, or kitchenware parts, are considered.

[0059] The following methods, rapid prototyping or rapid manufacturing (methods for producing workpieces, for example dental prosthetic parts), or rapid tooling (methods for producing workpieces), respectively include the stereolithography method and the DLP method. Optionally, after the polymerizable composition has hardened in the above-mentioned methods, a post-treatment with UV, visible or UV / visible light can be carried out. Advantageously, the post-treatment of the polymerized composition or dental prosthetic part, orthodontic appliance, or dental preform, or semi-finished product is carried out simultaneously on at least three sides, preferably 5-6 sides, which is possible, for example, in a light oven.

[0060] Dental prosthetic parts include prosthetic bases or parts thereof, e.g. gingival replicas or parts thereof, artificial teeth, artificial teeth with at least 2-16 interdental spaces bonded with a single strip of material, crowns, temporary crowns, total prostheses, full crowns, orthodontic splints (similar to Invisalign), dental bridges, abutments, superstructures, dental stege, inlays, veneers, onlays, orthodontic appliances, e.g. bite splints, dental preforms for artificial teeth, drilling templates for implant technology, mouthguards and / or implants.

[0061] The present invention also relates to the use as bone cement for cementing artificial joint prostheses, crowns, telescopes, veneers, dental bridges, prosthetic teeth, implants, implant parts, abutments, superstructures, orthodontic appliances. In addition to dental prosthetic parts, the use as medical implants or in the veterinary field, especially as hoof repair material, is also preferred.

[0062] Additionally, color pigments can be added to the composition to adjust the color. Furthermore, red fibers can be added to the composition to mimic the blood vessels of the gums. In the polymerized composition, layer thicknesses ranging from 5 μm to 250 μm per hardened layer can be achieved.

[0063] In one alternative, the monofunctional monomer may contain at least one of the mentioned monomers: 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, mixtures containing at least one of these (meth)acrylates, and / or copolymers comprising one or at least two of the above monomers.

[0064] Additionally, the composition may comprise a tri-, tetra- or polyfunctional monomer that is not a urethane (meth)acrylate, such as a monomer selected from pentaerythritol tetraacrylate, trimethylolpropane tri(meth)acrylate and / or pentaerythritol tetra(meth)acrylate.

[0065] As photoinitiators, 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, anisyl, 4,4'-dichlorobenzyl and 4,4'-dialkoxybenzyl or camphorquinone, come into consideration. The photoinitiators are advantageously used in combination with reducing agents. Examples of reducing agents are amines, such as aliphatic or aromatic tertiary amines, such as N,N-dimethyl-p-toluidine or triethanolamine, cyanoethylmethylaniline, triethylamine, N,N-dimethylaniline, N-methyldiphenylamine, N,N-dimethyl-sym.-xylidine, N,N-3,5-tetramethylaniline and 4-dimethylaminobenzoic acid ethyl ester or organic phosphites. Common photoinitiator systems are, for example, camphorquinone plus ethyl-4-(N,N-dimethylamino)benzoate, 2-(ethylhexyl)-4-(N,N-dimethylamino)benzoate or N,N-dimethylaminoethyl methacrylate.

[0066] As initiators for UV-initiated polymerization, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (bis-trimethylbenzoyl)phenylphosphine oxide, 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-hydroxycyclohexyl phenyl ketone, camphorquinone, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, dimethylhydroxyacetophenone, 4,4-bis(diethylamino)benzophenone, 1-(9,9-diphenyl)phenylphosphine oxide ... Particularly suitable are butyl-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-trimethylbenzoyl-diphenylphosphine oxide, dimethylhydroxyacetophenone, methyl-o-benzoyl-benzoate, methylbenzoyl-formate, 4-phenylbenzophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinpropan-1-one and / or ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate, as well as mixtures comprising at least two of the abovementioned photoinitiators. UV photoinitiators can be used alone or in combination with initiators for visible light.

