Free radical polymerizable compounds and compositions

Abstract

This invention relates to a radical polymerizable compound represented by the structural formula I: PG-Sp-PCA-Sp-[OC(O)NH-K-NHC(O)O-Sp-PCA-Sp] n -PG (Formula I), where PG is independently a radical polymerizable group, R 1 = Selected from hydrogen, C1-C8 alkyl groups, aryl groups, and aromatic aliphatic groups having C6-C8 carbon atoms, R 2 = hydrogen, selected from C1-C4 alkyl groups; Sp = independently selected from unbranched and branched alkylenes having C1-C19 carbon atoms, and the carbon chain may further contain oxygen, sulfur and / or -OOC-, or Sp may not be present; PCA = independently a polycyclic group; K = aliphatic acyclic saturated or unsaturated unit having C1-C15 carbon atoms, aliphatic cyclic saturated or unsaturated unit having C3-C15 carbon atoms, or an aromatic aliphatic saturated or unsaturated unit having C6-C14 carbon atoms; n = 1 to 9. The present invention also relates to methods for producing such compounds, radical polymerizable compositions containing such compounds, their uses, and hardened dental materials.

Description

Technical Field

[0001] The present invention relates to free radical polymerizable compounds, methods for preparing such compounds, free radical polymerizable compositions containing such compounds, their uses, and cured dental materials.

Background Art

[0002] Free radical polymerizable dental materials mainly contain (meth)acrylate monomers. Dimethacrylate systems are usually used for restorative and prosthetic dental materials such as dental fillings or dentures because of their properties, such as rapid free radical polymerization, good mechanical properties, and aesthetic appearance. For example, ordinary monomers have a high molecular weight linear structure containing an aliphatic group or an aromatic group and having terminal methacrylate functional groups, such as 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (bis-GMA) and 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diylbis(2-methylacrylate) (UDMA).

[0003] Efforts have been made for some time to substantially discontinue the use of monomers having structural elements derived from bis-GMA or bisphenol A and replace them with other compounds to at least some extent. Here, particular focus has been on urethane monomers and oligomers. In the field of dental materials, the most widely commercially used substance as at least a partial alternative to bis-GMA is UDMA.

[0004] Monomers such as bis-GMA and UDMA are present in a wide range of commercially available free-radical polymerizable compositions for the manufacture of dental materials, but they have several drawbacks. These are generally high-viscosity to solid substances. Therefore, mixtures with monomers having significantly lower viscosity, such as triethylene glycol dimethacrylate (TEDMA), are used. TEDMA is a very versatile, low-molecular-weight monomer with low viscosity (0.01 Pa·s at 23°C) and high mobility during polymerization, which promotes conversion during polymerization.

[0005] However, polymerizable compositions containing these monomer mixtures and dental materials obtained therefrom possess several problematic properties that can adversely affect clinical treatment outcomes. For example, compositions containing dimethacrylate monomers exhibit relatively low polymerization conversion rates, significant polymerization shrinkage, insufficient toughness, and undesirable water absorption. Known systems often achieve relatively low double bond conversion rates, which not only contributes to insufficient mechanical properties and poor wear resistance but is also detrimental in terms of the toxicity and biocompatibility of the polymerized dental materials. Furthermore, the volume shrinkage of currently used dimethacrylate monomers and the shrinkage stress of tooth fillings can lead to failure of the bond between the tooth and the filling, resulting in microleakage and consequently secondary caries, which can significantly reduce the lifespan of the restoration. Attempts to increase the double bond conversion rate to reduce the level of unconverted monomers unfortunately result in increased polymerization shrinkage and shrinkage stress.

[0006] Low molecular weight monomers containing oligo[ethyleneoxy] groups that have some solubility in water and thus possess bioavailability, such as TEDMA, are currently being critically assessed due to their toxicological properties and susceptibility to biodegradation processes. Monomers containing the bis-2,2[p-oxyphenyl]propane structural element, i.e., bisphenol A-based monomers, are similarly being critically assessed because dental materials containing monomers or oligomers with these structural elements have been found to release detectable amounts of bisphenol A due to toxicologically significant properties.

[0007] Various approaches exist to increase conversion rates or reduce volume shrinkage. In dental composites for dental fillings, which contain fillers in an organic resin matrix, attempts have been made to reduce volume shrinkage by increasing the filler content. However, if the filler content is too high, mixing with the organic resin becomes difficult. Furthermore, the filler content is limited for dental composites, which must have a certain fluidity. To increase conversion rates and reduce polymerization shrinkage, the development of novel monomers, such as high molecular weight urethane methacrylate monomers, is underway. The synthesis of these monomers is complex and typically requires a purification process, which limits the availability of such monomers. Increased molecular weight is generally associated with less favorable mechanical properties in cured dental materials for a given monomer functional group. Furthermore, the high viscosity of such monomers means that they must be used with larger amounts of lower viscosity monomers for use in dental composites, which negatively impacts shrinkage.

[0008] EP 2436365 B1 describes a low-shrinkage dental composite comprising a monomer mixture containing monomers (b1) and (b2) in a ratio of 1:20 to 5:1. The compositions of the examples each contain 4.8 to 76.6% by weight of bis((meth)acryloyloxymethyl)tricyclo[5.2.1.0 2,6The composite contains decane (b1), 90.9–19.1% by weight of UDMA (b2), and 4.3% by weight of TEDMA (b2). These composites exhibit polymerization shrinkage of approximately 1.50%, regardless of the ratio of (b1) to (b2). As in Comparative Example 11, decreasing the filler content and increasing the proportion of TEDMA increases polymerization shrinkage.

[0009] Vaidyanathan et al., in "Visible light cure characteristics of a cycloaliphatic polyester dimethacrylate alternative oligomer to bis-GMA," Acta Biomater Odontol Scand. 2015;1:59-65, discloses the use of PEM-665 as a BPA-free alternative to bis-GMA in combination with 30% or 50% by weight of TEDMA. When the polymerization conversion rates of these mixtures were examined, it was found that the combination of PEM and TEDMA exhibited a higher polymerization conversion rate than the combination of bis-GMA and TEDMA.

[0010] There remains a demand for free radical polymerizable compounds, or free radical polymerizable compositions containing such compounds, that can reduce the potential toxicity of the dental materials manufactured therefrom, reduce volume shrinkage, and enable good mechanical properties, while also being readily available. [Overview of the project] [Problems that the invention aims to solve]

[0011] Accordingly, an object of the present invention is to provide a free radical polymerizable compound or a free radical polymerizable composition containing such a compound that overcomes the drawbacks of the prior art described above. In particular, it is possible to provide a free radical polymerizable compound and a free radical polymerizable composition that reduces polymerization shrinkage, while simultaneously obtaining a dental material having good mechanical properties, such as very good flexural strength and tensile strength, and good fracture toughness, and is also toxicologically safe. Furthermore, it is possible to obtain a free radical polymerizable compound or a free radical polymerizable composition containing such a compound having a refractive index particularly suitable for producing a material containing a conventional filler in the dental field and having optical properties that are particularly advantageous with respect to translucency and opacity. Furthermore, an object of the present invention is to provide a method that enables the production of such a free radical polymerizable compound in a simple manner, with high purity, and without undesirable discoloration. [Means for solving the problem]

[0012] This objective is achieved by the present invention, which uses a free radical polymerizable compound represented by the structure of Formula 1: PG-Sp-PCA-Sp-[OC(O)NH-K-NHC(O)O-Sp-PCA-Sp] n -PG (Equation 1) [Here, PG = Each is independently selected from free radical polymerizable groups, preferably (NR 1 )OC-CR 2 =CH2 and OOC-CR 2 = Selected from CH2, more preferably OOC-CR 2 Selected from =CH2, R 1 = Selected from hydrogen, C1-C8 alkyl groups, aryl groups, and araliphatic groups having C6-C8 carbon atoms, preferably selected from C1-C8 alkyl groups and benzyl groups. R 2 = Selected from hydrogen, C1-C4 alkyl groups, preferably selected from hydrogen and methyl; Sp = A spacer group independently selected from unbranched and branched alkylenes having C1-C19 carbon atoms, wherein the alkylene may further have oxygen atoms, sulfur atoms and / or -OOC- in its carbon chain. Alternatively, Sp does not exist; Each PCA is independently a polycyclic group, preferably an aliphatic polycyclic group, preferably an aliphatic bicyclic group or an aliphatic tricyclic group; K = an aliphatic acyclic saturated or unsaturated unit having C1-C15 carbon atoms, preferably C3-C13 carbon atoms, more preferably C6-C9 carbon atoms, which may be substituted with one or more C1-C3 aliphatic carbon substituents. A polyphatic cyclic saturated or unsaturated unit having C3-C15 carbon atoms, preferably C5-C13 carbon atoms, more preferably C6-C13 carbon atoms, which may be substituted by one or more polyphatic C1-C3 carbon substituents, or Aromatic or aromatic aliphatic unit having C6-C14 carbon atoms, preferably C6-C13 carbon atoms, which may be substituted by one or more aliphatic C1-C3 carbon substituents; n = 1 to 9, preferably 1 to 6.

[0013] Preferred embodiments may be found in the dependent claims. [Modes for carrying out the invention]

[0014] First, some terms used in the context of this invention will be explained.

[0015] In the context of the present invention, (polymerizable) dental materials mean materials for (bio)medical applications, particularly on hard tooth tissue such as enamel and dentin, or on bone tissue such as jawbone.