[0067] Suitable optional photoinitiators and / or initiator systems may include a) at least one radical photoinitiator, in particular at least one peroxide and / or azo compound, in particular LPO: dilauroyl peroxide, BPO: dibenzoyl peroxide, t-BPEH: tert.-butyl per-2-ethylhexanoate, AIBN: 2,2'-azobis-(isobutyronitrile), DTBP: di-tert.-butyl peroxide, or α-hydroxyketones, camphorquinone, acylphosphine oxides. Optionally, stabilizers and optionally b) at least one coinitiator, such as amines, usually tert-amines, in particular at least one aromatic amine, such as N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidine and / or p-dibenzylaminobenzoic acid diethyl ester, may be added.

[0068] Typical stabilizers include 2,6-di-tert.-butyl-4-methylphenol (BHT), 2-hydroxy-4-methoxybenzophene and / or hydroquinone monomethyl ether (MEHQ). EXAMPLES

[0069] The present invention will be described in more detail by the following examples, but the present invention is not limited to these examples.

[0070] Post-curing / post-processing was done using inter alia a laboratory lighting system HiLite Power 3D.

[0071] How to explain: The sample bodies were printed with Cara Print 4.0 (wavelengths: 385 nm and 405 nm) with a layer thickness of 50 μm using the appropriate print data set according to the manufacturer's instructions and subsequently post-cured for 2×5 min with HiLite Power 3D.

[0072] method: Unless otherwise stated, the measurements in Table 3 were carried out in accordance with DIN EN ISO 10477:2020 (23±2° C., relative humidity at least 30%). DIN EN ISO 10477:2020 is incorporated in its entirety by reference, i.e. its disclosure content is disclosed. The preparation of the sample bodies was carried out from printed sample bodies or post-cured flat bars.

[0073] The bending strength is specified according to DIN EN ISO 10477:2020, chapters 5.4 and 7.5 (see ISO 10477, Figure 2). f =2±0.1mm and width b f =2.0±0.1mm, length l f Flexural strength specimens with a diameter of 25±2 mm were printed and exposed as described above. The specimens were tested after immersion in water at 37° C. for 24 hours. The tests were carried out on a Zwick universal testing machine with an initial load of 0.4 N and a test speed of 0.75 mm / min. From the flexural strength measurements according to 7.5 of ISO 10477, the corresponding elastic modulus was determined from the slope of the curve (1 N to 7 N) (calculation of the elastic modulus as a secant line).

[0074] The three-media abrasion measurements are carried out according to the ACTA method (ISO / TS 14569-2, 2001, Guidance on dental materials - Abrasion testing, Part 2, Chapter 5). Test specimens with dimensions 10 x 12 mm are printed, post-exposed (as described above) and correspondingly fixed on the specimen wheel. After grinding (= production of a homogeneous surface with a diamond grinding wheel), abrasion is carried out in the same device (three-media abrasion machine, DMA, SD Mechatronik) in a mixture of water and poppy seeds (110 g dried Braumön: 205 g water) for 300,000 cycles, with the antagonist wheel and specimen wheel moving in opposite directions (contact pressure 20 N, antagonist wheel: 240 rpm, specimen wheel: 180 rpm). After 150,000 cycles, the mixture of poppy seeds and water is replaced with a new one.

[0075] Since the sample wheel is wider than the mating wheel, an unabraded surface remains on each specimen, and this area is the reference height for the evaluation. 3 The volume loss at 1000 nm (volume loss at 100 nm) is performed using a non-contact surface laser scanner (OPM GmbH, resolution 100 P / mm, z-axis resolution 0.1 μm) over an area of ​​2 × 8 mm (of which approximately 1 mm of the unabraded surface on each side serves as the reference height).