[0016] In the context of the present invention, the radical polymerizable compound is a monomer when n=1, and an oligomer when n=2 to 9.

[0017] Preferably, K is selected from a linear aliphatic saturated unit having 6 to 9 carbon atoms (where the unit may be substituted by one or more aliphatic C1-C3 carbon substituents), an aliphatic cyclic saturated unit having 6 to 13 carbon atoms (where the unit may be substituted by one or more aliphatic C1-C3 carbon substituents), and an aromatic or araliphatic unit having 6 to 13 carbon atoms and having at least two aliphatic substituents, preferably C1-C3 substituents, on the aromatic ring.

[0018] Furthermore, K may be 1,3- and 1,4-cyclohexanylene, preferably 1,3-cyclohexanylene.

[0019] The spacer group Sp is preferably methylene, *CH2-(OC2H4) p 、*CH2-(OC3H6) p 、*(OC2H4) p 、*(OC3H6) p 、*CH2-(O-C(O)-R 5 -) p 、*(O-C(O)-R 5 -) p and *S-R 5 selected from, where p = 1 to 5, preferably 1 to 3, and R 5 is a C1-C12 alkylene group, preferably a C2-C6 alkylene group. The symbol * indicates the binding site to the PCA unit.

[0020] The spacer group Sp is more preferably methylene.

[0021] The polycyclic group PCA is preferably selected in each case from the structures of the following formulas 2 to 13: ​​These may be optionally substituted with one or more C1-C4 alkyl groups. Thus, in each case, all stereoisomers of these formulas, in particular enantiomers and diastereomers, are also included.

[0022] Furthermore, the polycyclic group PCA is preferably 2-methyl-3,3-norbornanediyl, 2-ethyl-3,3-norbornanediyl, 2-propyl-3,3-norbornanediyl, 2-butyl-3,3-norbornanediyl, bicyclo[2.2.2]octane-1,4-diyl, bicyclo[2.2.2]octane-2,3-diyl, bicyclo[2.2.2]octo-5-ene-5,6-diyl, 1,3-adamantanediyl, tetracyclo[6.6.2.0 2,7 .0 9,14 The polycyclic group PCA is selected from hexadeca-2,4,6,9,11,13-hexaene-15,16-diyl, 1,4-cubanediyl, 2,6,6-trimethylbicyclo[3.1.1]heptane-2,3-diyl, and 1,7,7-trimethylbicyclo[3.1.1]heptane-2,3-diyl. In preferred embodiments, the polycyclic group PCA is an aliphatic tricyclic group, more preferably tricyclo[5.2.1.0 / 2.6]decanylene (TCD) (Formula 2).

[0023] K is preferably selected from the following structures of formulas 14 to 26: TIFF2026515966000004.tif7775 TIFF2026515966000005.tif18287

[0024] Furthermore, K is preferably selected from the following groups: 1,5-naphthylene (from naphthylene 1,5-diisocyanate), 2,4,6-triisopropyl-m-phenylene (from 2,4,6-triisopropyl-m-phenylenediisocyanate), 2,5-bis(methanediylbicyclo[2.2.1]heptane), and 2,6-bis(methanediyl)bicyclo[2.2.1]heptane (from norbornane-2,5-diylbis(methylene)diisocyanate or norbornane-2,6-diylbis(methylene)diisocyanate).

[0025] K is more preferably selected from the structures of formulas 14, 15, 16, 17, 18, 19, and 20.

[0026] In one embodiment, the free radical polymerizable compound is preferably represented by the structure of formula 27: TIFF2026515966000006.tif28140 (Formula 27) [Here, R 2 = hydrogen or methyl group; Sp = A spacer group independently selected from unbranched and branched alkylenes having C1-C19 carbon atoms, wherein the alkylene may further have oxygen atoms, sulfur atoms and / or -OOC- in its carbon chain. Or Sp does not exist; PCA = Each is independently a polycyclic group, preferably an aliphatic polycyclic group, preferably an aliphatic bicyclic or aliphatic tricyclic group, more preferably a tricyclic group, most preferably tricyclo[5.2.1.0 / 2,6]decanylene; K = an aliphatic acyclic saturated or unsaturated unit having C1-C15 carbon atoms, preferably C3-C13 carbon atoms, more preferably C6-C9 carbon atoms, which may be substituted with one or more C1-C3 aliphatic carbon substituents. A polyphatic cyclic saturated or unsaturated unit having C3-C15 carbon atoms, preferably C5-C13 carbon atoms, more preferably C6-C13 carbon atoms, which may be substituted by one or more polyphatic C1-C3 carbon substituents, or Aromatic or aromatic aliphatic unit having C6-C14 carbon atoms, preferably C6-C13 carbon atoms, which may be substituted by one or more aliphatic C1-C3 carbon substituents; r = 1 to 9, preferably 1 to 6.

[0027] Free radical polymerizable compounds are preferably represented by a structure selected from the following formulas 28 to 31: TIFF2026515966000007.tif32136 (Formula 28) TIFF2026515966000008.tif21143 (Formula 29) TIFF2026515966000009.tif23141 (Formula 30) TIFF2026515966000010.tif21137 (Formula 31) [Here, t, u, v, and w are each independently 1 to 9, preferably 1 to 6; and R 2 = Selected from hydrogen and C1-C4 alkyl groups, preferably selected from hydrogen and methyl groups.

[0028] Note that in the case of free radical polymerizable compounds represented by structures selected from formulas 28-31, the opposite orientations of the tricyclo[5.2.1.0 / 2,6]decanylene group are included.

[0029] The present invention further provides a method for preparing a free radical polymerizable compound, characterized by comprising the following steps: a) A step of reacting a diol of a polycyclic group PCA with a (meth)acrylic acid ester to obtain a PCA mono(meth)acrylate having a hydroxyl group by enzyme catalysis, b) A step of reacting the hydroxyl group-containing PCA mono(meth)acrylate from step a) with a diisocyanate compound, preferably using a catalyst.

[0030] The hydroxyl group-containing PCA mono(meth)acrylate reaction product from step a) can be prepared by transesterification of PCA di(meth)acrylate and PCA diol, preferably TCD di(meth)acrylate (TCD D(M)A) and TCD dimethanol. The corresponding mono(meth)acrylate is preferably formed in each case with one (meth)acrylate group and one OH group in a mixture with residues of PCA D(M)A and PCA dimethanol. Surprisingly, this reaction step makes it possible to produce low-color to colorless reaction products, which are clearly different from compounds prepared by acid catalysts that are usually strongly colored, for example. In the case of the latter compounds, more complex washing procedures are generally required before use, at least in areas where appearance is important.

[0031] The reaction (transesterification) in step a) is carried out by enzyme catalysis. The preferred enzyme is lipase or a mixture of lipases. In preferred embodiments, CALB is used. In particularly preferred embodiments, CALB immobilized on a support is used.

[0032] The diol from step a) is preferably selected from primary and secondary alcohols containing a polycyclic group PCA. Suitable primary diols include bis(hydroxymethyl)tricyclo[5.2.1.0 2,6Decane (isomer mixture), 5-norbornene-2,2-dimethanol, 5-norbornene-2,3-dimethanol, bicyclo[2.2.1]heptane-2,3-dimethanol, 2-methyl-3,3-norbornanedimethanol, 2-ethyl-3,3-norbornanedimethanol, 2-propyl-3,3-norbornanedimethanol, 2-butyl-3,3-norbornanedimethanol, bicyclo[2.2.2]octane-1,4-dimethanol, bicyclo[2.2.2]octo-5-ene-5,6-diyldimethanol, bicyclo[2.2.2]octane-2,3-dimethanol, tricyclo[3.3.1.1 3,7 ] Decane-1,3-diethanol, 1,3-adamantanedimethanol, pentacyclopentadecanedimethanol, tetracyclo[6.6.2.0 2,7 .0 9,14 The following may be used: hexadeca-2,4,6,9,11,13-hexaene-15,16-diyldimethanol, 1,4-bis(hydroxymethyl)cubane, and [5-(hydroxymethyl)-5,6-dimethyl-6-bicyclo[2.2.1]hept-2-enyl]methanol. Suitable secondary diols include bicyclo[2.2.1]hept-2-ene-1,2-diol, bicyclo[2.2.1]heptane-1,2-diol, bicyclo[2.2.1]heptane-2,5-diol, bicyclo[2.2.1]heptane-1,4-diol, 2,6,6-trimethylbicyclo(3.1.1)heptane-2,3-diol, 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diol, 2,3-dihydroxynorbornane, 2-(propyl-1,2-diol)norbornane, tricyclo[5.2.1.0 2,6 These may be decane-3,4-diol and 2,6-dihydroxyadamantane. Commercially available diols are generally available.

[0033] The (meth)acrylic acid ester from step a) is preferably selected from alkyl esters, vinyl esters, aryl esters, and further active esters. Both mono(meth)acrylates and di(meth)acrylates can be used. In the case of mono(meth)acrylates, it is preferable to remove the resulting monoalcohol from the mixture during the reaction. In the case of di(meth)acrylates, it is preferable to use the di(meth)acryloyl ester of the PCA diol. In this case, the resulting products are the mono(meth)acryloyl ester of the PCA diol and the di(meth)acryloyl ester of the PCA diol in a mixture with the diol. It is particularly advantageous that this mixture is especially low in color and contains a high proportion of mono(meth)acrylate, which is preferable in the subsequent reaction in step b).