[0076] The water absorption and solubility are determined according to DIN EN ISO 10477:2020, chapters 5.6, 5.7 and 7.7. Round specimens with a diameter of 15 ± 1 mm and a thickness of 1 ± 0.1 mm are printed, post-exposed (printing method described above), polished to high gloss according to the application conditions, and the diameter and thickness are measured individually to determine the volume (V). Five specimens are conditioned in a desiccator on silica gel at 37 ° C to constant mass (m1). They are subsequently immersed in water for 7 days at 37 ° C. The mass after immersion is determined after 1 min after removal and wiping with pulp (m2). Redrying is again carried out in a desiccator at 37 ° C to constant mass (m3).

[0077] Water absorption is given by (m2-m3) / V. Solubility is given by (m1-m3) / V. The upper limit for water absorption is <40μg / m according to the standard. 3 and the limit for water solubility is <7.5 μg / m 3 It is.

[0078] Working Example: The mixture produced is used to print the test specimens for the following tests in a 3D precision printer at a wavelength of 405 nm (Carla Print 4.0). After the printing process, the test specimens are washed with isopropanol and subjected to a post-treatment process. This is carried out by exposing each side for 5 minutes or in a laboratory lighting device HiLite Power 3D, 200 W (Kulzer GmbH) according to the manufacturer's instructions. The properties of the mixture according to the invention as a printed material, especially as a printed dental material, are tested according to ISO 10477 (in water at 37 ° C) as well as according to the above-mentioned poppy seed abrasion.

[0079] Competitor Nextdent is supposed to avoid brittleness in product C&B MFH by a high percentage of HEMA (15-25% according to MSDS). The resulting printed blanks therefore have too high a water absorption rate and moreover significant settling is observed. The composition of Nextdent is described in the MSDS as follows: urethane dimethacrylate 50-75% by weight, 2-hydroxymethacrylate <25% by weight, ethylene glycol dimethacrylate <10% by weight, ethoxylated bisphenol A dimethacrylate <10% by weight, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide 1-5% by weight.

[0080] [Table 1]

[0081] [Table 2]

[0082] [Table 3]

[0083] It is believed that the monofunctional dicyclopentanyl methyl acrylate acts as a diluent and counteracts the shrinkage of the photocured composition. The compositions with dicyclopentanyl methacrylate content further show very low water absorption as well as good elastic modulus and high values ​​for flexural strength. Acrylic esters with additional carboxy groups are used as monofunctional monomers and as plasticizers, which themselves have a high viscosity (>4000 mPa·s according to the specifications) compared to HEMA. The use of acrylic esters on the one hand counteracts settling and has a good effect on the shrinkage of the composition, which is less pronounced than the effect of HEMA. The composition of Example 2, which combines UDMA and an acrylic ester with an additional carboxy group, has the highest value for flexural strength without water immersion as well as a high value for elastic modulus. Example 3, which contains a combination of UDMA, dicyclopentanyl methyl acrylate and an acrylic ester with an additional carboxy group, shows the highest elastic modulus without water immersion and the lowest value for water solubility. Both Examples 1 and 3 show the lowest water absorption and the lowest water solubility.

Claims

1. (i) a monomer; (ii) at least one further component and (i) a polymerizable, photocurable composition comprising: (a) 30 to 70% by weight of at least one at least difunctional urethane (meth)acrylate; (b) 10 to 40% by weight of at least one monofunctional acrylate having an alicyclic group and / or at least one monofunctional methacrylate having an alicyclic group; (d) 5 to 40% by weight of at least one acrylic acid ester having additional carboxy groups; (e) 1 to 5% by weight of Formula I 【Chemistry 1】 wherein R 1 , R 2 , R 5 and R 6 are each independently selected from H or C 1 -C 4 -alkyl, and R 3 and R 4 are each divalent C 1 -C 4 -alkylene, n=0 to 6 and m=0 to 6. at least one disubstituted 4,4′-di(oxabenzene)dialkylmethane of the formula (f) 0 to 35% by weight of inorganic fillers including inorganic oxides or inorganic mixed oxides and / or dental glass and (ii) at least one further component comprises (c) 0.01 to 10% by weight of at least one photoinitiator for the ultraviolet and / or visible light range, or a photoinitiator system for the ultraviolet and / or visible light range wherein the total composition is 100% by weight.

2. (f) 0 to 35% by mass of an inorganic filler containing an inorganic oxide or inorganic mixed oxide and / or dental glass; (g) 0 to 10% by weight, in particular 1 to 10% by weight, of alkylene dimethacrylates and / or alkylene diacrylates, (h) optionally 0.1 to 5% by weight of hydroxyethyl acrylate 10. The composition of claim 1, wherein the total composition is 100% by weight.

3. The composition described in claim 2, characterized in that it contains ethylene glycol dimethacrylate as the alkylene dimethacrylate (g).

4. 3. The composition of claim 1, wherein the composition is suitable for use in a generative printing method using layer-by-layer light-induced polymerization of the composition to produce three-dimensional objects.

5. (d) at least one acrylic acid ester having an additional carboxy group is represented by Formula II or III 【Chemistry 2】 [In the formula, R 7 are each independently selected from divalent radicals containing C, H, O and optionally N and having 1 to 25 C atoms, in particular divalent aromatic esters, aromatic urethanes, alkylene esters, alkylurethanes, aromatic ethers, alkyl ethers, and R 8 is selected from H and 1-4C-alkyl, preferably R 7 is a divalent aromatic ester. 【Transformation 3】 [In the formula, R 9 are independently selected from divalent benzoyl, salicyloyl and derivatives thereof, or —C—; R 10 is a divalent -(OR 11 ) r - and R 11 is ethylene or propylene, and r is 0 to 10, in particular 1 to 6, preferably r=1, or R 10 are independently selected from divalent alkylenes, and / or R 8 is selected from H and 1-4C-alkyl, preferably R 8 is H, methyl or ethyl] 3. The composition according to claim 1, wherein the acrylic acid ester has an additional carboxy group selected from the group consisting of:

6. 3. The composition according to claim 1 or 2, characterized in that (b) the at least one monofunctional acrylate having an alicyclic group and / or the at least one monofunctional methacrylate having an alicyclic group comprises at least one monofunctional acrylate having a dicyclopentanyl group and / or at least one monofunctional methacrylate having a dicyclopentanyl group, or a mixture containing them.

7. 3. The composition according to claim 1 or 2, wherein (b) the at least one monofunctional acrylate having an alicyclic group and / or the at least one monofunctional methacrylate having an alicyclic group comprises at least one monofunctional acrylate having a monovalent alicyclic group and / or at least one monofunctional methacrylate having a monovalent alicyclic group.

8. 3. The composition of claim 2, wherein (d) the at least one additional acrylic acid ester having a carboxy group comprises phthalic acid mono-[2-(methacryloyloxy)-ethyl ester], 2-acryloyloxyethyl hydrogen phthalate, polyether-functionalized acrylic acid esters having a carboxy group, and mixtures thereof.

9. 3. The composition according to claim 1, wherein (a) the at least one difunctional urethane (meth)acrylate is selected from difunctional urethane (meth)acrylates having a divalent alkylene group.

10. 8. The composition according to claim 7, characterized in that (b) the at least one monofunctional acrylate having a monovalent cycloaliphatic group and / or the at least one monofunctional methacrylate having a monovalent cycloaliphatic group comprises a tricyclodecane alkanol methacrylate, a tricyclodecane alkanol acrylate, wherein the alkanol has 1 to 10 C atoms, or a mixture containing at least one of these monomers.

11. (e) Formula I 【Chemistry 4】 [In the formula, R 1 and R 2 are each methyl, and R 5 and R 6 are the same and are selected from H, methyl and ethyl, in particular R 5 and R 6 are the same and selected from H and methyl, and R 3 and R 4 are each independently a divalent ethylene or propylene, n=1 to 6, preferably n=2 to 4, and m=1 to 6, preferably m=2 to 4, preferably n=2 and m=2, or n=4 and m=4.

3. The composition of claim 1, comprising at least one disubstituted 4,4'-di(oxabenzene)dialkylmethane of the formula: and mixtures thereof.