[0034] A catalyst can be used for step b). A suitable catalyst in step b) is preferably a urethane catalyst. Such a catalyst accelerates the reaction rate between the hydroxyl group and the isocyanate group. Examples of urethane catalysts include organotin compounds such as dimethyltin dineodecanoate, dibutyltin dilaurate, dibutyltin diocate, and tin octoate; organobismuth compounds such as bismuth neodecanoate; and copper naphthenate, cobalt naphthenate, zinc naphthenate, acetylacetonatozirconium, acetylacelacetonatoiron, and acetylacetonatogermanium. Examples include organic compounds of metals other than tin; triethylamine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undecene, N,N-dimethylcyclohexylamine, pyridine, N-methylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N,N',N'-pentamethyldiethylenetriamine, N,N,N',N'-tetra(340-dimethylaminopropyl)methanediamine, N,N'-dimethylpiperazine, 1,2-dimethylimidazole, and other amine compounds and their salts; and trialkylphosphine compounds such as tri-n-butylphosphine, tri-n-hexylphosphine, tricyclohexylphosphine, and tri-n-octylphosphine. Here, dibutyltin dilaurate, dimethyltin dineodecanoate, and bismuth neodecanoate are preferred.

[0035] The diisocyanate compound used in step b) is preferably selected from diisocyanates containing aliphatic, alicyclic, polycyclic, aromatic aliphatic, or aromatic structural elements. Suitable diisocyanate compounds include 4,4'-methylenediphenyl diisocyanate (MDI), 4-methyl-m-phenylenediisocyanate and other isomers (TDI), 1,5-naphthylenediisocyanate (NDI), 1,3-bis(isocyanatomethyl)benzene (XDI), 1,3-bis(1-isocyanato-1-methylethyl)benzene (TMXDI), 2,4,6-triisopropyl-m-phenylenediisocyanate (TRIDI), 3,3'-dimethylbiphenyl-4,4'-diyldiisocyanate (TODI), 1,4-phenylenediisocyanate, hexamethylenediisocyanate (HDI), 2,2 These may be 4- and 2,4,4-trimethylhexamethylene 1,6-diisocyanate (TMDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate and other isomers (IPDI), 4,4'-methylenedicyclohexyl diisocyanate (H12MDI), 2,5- and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (NBDI), 1,4-cyclohexane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane (BIMC), and octahydro-2,5-bis(isocyanatomethyl)-4,7-methano-1H-indene (TCDDI). In general, diisocyanate compounds are commercially available.

[0036] The ratio of the number of moles of hydroxyl groups in PCA mono(meth)acrylate to the number of moles of isocyanate groups in the diisocyanate compound is preferably 0.5 to 1.5, and more preferably 0.8 to 1.2. Even more preferably, this ratio is 1.0. The ratio of the total amount of hydroxyl groups to the total amount of isocyanate groups in the reaction in step b) is preferably 1.1 to 1.0, and more preferably 1.02 to 1.0.

[0037] The conversion or reaction in steps a) and b) can be carried out in an inert solvent or a solvent mixture, or possibly without a solvent.

[0038] The solvent used in step a) can be a wide variety of solvents, as long as they are inert to the reaction. Examples include nonpolar hydrocarbon solvents such as n-hexane, benzene, toluene, and xylene; nonpolar halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and perchloroethylene; medium-polar ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; medium-polar ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran, and dioxane; and polar solvents such as acetonitrile, tert-butyl alcohol, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidinone, dimethyl sulfoxide, and sulfolane. These solvents may be used individually or in mixtures. Nonpolar and medium-polar solvents are preferred.

[0039] The solvent used in step b) can be any variety of solvents as long as they are inert to the reaction. Examples include hydrocarbon solvents such as n-hexane, benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran, and dioxane; halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and perchloroethylene; and polar solvents such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidinone, dimethyl sulfoxide, and sulfolane. These solvents may be used individually or in mixtures.

[0040] The reactions in steps a) and b) can be carried out within a temperature range of 0°C to 100°C. A temperature range of 20°C to 80°C is preferred, and more preferably 40°C to 60°C.

[0041] The reactions in steps a) and b) can be carried out in the presence of a polymerization inhibitor. The polymerization inhibitor prevents free radical polymerization of the indicated (meth)acrylate group. Examples of polymerization inhibitors include 2,6-di-tert-butyl-4-methylphenol (BHT), hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO), and phenothiazine (PTZ).

[0042] After step b), it may be necessary, in some cases, to remove any remaining solvent from the resulting reaction mixture in a further step c).

[0043] The present invention further provides free radical polymerizable compositions comprising the following: a) One or more free radical polymerizable compounds according to any one of claims 1 to 7 of the present invention; b) Optionally, one or more further free radical polymerizable monomers and / or oligomers not covered by at least one free radical polymerizable compound of Formula 1; c) Optionally, at least one initiator or initiator system for polymerization; d) One or more stabilizers, at the discretion of the party; e) One or more fillers, at the discretion of the user; f) Optionally, conventional dental additives.

[0044] It is preferable that one or more free radical polymerizable compounds of formula 1 are present in the free radical polymerizable composition in a mass ratio of 1 to 100% by weight, preferably 2 to 80% by weight, preferably 2 to 65% by weight, and more preferably 10 to 65% by weight, based on the total mass of all free radical polymerizable monomers and oligomers in the polymerizable composition.

[0045] The free radical polymerizable composition preferably comprises several compounds of formula 1, selected from monomers (n=1) and / or oligomers (n=2 to 9, preferably n=2 to 5).

[0046] One or more of the following components may be present in the free radical polymerizable composition in the following mass proportions, based on the total mass of the polymerizable composition: a) One or more free radical polymerizable compounds of formula 1: 1% to 99% by weight, preferably 2% to 95% by weight, more preferably 2% to 80% by weight, even more preferably 2% to 65% by weight, and even more preferably 10% to 65% by weight; b) One or more other free radical polymerizable monomers or oligomers not covered by at least one compound of formula 1: 0% to 99% by weight, more preferably 10% to 99% by weight, more preferably 20% to 98% by weight, and even more preferably 35% to 90% by weight; c) At least one initiator or initiator system for polymerization: 0% to 5% by weight, preferably 0.01% to 5% by weight; d) Stabilizer: 0% to 5% by weight, preferably 0.001% to 5% by weight, more preferably 0.005% to 2% by weight; e) - Filler or filler particles: 0% to 95% by weight, preferably 1% to 95% by weight, more preferably 5% to 92% by weight; f) Conventional dental additives: 0% to 5% by weight, preferably 0.001% to 5% by weight.

[0047] In a preferred embodiment, the free radical polymerizable composition is a free radical polymerizable dental material.

[0048] b) Further polymerizable monomers or oligomers The free radical polymerizable composition may contain, in addition to at least one free radical polymerizable compound of formula 1, one or more further free radical polymerizable monomers or oligomers not covered by at least one free radical polymerizable compound of formula 1.

[0049] The selection of these further free-radical polymerizable monomers and oligomers is preferably made depending on which material is to be produced. This also applies to the proportion of further free-radical polymerizable monomers and / or oligomers in the free-radical polymerizable composition.

[0050] Suitable further free-radical polymerizable monomers are selected from, for example, bis(methacryloyloxymethyl)tricyclo[5.2.1.0 / 2,6]decane and bis(acryloyloxymethyl)tricyclo[5.2.1.0 / 2,6]decane. The monomers may be obtained by esterification reactions, for example, according to the production examples in EP 0235836 B1 or US 4131729 / DE 2816823.

[0051] Suitable further free-radical polymerizable monomers can be selected from urethane (meth)acrylates having two or more (meth)acrylate groups. These are preferably urethane di(meth)acrylates and / or urethane tri(meth)acrylates. The urethane (meth)acrylates are preferably selected from linear or branched alkylene-functionalized urethane (meth)acrylates and urethane (meth)acrylate-functionalized polyethers.

[0052] A bifunctional urethane (meth)acrylate selected from a bifunctional urethane (meth)acrylate having a divalent alkylene group and a bifunctional urethane (meth)acrylate having a divalent cyclic aliphatic hydrocarbon group is preferred. Such a bifunctional urethane (meth)acrylate having a divalent alkylene group is preferably selected from a linear or branched urethane di(meth)acrylate functionalized with a divalent alkylene group, or a urethane di(meth)acrylate-functionalized polyether having an alkylene group (e.g., bis(methacryloyloxy-2-ethoxycarbonylamino)alkylene, bis(methacryloyloxy-2-ethoxycarbonylamino)-substituted polyalkylene ether, etc.). A bis(methacryloyloxy-2-ethoxycarbonylamino)alkylene containing a linear or branched C3-C20 alkylene group, preferably a C3-C9 alkylene group, is preferred. Particularly preferred is an alkylene substituted with a methyl group.

[0053] Furthermore, additional free radical polymerizable monomers may be reaction products of 3-hydroxypropyl methacrylate and trimethylhexamethylene diisocyanate, or reaction products of 3-hydroxypropyl acrylate and trimethylhexamethylene diisocyanate.

[0054] Further suitable free-radical polymerizable monomers are available, for example, under the following trade names or brand names: Ebecryl 230 (aliphatic urethane diacrylate), Actilane 9290, Craynor 9200 (diurethane acrylate oligomer), Ebecryl 210 (aromatic urethane diacrylate oligomer), Ebecryl 270 (aliphatic urethane diacrylate oligomer), Actilane 165, Actilane 250, Photomer 6210 (aliphatic urethane diacrylate), Photomer 6623 (hexafunctional aliphatic urethane resin), Photomer 6891 (aliphatic urethane triacrylate), UDMA, Roskydal LS 2258 (aliphatic urethane acrylate oligomer), Roskydal XP 2513 (unsaturated aliphatic urethane acrylate), Genomer 4256, Genomer 4267 (urethane acrylate), Genomer 4259 (aliphatic urethane dimethacrylate), RCX 18-059 (aliphatic urethane dimethacrylate), UN 1963 CG (aliphatic urethane methacrylate), CN 1993 CG (aliphatic urethane methacrylate), PRO 21252 (aliphatic urethane acrylate), H1391 (hydroxypropyl urethane dimethacrylate), H1391 (urethane dimethacrylate), X851-1066 (urethane dimethacrylate IP-DI), X726-000 (PEG 400 elongated urethane dimethacrylate), urethane methacrylate 11-70 and urethane methacrylate 14-774.

[0055] Particularly preferred is a further free radical polymerizable monomer having the structure of the following formula 32: PG'-Sp'-PCA'-Sp'-PG (Equation 32) [Here, PG = Each is independently selected from free radical polymerizable groups, preferably (NR 3 )OC-CR 4 =CH2 and OOC-CR4=CH2 are selected, and more preferably OOC-CR 4 Selected from =CH2, R3 = Selected from hydrogen, C1-C8 alkyl groups, aryl groups, and aromatic aliphatic groups having C6-C8 carbon atoms, preferably selected from C1-C8 alkyl groups and benzyl groups; R 4 = Selected from hydrogen, C1-C4 alkyl groups, preferably selected from hydrogen and methyl groups; Sp' = A spacer group selected from unbranched and branched alkylenes having C1 to C19 carbon atoms, each independently containing an oxygen atom, a sulfur atom and / or -OOC- in the carbon chain, preferably a spacer group selected from methylene, *CH2-(OC2H4)q, *CH2-(OC3H6)q, where q=1 to 5 and the * symbol indicates the bond position to PCA'. Or Sp' does not exist; Each PCA' is independently a polycyclic group, preferably an aliphatic polycyclic group, preferably an aliphatic bicyclic or tricyclic group, more preferably a tricyclic group, and most preferably tricyclo[5.2.1.0 / 2,6]decanylene.

[0056] The monomer of formula 32 may be, in particular, bis(methacryloyloxymethyl)tricyclo[5.2.1.0 / 2,6]decane and bis(acryloyloxymethyl)tricyclo[5.2.1.0 / 2,6]decane.

[0057] Suitable further free radical polymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate or isobornyl (meth)acrylate, p-cumylphenoxyethylene glycol methacrylate, bisphenol A di(meth)acrylate, bis-GMA, ethoxy or propoxylated bisphenol A dimethacrylate having three ethoxy groups (e.g., SR-348). c(Sartomer)), 2,2-bis[4-(2-methacryloyloxypropoxy)phenyl]propane, di-, tri- and tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol dimethacrylate and glycerol trimethacrylate, 1,4-butanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and 1,12-dodecanediol di(meth)acrylate. Preferred monomers are 1,6-hexanediol dimethacrylate, benzyl methacrylate, tetrahydrofurfuryl methacrylate or isobornyl methacrylate, p-cumylphenoxyethylene glycol methacrylate, 2,2-bis[4-(2-methacryloyloxypropoxy)phenyl]propane, bis-GMA, and SR-348C(Sartomer).

[0058] Suitable further free radical polymerizable monomers can be selected from, for example, N-monosubstituted and N-disubstituted acrylamides (such as N-ethylacrylamide and N,N-dimethacrylamide), and bisacrylamides (such as N,N'-diethyl-1,3-bis(acrylamide)propane, 1,3-bis(methacrylamide)propane, 1,4-bis(acrylamide)butane, and 1,4-bis(acryloyl)piperazine).

[0059] The free radical polymerizable composition preferably comprises a further radical polymerizable monomer or oligomer, the viscosity of which is lower than that of the free radical polymerizable compound represented by the structure of Formula 1. In such cases, the further free radical polymerizable monomer or oligomer is called a diluent. The diluent preferably has a viscosity of less than 10 Pa·s, more preferably less than 5 Pa·s, and more preferably less than 1 Pa·s. This is particularly preferable and advantageous for the production of materials by tank-based photopolymerization.

[0060] Preferably, the free radical polymerizable composition contains one or more further free radical polymerizable monomers or oligomers not covered by at least one compound of formula 1, in a mass proportion of 0% to 99% by weight, preferably 10% to 99% by weight, more preferably 20% to 98% by weight, and even more preferably 35% to 90% by weight, based on the total mass of the polymerizable composition.

[0061] In certain embodiments, the composition is preferably free from any monomer or oligomer having a bisphenol A structure. In particular, it is free from 2,2-bis[4-(2-hydroxy-3-(meth)acryloyloxypropoxy)phenyl]propane (bis-GMA) and / or ethoxylated bisphenol A di(meth)acrylate (bis-EMA).

[0062] For dental adhesives or self-adhesive composite cements, it is possible to use acidic monomers and / or water-soluble monomers in particular. Typical proportions of acidic monomers are known from the prior art. Acidic monomers are compounds having an acidic group and a free-radical polymerizable group in one molecule. Examples of free-radical polymerizable unsaturated groups include (meth)acryloyl, (meth)acrylamide, styryl, vinyl, and allyl groups. Examples of acidic groups that may be representative of acidic monomers include carboxylic acids, carboxylic acid anhydrides, phosphates, thiophosphates, pyrophosphates, thiopyrophosphates, phosphonates, thiophosphonates, and sulfonate groups. The acidic group may exist in the form of acid chlorides, alkali metal salts, alkaline earth metal salts, or ammonium salts. Suitable acidic monomers include, for example, 2-(methacryloyloxyethyl)phenyl hydrogen phosphate (phenyl-P); 2-hydroxyethyl methacryloyl dihydrogen phosphate (HEMA phosphate); dipentaerythritol pentamethacrylate phosphate (PENTA); di-2-hydroxyethyl methacryloyl hydrogen phosphate (di-HEMA phosphate); 10-methacryloyloxydecyl dihydrogen phosphate (MDP); 1,3-glycerol dimethacrylate phosphate (GDMAP), 2,5-di Examples include methacryloyloxyethyloxycarbonyl-1,4-benzenedicarboxylic acid (PMDM), butane-1,2,3,4-tetracarboxylic acid di(2-hydroxyethyl methacryloyl) ester (TCB), 4-methacryloyloxyethyl trimellitic acid (4-META), 4-methacryloyloxyethyl trimellitic anhydride (4-META), pyromellitic acid bis(glycerol dimethacrylate) (PMGDM), and 11-methacryloyloxy-1,1-undecanedicarboxylic acid (MAC-10).

[0063] Furthermore, the additional monomers used may be free radical polymerizable antimicrobial monomers.

[0064] c) Initiator or initiator system Suitable initiators or initiator systems can initiate free radical polymerization reactions. Such initiators and initiator systems are known to those skilled in the art.

[0065] The initiator system comprises at least one initiator, at least one further compound, and, for example, a co-initiator. These can be separated among different components of the polymerizable dental material. The dental material of the present invention can be cured thermally, chemically, or photochemically, i.e., by irradiation with UV and / or visible light.

[0066] Suitable initiators may be, for example, photoinitiators. These are characterized by their ability to bring about the curing of the material by absorbing light in the wavelength range of 300 nm to 700 nm, preferably 350 nm to 600 nm, more preferably 380 nm to 500 nm, and optionally through additional reactions with one or more coinitiators. Here, it is preferable to use, for example, phosphine oxides, acylphosphine oxides, bisacylphosphine oxides and their derivatives, acylgermanes, acylsilanes and tin compounds, benzoin ethers, benzyl ketals, acetophenones, benzophenones, thioxanthones, bisimidazoles, metallocenes, fluorones, α-dicarbonyl compounds, aryldiazonium salts, arylsulfonium salts, aryliodonium salts, ferrocenium salts, phenylphosphonium salts or mixtures thereof, as described in EP2649981A1, 2017 / 055209A1, WO2017 / 060527A1, EP3068363A1, US2020 / 0087329A1, EP3868767A1, EP3293215A1 and EP3153150A1.

[0067] Particularly preferred are diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, benzoin, benzoin alkyl ether, benzyl dialkyl ketal, α-hydroxyacetophenone, dialkoxyacetophenone, α-aminoacetophenone, isopropylthioxanthone, camphorquinone, phenylpropanedione, 5,7-diiodo-3-butoxy-6-fluorone, (η 6 -Kumen)(η 5 -Cyclopentadienyl)iron hexafluorophosphate, (η 6 -Kumen)(η 5 -Cyclopentadienyl)irone tetrafluoroborate, (η 6 -Kumen)(η 5 -Cyclopentadienyl) iron hexafluoroantimonate, substituted diaryliodonium salts, triarylsulfonium salts, or mixtures thereof.