12. The composition further comprises an inorganic filler, the inorganic filler comprising:

3. The composition according to claim 1 or 2, characterized in that (f) inorganic fillers are selected from inorganic oxides or inorganic mixed oxides and / or dental glasses, in particular silicon dioxide, zirconium dioxide, mixed oxides of metal oxides and silicon dioxide, and / or mixed oxides of silicon dioxide and zirconium dioxide, and mixtures comprising one of the above inorganic oxides, preferred fillers comprising silicon dioxide and / or mixed oxides of metal dioxide and silicon dioxide.

13. The composition comprises: (a) 40 to 60% by weight of at least one at least difunctional urethane (meth)acrylate; (b) 15 to 30% by weight of at least one monofunctional acrylate having an alicyclic group and / or at least one monofunctional methacrylate having an alicyclic group; (c) 0.01 to 10% by weight of at least one photoinitiator for the ultraviolet and / or visible light range or a photoinitiator system for the ultraviolet and / or visible light range; (d) 5 to 30% by weight of at least one acrylic acid ester having additional carboxy groups; (e) 1 to 15% by weight of Formula I 【Transformation 5】 [In the formula, R 1 , R 2 , R 5 and R 6 are each independently H or C 1 ~C 4 - alkyl, and R 3 and R 4 are divalent C 1 ~C 4 -alkylene, n=0 to 6 and m=0 to 6. at least one disubstituted 4,4′-di(oxabenzene)dialkylmethane of the formula (f) 0 to 35% by weight of inorganic oxides or inorganic mixed oxides and / or dental glass, especially inorganic fillers containing silicon dioxide, zirconium dioxide, mixed oxides of metal oxides and silicon dioxide, preferably silicon dioxide and / or mixed oxides of metal dioxide and silicon dioxide.

3. The composition of claim 1 or 2, wherein the total composition is 100% by weight.

14. 3. The composition according to claim 1, wherein the composition has a viscosity of less than 7500 mPa·s, in particular from 500 to less than 4000 mPa·s, preferably from 500 to 3000 mPa·s.

15. 3. A three-dimensional shaped body of the polymerized composition according to claim 1 or 2 in the form of a dental prosthetic part, an orthodontic device, a dental preform, an industrial part, a tool, an instrument, a hoof repair part or an implant in medical prosthetics, wherein the shaped body has a) a bending strength according to DIN EN ISO 10477:2020 of 75 MPa or more, and / or b) an elastic modulus according to DIN EN ISO 10477:2020 of 2600 MPa or more, and / or c) a modulus of elasticity according to DIN EN ISO 10477:2020 of 45 [μg / mm 3 The three-dimensional molded body has a water absorption rate of less than 1000 kJ / cm.sup.

2.

16. 3. A blank in the form of a three-dimensional shaped body of the polymerized composition according to claim 1 or 2 for producing dental prosthetic parts, orthodontic appliances, dental preforms, industrial parts, tools, instruments, hoof repair parts or implants in medical prosthetics, said blank having a) a flexural strength according to DIN EN ISO 10477:2020 of 75 MPa or more, and / or b) a modulus of elasticity according to DIN EN ISO 10477:2020 of 2600 MPa or more, and / or c) a modulus of elasticity according to DIN EN ISO 10477:2020 of 45 [μg / mm 3 The semi-processed product has a water absorption rate of less than 1000 kJ / cm.sup.

2.

17. 10. Use of a composition according to claim 1 or 2 for producing dental prosthetic parts, orthodontic appliances, dental preforms, industrial parts, tools, instruments, hoof repair parts, implants in medical prosthetics, in particular in rapid prototyping or in rapid manufacturing or rapid tooling methods.

18. A composition as described in claim 1 or 2 for use as a bone cement for cementing artificial joint prostheses, crowns, telescopes, veneers, dental bridges, prosthetic teeth, implants, implant components, abutments, superstructures, and orthodontic devices.

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