[0068] The co-initiators used for photochemical curing are preferably tertiary amines, borates, organophosphites, diaryliodonium compounds, thioxanthones, xanthenes, fluorenes, fluorones, α-dicarbonyl compounds, dicarbonyl compounds as described in WO2021 / 048313A1, condensed polycyclic aromatics, or mixtures thereof. Particularly preferred are N,N-dimethyl-p-toluidine, N,N-dialkylalkylaniline, N,N-dihydroxyethyl-p-toluidine, 2-ethylhexyl p-(dimethylamino)benzoate, ethyl p-(dimethylamino)benzoate, butyrylcholine triphenylbutyl borate, or mixtures thereof.

[0069] The initiator used may be a so-called thermal initiator, which can cause the material to harden by absorbing thermal energy at high temperatures. Preferably, inorganic and / or organic peroxides, inorganic and / or organic hydroperoxides, diethyl α,α'-azobisisobutyrate, α,α'-azobis(isobutyronitrile), benzpinacol, or mixtures of these compounds are used. Particularly preferred are diacyl peroxides (e.g., benzoyl peroxide or lauroyl peroxide), cumene hydroperoxide, benzpinacol, 2,2'-dimethylbenzopinacol, or mixtures of these compounds.

[0070] For chemical curing at room temperature, a redox initiator system consisting of one or more initiators and one or more co-initiators functioning as activators is commonly used. For reasons of storage stability, the individual components of the initiator system are incorporated into spatially separated components of the dental material of the present invention, i.e., the material is a multi-component material, preferably a two-component material. The initiators used are preferably inorganic and / or organic peroxides, inorganic and / or organic hydroperoxides, barbituric acid derivatives, malonyl sulfamides, protic acids, Lewis acids or Brønsted acids or compounds that release such acids, carbenium ion donors, e.g., methyl triflate or triethyl perchlorate or mixtures of the above compounds. The co-initiators used are preferably tertiary amines, heavy metal compounds, particularly compounds of Group 8 and Group 9 of the periodic table ("iron and copper groups"), compounds containing ionogenically bonded halogens or pseudohalogens, e.g., quaternary ammonium halides, weak Brønsted acids, e.g., alcohols and water, or mixtures of these compounds.

[0071] The dental materials of the present invention may also include any conceivable combination of the initiators and co-initiators described above. The above examples are known as dual-curing dental materials, which include both a photoinitiator and optionally a corresponding co-initiator for photochemical curing, and an initiator and a corresponding co-initiator for chemical curing at room temperature.

[0072] The polymerizable composition or polymerizable dental material is preferably photocurable. In a preferred embodiment, the polymerizable composition includes an initiator system that initiates free radical polymerization in the wavelength range of 395 to 700 nm, preferably 400 to 500 nm. The preferred initiator system contains camphorquinone (CQ) as the initiator and a tertiary aromatic amine and an aliphatic amine as co-initiators. The preferred aliphatic amine is N,N-(dimethylamino)ethyl (meth)acrylate. The preferred aromatic co-initiator is an aromatic amine, such as 2-ethylhexyl p-(dimethylamino)benzoate (EHA) or ethyl p-(dimethylamino)benzoate (EDAB). In addition to camphorquinone and the tertiary amine, the photoinitiator system may also contain a further synergist. Preferred synergists may be diaryliodonium salts such as EP3427716A1, EP3888616A1, EP3881818A1, and M. Topa, J. Ortyl (J. Horton), Materials 13, 4093 (2020).

[0073] In another preferred embodiment particularly suitable for 3D printing applications, the dental material of the present invention contains an initiator system that initiates free radical polymerization in the wavelength range of 300 to 500 nm, preferably 350 to 420 nm, and particularly preferably 365 to 410 nm. The preferred type of initiator is one that acts by a Norrish type 1 mechanism.

[0074] At least one initiator or initiator system for polymerization may be present in the polymerizable composition in a mass ratio of 0% to 5% by weight, preferably 0.01% to 5% by weight, based on the total mass of the polymerizable composition.

[0075] d) Stabilizers The free radical polymerizable composition may contain one or more stabilizers. Such stabilizers are known to those skilled in the art.

[0076] Suitable stabilizers are preferably benzotriazole, triazine, benzophenone, cyanoacrylate, salicylic acid derivatives, hindered amine light stabilizers (HALS), and mixtures thereof.The following are particularly suitable: o-hydroxyphenylbenzotriazoles, e.g., 2-2H-benzotriazole-2-yl-4-methylphenol, 2-(5-chloro-2H-benzotriazole-2-yl)-4-methyl-6-tert-butylphenol, 2-(5-chloro-2H-benzotriazole-2-yl)-4,6-di-tert-butylphenol, 2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol, 2-(2H-benzotriazole-2-yl)-4-methyl-6-dodecyl Phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, and 3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxybenzenepropanoate, o-hydroxyphenyltriazine For example, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine or 2-(2-hydroxy-4-[2-hydroxy-3-dodecyloxypropyloxy]phenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine, o-hydroxybenzophenone, for example 2-hydroxy-4-octyloxybenzophenone, cyanoacrylate, for example ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate and tetrakis[(2-cyano-3,3-diphenylacryloyl)oxymethyl]methane, hindered amine light stabilizers (HALS), such as N,N'-bisformyl-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, salicylic acid esters and mixtures thereof.

[0077] Further suitable stabilizers include phenols such as hydroquinone monomethyl ether (HQME), 2,6-di-tert-butyl-4-methylphenol (BHT), or tert-butylhydroxyanisole (BHA). The stabilizer used may be 2,6-di-tert-butyl-4-methylphenol (BHT) in particular.

[0078] The stabilizer may be present in the free radical polymerizable composition in a mass ratio of 0% to 5% by weight, preferably 0.001% to 5% by weight, and more preferably 0.005% to 2% by weight, relative to the total mass of the polymerizable composition.

[0079] In one embodiment, the free radical polymerizable composition may contain stabilized free radicals. Suitable stabilized free radicals are preferably 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) and bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl) sebacate. Bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl) sebacate is particularly preferred.

[0080] The stabilized free radicals are preferably present in the free radical (photo) polymerizable composition in a mass proportion of 0.005% to 0.01% by weight, based on the total mass of the polymerizable composition.

[0081] e) Fillers The free radical polymerizable composition may contain a filler or filler particles. The filler particles are not defined as having a specific particle shape. Instead, fillers having spherical, flake-like, plate-like, needle-like, leaf-like, or irregular shapes can be very useful. The average particle size of the filler particles is preferably 5 nm to 100 μm, and more preferably 5 nm to 50 μm.

[0082] Suitable fillers can be selected from a wide variety of materials commonly used in dental materials or products. The choice of filler allows for adjustment of, for example, the fluidity, viscosity, consistency, color, radiopaqueness, and mechanical stability of the composition or dental material. Fillers can be broadly classified into three distinct classes according to their chemical properties: inorganic fillers, organic fillers, and organic-inorganic composite fillers. Fillers can be used individually or in combination with each other.

[0083] As inorganic fillers, ground powders of natural or synthetic glass, or crystalline inorganic materials of various sizes and states (monodisperse, polydisperse) may be used. Suitable materials include quartz, cristobalite, glass ceramics, feldspar, barium silicate glass (e.g., available under the trade names Kimble Ray-Sorb T3000, Schott 8235, Schott GM27884, Schott G018-053, and Schott GM39923), barium fluorosilicate glass, strontium silicate glass, strontium borosilicate glass (e.g., available under the trade names Ray-Sorb T4000, Schott G018-093, Schott G018-163, and Schott GM32087), lithium aluminosilicate glass, barium glass, calcium silicate, sodium aluminosilicate, and fluoroaluminosilicate glass (e.g., Schott G018-091 and Schott Examples include zirconium or cesium boroaluminosilicate glass (available under the trade name G018-117), zeolite, and apatite. The filler preferably has a median particle size d50 of 0.01 to 15 μm, preferably 0.2 to 5 μm, and more preferably 0.2 to 1.5 μm. A median particle size d50 of 0.1 to 0.5 μm may be preferred. In this case, it is particularly preferred that the median particle size d90 be less than 1.0 μm. Furthermore, discrete, non-aggregated, non-aggregated, organically surface-modified nanoparticles can be used to achieve more uniform filling of the dental material and increase hardness and wear resistance.

[0084] In this context, nanoparticles refer to spherical particles having a median particle size of less than 200 nm. The median particle size is preferably less than 100 nm, more preferably less than 60 nm. The smaller the nanoparticles, the better they can perform the function of filling cavities between coarser particles. The material of the nanoparticles is preferably an oxide or mixed oxide, preferably selected from the group consisting of oxides and mixed oxides of the elements silicon, titanium, yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, ytterbium, lanthanum, cerium, and aluminum, as well as mixtures thereof. Preferred oxide nanoparticles are non-aggregated. To enable good integration of nanoparticles into the polymer matrix of the composite material, the surface of the nanoparticles is organically modified. The filler is preferably surface-treated with a silanizing agent. A particularly preferred adhesion promoter is methacryloyloxypropyltrimethoxysilane. Commercially available nanoscale non-aggregating and non-coagulating silica sols that can be used are, for example, marketed under the names "Nalco Colloidal Silicas" (Nalco Chemical Co.), "Ludox colloidal silica" (Grace), or "Highlink OG" (Clariant).

[0085] Submicron or microfillers consisting of aggregated nanoscale particles, particularly those with a specific surface area (determined by the Brunauer-Emmett-Teller method) of 100-400 m², are also considered. 2It can be used similarly if it is in the range of / g. Fumed silica or wet-settled silica is preferred. Suitable non-surface-treated silicon dioxide filler products that can be used are commercially available under the names Aerosil™ ("OX50", "90", "130", "150", "200", "300", "380", and "R8200" from Evonik Industries (AG, Essen, Germany)), Cab-O-Sil ("LM-150", "M-5", "H-5", and "EH-5" from Cabot Corp. (Tuscola, IL)), HDK™ ("S13", "V15", "N20", "T30", and "T40" from Wacker-Chemie AG (Munich, Germany)), and Orisil™ ("200", "300", "380", Orisil (Toshiba) (Liviv, Ukraine)).

[0086] Particularly advantageous abrasion resistance and gloss resistance of compositions or dental materials can be achieved by using aggregated nanoscale particles based on a mixed oxide of silicon dioxide and zirconium dioxide. Suitable fillers can be manufactured, for example, by the method described in U.S. Patent No. 6730156 (Example A). Fillers thus manufactured can then be surface-treated by a method as described in U.S. Patent No. 6730156 (e.g., Manufacturing Example B).

[0087] To achieve high filler content along with good aesthetics and wear stability, it may be particularly advantageous to use spherical submicroparticles based on silicon-zirconium mixed oxide, such as those described in DE 19524362 A1 or US2020 / 0121564 A1.

[0088] The aggregated filler preferably has a median particle size of 1 to 15 μm, more preferably 1 to 10 μm, and more preferably 2 to 5 μm.

[0089] A considerable amount of selected radiopaque fillers may be present. The addition of radiopaque particles to polymerizable compositions or dental materials is advantageous because it allows for differentiation between the hard material of healthy teeth and the restoration. Suitable radiopaque fillers include particles of metal oxides, metal fluorides, or barium sulfate. Oxides and fluorides of heavy metals with atomic numbers greater than 28 are preferred. Metal oxides and fluorides should be selected so as not to affect the color of the restoration as much as possible. Metal oxides and fluorides with atomic numbers greater than 30 are more preferred. Suitable metal oxides are oxides of yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, lanthanides (elements with atomic numbers 57-71), cerium, and combinations thereof. Suitable metal fluorides are, for example, yttrium trifluoride and ytterbium trifluoride. Particularly preferred here are irregularly shaped or spherical YbF3 or YF3 particles having an average primary particle diameter of 40 nm to 1.5 μm, more preferably core-shell combination products having a YF3 or YbF3 core and an SiO2 shell, and very particularly preferred, the surface of the SiO2 shell is silanized. In particular, such core-shell combination products have a refractive index of 1.48 to 1.54 and a median particle size of aggregated particles of 0.5 to 5 μm.

[0090] Examples of suitable organic fillers include filled and unfilled powdered polymers or copolymers based on polymethyl methacrylate (PMMA), polyethylene methacrylate, polypropylene methacrylate, polybutyl methacrylate (PBMA), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyurethane (PU), polyurea, methyl methacrylate-ethyl methacrylate copolymer, ethylene-vinyl acetate copolymer, and styrene-butadiene copolymer. Organic fillers may also contain physiologically active ingredients, specific pigments, polymerization initiators, stabilizers, etc., added during the manufacturing process. Organic fillers can be used alone or in mixtures.

[0091] When using so-called organic-inorganic composite fillers, advantageous polishing properties can be achieved in the composition or dental material in conjunction with a higher filler level. These fillers can be manufactured by forming a paste with polymerizable monomers and inorganic fillers, polymerizing and curing it, and then finely grinding it before use as a filler. Here, it is preferable to use microfillers as the inorganic fillers. After grinding, the fillers preferably have a median particle size of 0.05 to 100 μm, more preferably 0.5 to 50 μm, and even more preferably 1 to 30 μm.

[0092] The median particle size is preferably determined by static and / or dynamic light scattering by particles in a dispersion using a suitable dispersant (e.g., Coulter LS, Beckman Coulter GmbH, Krefeld, Germany, and / or, e.g., Zetasizer, Malvern Panalytical GmbH, Kassel, Germany). Other methods particularly preferred for this purpose are field-flow fractionation (e.g., AF2000 AT, Postnova Analytics GmbH, Landsberg, Germany) or calibration using particle size standards. The median particle size can also be determined by microscopy, particularly electron microscopy. The reported value is preferably the absolute particle size, preferably the d50 value.

[0093] The filler is preferably surface-modified in the free-radical polymerizable composition or in the dental material. This is done, for example, by subjecting the inorganic or organic-inorganic composite filler to surface treatment before use, which improves compatibility, affinity, and integration of the filler into the resin mixture. This treatment organically modifies the surface of the inorganic particles, i.e., the surface has organic structural elements. All methods known to those skilled in the art can be used here. Silanating agents are preferred in inorganic fillers having surface OH groups. Examples include γ-methacryloyloxyalkyltrimethoxysilane (number of carbon atoms between the methacryloyloxy group and the silicon atom: 3 to 12), γ-methacryloyloxyalkyltriethoxysilane (number of carbon atoms between the methacryloyloxy group and the silicon atom: 3 to 12), or silicone compounds such as vinyltrimethoxysilane, vinylethoxysilane, and vinyltriacetoxysilane. The silanating agent is particularly preferably methacryloyloxypropyltrimethoxysilane.

[0094] Inorganic fillers having few or no surface OH groups are preferably used with various surface modifiers, such as titanates, aluminates, zircoaluminates, surfactants, fatty acids, organic acids, inorganic acids, or metal alkoxides, which are surface-treated with these agents. Surface modifiers for barium, strontium, and rare earth metal salts are particularly preferably organic compounds having N-, P-, S, and / or O-containing functional groups (e.g., polyols, sulfoxides, phosphinic acid esters, phosphonic acid esters, trialkylphosphines, carboxylic acids, and carboxylic acid esters). In this case, 10-methacryloyloxydecyl dihydrogen phosphate is particularly suitable.

[0095] In particular, in the case of aggregated silicon dioxide-based nanofillers, surface modification can consist of groups that are reactive to free radicals, such as the methacryloyloxyalkyl groups mentioned above, or groups that are inactive to free radicals. Suitable inactive groups include, for example, trimethylsilyl groups, dimethylsilylene groups, or methylsilylidene groups, which can be applied to the surface by silanization using, for example, hexamethyldisilazane, dimethyldimethoxysilane, or methyltrimethoxysilane. Suitable inactive surface-modified aggregated nanofillers are commercially available under the names Aerosil R8200, Aerosil R812S, Aerosil R805, Aerosil R202, and Aerosil R974 (Evonik Industries AG, Essen, Germany) or HDKH2000 and HDKH200 / 4 (Wacker Chemie, Burghausen, Germany). More preferably, the aggregated nanofillers may be modified with a group that is reactive in the free radical process, such as a methacryloyl group. A commercially available aggregated nanofiller product modified to be reactive to free radicals is available under the name Aerosil R7200 (Evonik Industries AG, Essen, Germany).

[0096] The aggregated nanofillers may preferably exist in a mostly deaggregated form, as described, for example, in EP 1720206.

[0097] The free radical polymerizable composition of the present invention may contain a filler or filler particles in a mass proportion of 0% to 95% by weight, preferably 1% to 95% by weight, more preferably 5% to 92% by weight, and even more preferably 15% to 85% by weight, based on the total mass of the polymerizable composition.

[0098] The amount of filler fraction may be selected according to the indication of the dental product. For example, the maximum amount of filler may be used for rigid, modelable filling composites, for dental compositions for manufacturing inlays, onlays, or overlays, and for compositions for manufacturing dental CAD-CAM materials. These compositions generally have a filler content of 75% to 92% by weight relative to the total composition. Free-flow dental composites, luting composites, core build-up materials, crown materials, and bridge materials generally have an average filler content ranging from 40% to 80% by weight relative to the total composition. On the other hand, dental lacquers, dental sealing materials, dental fusion materials, or dental adhesives use fillers in a content ranging from 1% to 40% by weight relative to the total composition. The above filler content ranges should be understood as guideline values ​​only, and deviations from these are possible depending on the selected filler.

[0099] In a preferred embodiment, the free radical polymerizable composition contains microfillers selected such that the difference in refractive index between the microfillers and the remaining components of the polymerization composition (polymer matrix) is minimized. Preferably, Δn ≤ 0.03, more preferably ≤ 0.02, and more preferably ≤ 0.01.

[0100] f) Conventional dental additives The free radical polymerizable composition may contain further dental additives. Suitable conventional dental additives are preferably those that may be present in free radical polymerizable dental and orthodontic materials. Conventional dental additives are known to those skilled in the art.

[0101] Conventional dental additives used may include, for example, solvents or solvent mixtures. For example, for the manufacture of dental adhesives, it is preferable to use a mixture of water and a water-miscible solvent (e.g., ethanol or acetone).

[0102] Furthermore, additional components of the free radical polymerizable composition may be pharmacologically active compounds, such as antimicrobial compounds, chlorhexidine, or other enzyme inhibitory substances.

[0103] Conventional dental additives present in the composition may contain one or more fluoride-releasing substances in the form of fine particles. The fluoride-releasing substances may be water-soluble fluorides such as sodium fluoride or fluoramine fluorides. Other suitable fluoride-releasing substances are mainly sparingly soluble fluorides of Group 2. Fluoride-containing glass is also a suitable source of fluoride.

[0104] Other suitable additives are particulate materials that release calcium and / or phosphates and thus have a remineralizing effect. Suitable remineralizing materials are calcium phosphate compounds such as hydroxyapatite, bruscheit, monocalcium phosphate, fluoroapatite, and bioactive glass as described in DE10111449A1, DE102005053954A1, or US9517186B2.

[0105] The dental material of the present invention may contain a coloring agent or a mixture of coloring agents selected from fluorescent dyes, fluorescent pigments, organic coloring pigments, inorganic coloring pigments, and mixtures thereof.

[0106] The fluorescent colorant or pigment is preferably an organic fluorescent dye or organic fluorescent pigment, in particular a non-polymerizable organic fluorescent colorant that optionally contains an ester of an aryl carboxylic acid (e.g., diethyl 2,5-dihydroxyterephthalate, aryl carboxylic acid, coumarin, rhodamine, naphthalimide, or a derivative thereof). An example of an inorganic fluorescent pigment is CaAl4O7:Mn 2+ (Ba0.98Eu0.02)MgAl 10 O 17 BaMgF4:Eu 2+Examples include Y(1.995)Ce(0.005)SiO5. The coloring pigments contained in the dental materials of the present invention may include organic and inorganic pigments, such as N,N'-bis(3,5-xylyl)perylene-3,4:9,10-bis(dicarboximide), copper phthalocyanine, and titanate pigments, particularly chromium antimony titanate (rutile structure), spinel black, particularly iron oxide (Fe2O3) or iron oxide black (Fe3O4) in which iron is partially substituted with chromium and copper or nickel and chromium or manganese, zinc iron chromite brown spinel ((Zn,Fe)(Fe,Cr)2O4), cobalt zinc aluminate blue spinel, and / or titanium oxide-based pigments.

[0107] Conventional dental additives may be present in the polymerizable composition in a mass ratio of 0% to 5% by weight, preferably 0.001% to 5% by weight, relative to the total mass of the free radical polymerizable composition.

[0108] The present invention has the advantage that the free radical polymerizable compounds and free radical polymerizable compositions of the present invention overcome the above-mentioned drawbacks of the prior art. The free radical polymerizable compounds and free radical polymerizable compositions have excellent properties that are necessary or desirable, particularly for the manufacture of dental materials.

[0109] Furthermore, the present invention has the remarkable advantage that the free radical polymerizable compounds of the present invention can be synthesized not only inexpensively but also in high purity and without undesirable discoloration by the production method of the present invention. Moreover, the free radical polymerizable compositions have a high monomer conversion rate in free radical polymerization. As a result, dental materials and devices produced from the free radical polymerizable compositions contain only small amounts of residual monomers.

[0110] Free radical polymerizable compositions can be further manufactured from readily available monomers with reduced toxicity. Since free radical polymerizable compositions preferably do not contain any compounds containing a bisphenol A group and / or another bisphenol group, the resulting dental materials and devices manufactured therefrom can be substantially eliminated from being harmful to health.

[0111] The use of free radical polymerizable compounds or compositions for the manufacture of dental materials results in good mechanical properties in the resulting dental materials, as well as reduced polymerization shrinkage. This means that free radical polymerizable compositions have low polymerization shrinkage and reduced shrinkage stress. Free radical polymerized compositions and dental materials manufactured therefrom have good mechanical properties, such as particularly good flexural and tensile strength, as well as good fracture resistance. As those skilled in the art would expect, these advantageous properties of the free radical polymerizable compounds and corresponding compositions of the present invention are remarkable in terms of the molecular size and structure of the free radical polymerizable compounds, as this would be accompanied by a decrease in crosslinking density and flexural strength.

[0112] Surprisingly, radical polymerizable compounds or compositions contain conventional fillings in the dental field and have refractive indices that are particularly suitable for the manufacture of dental materials having desired optical properties, especially with respect to translucency or opacity.

[0113] Furthermore, the free radical polymerized composition (i.e., the manufactured dental material) has low water solubility and low water absorption, which is also advantageous.

[0114] The present invention also provides the use of a free radical polymerizable compound (preferably as described in any one of claims 1 to 7) or a free radical polymerizable composition (preferably as described in any one of claims 9 to 12) for manufacturing polymerizable dental materials, preferably dental composites, dental cements, self-adhesive dental cements, dental lacquers, core build-up materials, root canal filling materials, filling materials, lining materials, luting materials, crown materials, bridge materials, restorative materials, orthodontic materials and / or prosthetic materials.

[0115] In this case, the filler material may be a moldable and / or freely flowing filler material, preferably a moldable filler material.

[0116] In a preferred embodiment, polymerizable dental material is used as a 3D printing material. In this way, polymerizable dental material can be used to manufacture orthodontic materials, aligners, rail materials, prosthetic base materials, modeling materials, crown and bridge materials, drill templates, gingival masks, spoon materials, mouthguards and / or veneers using a 3D printer.

[0117] Furthermore, the present invention also relates to dental materials produced from the free radical polymerizable composition of the present invention (preferably as described in any of claims 9 to 12).

[0118] The present invention further provides free radical polymerizable dental materials for use in treatment methods as dental composites, dental cements, dental lacquers, filling materials, lining materials, cementing materials, core build-up materials, root canal filling materials, crown materials, bridge materials, restorative materials, orthodontic materials and / or prosthetic materials.

[0119] The present invention similarly provides a cured dental material manufactured from a polymerizable composition of the present invention (preferably as described in any of claims 9 to 12). The cured dental material may be manufactured in a process in which a free radical polymerizable composition is provided and which is completely or partially solidified or cured. In certain embodiments, the free radical polymerizable composition can be 3D printed before curing. [Brief explanation of the drawing]

[0120] The present invention is illustrated by several advantageous embodiments with reference to the accompanying drawings. The drawings are as follows: [Figure 1] A GPC diagram showing the peaks of the free radical polymerizable compound of the present invention according to formula 31. [Figure 2] A GPC diagram showing the peaks of the free radical polymerizable compound of formula 33 of the present invention.

[0121] Examples 1. Chemical substances and their pretreatment / use The following chemicals were used in the preparation of the examples (Table 1) and treated as described in this section before further use.

[0122] Table 1: Compounds and substances used in the examples. TIFF2026515966000011.tif171160

[0123] Drying of TCD-DM TCD-DM was dried by azeotropic distillation with approximately 2.5 times its volume of toluene until a solution of 83.6% by weight of TCD-DM in toluene was obtained. Unless otherwise specified, TCD-DM was used in this solution form. Weight figures refer to TCD-DM.

[0124] 2. Method Thin-layer chromatography (TLC) TLC was performed using silica as the stationary phase (TLC plate: Polygram Sil G / UV). 254(Macherey-Nagel GmbH&Co. KG, Germany). Samples of the substances to be analyzed were diluted 1:10 with tetrahydrofuran. The eluent used was a 2:1 mixture of cyclohexane and ethyl acetate. The developed TLC plates were observed under UV light (wavelength 254 nm) and then stained in an iodine chamber.

[0125] drying loss Drying loss was determined by gravimetric analysis. For this purpose, the samples were dried in a convection oven at 110°C for 2 hours or at 50°C for 2 hours, and the residue was weighed.

[0126] viscosity Viscosity measurements were performed at 23°C using a rotational viscometer (Kinexus type, Malvern Instruments GmbH, Germany) with a plate-to-plate configuration (d=25mm, gap h=0.1mm, shear stress ramp 1-50Pa), and viscosity was determined at a shear stress of 50Pa.

[0127] FT-IR spectroscopy FT-IR spectra (iS10 and iS20 models, Thermo Scientific Nicolet) were generated using one ATR unit each. 4 cm -1 32 scans were acquired with this resolution.

[0128] Liquid chromatography-mass spectrometry coupling (HPLC-MS) This analysis was performed using a Waters Alliance 2695 HPLC system. The following column was used for separation: 250 / 2 Nucleodur C8 ec. The column temperature was 20°C. Elution was performed at a flow rate of 0.2 ml / min using the following eluent gradients: 0.1% formic acid in acetonitrile (A) and 0.1% formic acid in water (B). The TIFF2026515966000012.tif16147 sample was detected using a Waters Micromass ZQ mass detector. Ionization was performed in ESI+ mode.

[0129] HPLC method for the quantification of TCDDA HPLC content of TCDDA in the sample (content HPLC The (wt%) was determined using a Thermo Ultimate 3000 HPLC system. The following column was used for separation: 250 / 4 LiChrospher RP Select B (5 μm). The column temperature was 20°C. Elution was performed at a flow rate of 1 ml / min using the following eluent gradient: water (A) and methanol (B). Detection of TIFF2026515966000013.tif16150 was performed using a UV detector at 205 nm. The TCDDA reference sample concentration was approximately 25 mg per 50 ml of methanol. The sample concentration in the example was approximately 15 mg per 10 ml of methanol. 3 μl of sample was injected for measurement.

[0130] The content of the monomers and oligomers of the present invention in the sample is calculated as follows: The monomer + oligomer content (weight %) of the present invention = 100% - drying loss (weight %) - HPLC content of TCDDA (weight %).

[0131] Gel permeation chromatography (GPC) GPC was performed using a GPC Agilent 1200 (PSS, Germany) equipped with an RI detector. The following column combination (PSS, Germany) was used: pre-column / 100 Å / 100 Å / 1000 Å. The eluent was THF, and the flow rate was 1 ml / min. The sample concentration was approximately 5 mg / ml. GPC was performed at 20°C.

[0132] Determination of refractive index The refractive index of the uncured composition was determined based on the D-line of sodium light at 23°C ± 1°C relative to air using an Abbe refractometer AR (A. Kruss Optronik, Germany). Three measurements were performed for each component, and the average value was calculated.

[0133] The refractive index of the cured composition was determined on a test specimen using an Abbe refractometer AR (A. Kruss Optronik, Germany) according to ISO 489:1999. A droplet of cinnamon oil was applied to the sample and brought into contact with the measuring prism of the refractometer. Three measurements were taken for each sample, and the average was calculated. To prepare the test specimens, the composition was placed in a steel mold (8 mm × 20 mm × 0.5 mm) and placed on a slide covered with a transparent, colorless polyester film (Hostaphan®). Another film, followed by another slide, was placed on the resin, ensuring no air bubbles were present, and secured with clamps. The specimens were then exposed to light for 90 seconds using a photopolymerization apparatus (Hi-Lite Power®; Heraeus Kulzer). The cured specimens were then removed from the mold.

[0134] Determination of flexural strength (FS) and elastic modulus (ME) To determine the flexural strength and modulus of elasticity, test specimens were prepared in accordance with ISO 4049:2009. Initially, the specimens were prepared by exposure using a photopolymerization apparatus (Hi-Lite Power®; Heraeus Kulzer). For this purpose, dental composite specimens of the specified shape (40 mm × 2 mm × 2 mm) were irradiated from both sides for 90 seconds each. The specimens were stored in distilled water at 37°C for 24 hours. Flexural strength and modulus of elasticity were determined using a Zwick universal tester (model Z010 or Z2.5, Zwick-Roell, Germany). The reported values ​​are the mean and standard deviation.

[0135] Measurement of volume shrinkage of resin mixtures (liquid pycnometer) The volume shrinkage of the resin mixture was determined by measuring the change in density before and after curing at 20°C using a liquid pycnometer (Blaubrand, Brand GmbH+Co KG, Germany).

[0136] First, the density of the uncured composition was measured using a 10 ml liquid pycnometer. Higher viscosity compositions (viscosity > 10 Pas) were pre-equilibriumized to 60°C in a heating cabinet so that they could be introduced into the pycnometer with minimal bubbles. Bubbles were further removed by applying reduced pressure in a desiccator. The filled pycnometer was then equilibrated to 20°C. After reaching the measurement temperature, the mass of the filled pycnometer was measured, and the density of the uncured composition was then determined.

[0137] To determine the density of the cured composition, cubic test specimens (35 mm × 20 mm × 3 mm) were prepared. For this purpose, the uncured composition was introduced into the corresponding test specimen mold without air bubbles and cured for 90 seconds using the above and below photopolymerization apparatus (Hi-Lite Power®; Heraeus Kulzer). The cured test specimens were stored at 23°C for 24 ± 2 hours.

[0138] To determine the density of the cured composition, the mass m1 of the cured specimen and the empty weight m0 of the pycnometer were determined. The pycnometer was then filled to about 4 / 5 with distilled degassed water, and after equilibration at 20°C, the cured specimen was immersed in the pycnometer. The pycnometer was then completely filled with water. After reaching the measurement temperature of 20°C, the pycnometer was closed and dried from the outside. The mass m3 of the pycnometer filled with water and the specimen was measured, and the density ρ of the cured specimen was determined according to equation 1 below. NA They decided: TIFF2026515966000014.tif21148V2 = Specific volume of a pycnometer used at 20℃ In this way, three cured specimens were analyzed in each case.

[0139] Average (MW VS Volume shrinkage (VS) was calculated from the difference between the density before hardening (ρVA) and the average density after hardening (MWρNA) (equation 2). TIFF2026515966000015.tif20154

[0140] Standard deviation of volume contraction (SD) VS This was determined according to equation 3. SD VS = 100 × ρ VA ×SDρ NA / MW 2 ρ NA (equation 3)

[0141] Measurement of composite volume contraction (gas pycnometer) The volume shrinkage of the composite was determined by measuring the change in density before and after curing using a helium gas pycnometer (AccuPyc III 1340, Micromeritics, USA).

[0142] The density of the uncured composite was measured three times. In each measurement, approximately 0.3–0.4 g of the composite was placed in the measurement chamber of the gas pycnometer, ensuring that no voids were created. The weight of the uncured composite was measured using a balance, and the density of the uncured composite was determined by measuring its volume using a gas pycnometer with AccuPYKII 1340 software.

[0143] Subsequently, the density of the cured composite was measured three times. To determine the density, two cylindrical test specimens (h=2mm, D=8mm) of the composite were prepared by curing them using a HiLite Power photopolymerization apparatus (90 seconds from each side). The sample mold was filled without air bubbles, and the top and bottom were covered with slides during curing. After curing, the test specimens were removed from the mold, deburred, washed with ethanol, and dried with compressed air. Then, the two test specimens were placed stacked on top of each other in the measurement chamber of a gas pycnometer. The weight of the cured composite was measured using a balance, and the density of the cured composite was determined from the volume measurement using a gas pycnometer with AccuPYKII 1340 software. The density was measured within 15 to 60 minutes after curing.

[0144] Volume contraction as average (VS) (MW) VSThe density was calculated from the difference between the average density of the composite before curing (MWρVA) and the average density after curing (MWρNA) (equation 4). TIFF2026515966000016.tif17148

[0145] Standard deviation of volume contraction (SD) VS This is the standard deviation (SD) of the density of the cured composite. ρNA and the standard deviation (SDρ) of the density of the uncured composite VA This was confirmed by equation 5 from the corresponding mean MWρNA and MWρVA. SD VS =100 / MWρ NA 2 ×√((MWρ NA 2 ×SDρ VA 2 )+(MWρ VA 2 ×SDρ NA 2 )) (equation 5)

[0146] Measurement of conversion rate The conversion rate was determined by FT-NIR spectroscopy (Nicolet iS20, Thermo Scientific) before and after polymerization of the composition in transmission geometry. Conversion or progression of the polymerization reaction occurred at 6160–6170 cm⁻¹. -1 This was determined by measuring the decrease in the size of the C=C overtone band in the given context.

[0147] For this purpose, an uncured, i.e., unpolymerized composition or composite was prepared as a cylindrical specimen (D=15mm, h=1.0mm), covered with slides on the top and bottom, and then mounted in an IR holder. Twelve scans of the spectrum were obtained. The uncured, i.e., unpolymerized composition or composite was then cured from each side for 90 seconds using a photopolymerization apparatus (Hi-Lite Power®; Heraeus Kulzer). The FT-NIR spectrum of the polymerized composition was then recorded within 60 minutes. The spectrum was then measured at 6160–6170 cm⁻¹. -1 The integral value of the C=C overtone band at was determined using the IR software Omnic (Series 9.11.727; Inc. Thermo Scientific). The conversion rate C at % is calculated from the two integral values ​​according to equation 6: TIFF2026515966000017.tif16138

[0148] 3. Synthesis Examples Example 1 Enzymatic transesterification of TCDDA and TCD-DM to TCD-MA A solution of 24.00 g of TCD-DM and 92.16 g of TCDDA in 80 ml of MTBE was placed in a 250 ml round-bottom flask equipped with a magnetic stirrer bar. 2 g of CALB was added, and the flask was closed with a CaCl2 drying tube. The preparation was gently stirred in a water bath at 40°C for 42 hours and then allowed to stand at room temperature (RT) for 128 hours. The preparation was filtered, washed twice with a small amount of MTBE, and the filtrate was concentrated using a rotary evaporator and then dried under high vacuum. The residue was a low-viscosity, colorless oil. Yield: 104.5 g

[0149] TCD-DM (9.55), TCD-MA (21.5), and TCDDA (33.6) were detected by HPLC-MS. The retention time (minutes) for each is shown in parentheses. The drying loss (2 hours, 50°C) was 0.34% by weight.

[0150] Example 2 Synthesis of a free radical polymerizable compound with the structure of formula 33 9.55 ml of IPDI was slowly added dropwise at room temperature to an initial packing of 50 g of oil from Example 1 in 50 g of THF in a 250 ml two-necked flask equipped with a magnetic stirrer bar, an internal thermometer, and a dropping funnel with a CaCl2 drying tube. Then, 10 μl of catalyst solution (DMTND in toluene-t, weight ratio 1:1) was added, and the mixture was stirred at 40°C for 8 hours and at room temperature for 85 hours. For the conversion of the remaining isocyanate groups, 5.77 g of oil from Example 1 in 5.77 g of THF was added, and the mixture was stirred at 40°C for 2 hours. Thereafter, the isocyanate groups were no longer detectable by FT-IR spectroscopy.

[0151] The reaction mixture was transferred to a 250 ml necked flask, and THF was substantially removed using a rotary evaporator at 25 mbar and a water bath temperature of 50°C. Further volatile components were removed under high vacuum at 50°C. The remaining material was a clear, colorless oil. Yield: 57.68g Drying loss (2 hours, 110℃): 1.69%

[0152] HPLC-MS revealed TCDDA(M+H + =305) held for 34.0 minutes, the compound of formula 33 (M+H + (=724) was detected with a retention time of 45.4 minutes.

[0153] Figure 1 shows the elution profiles of the GPCs that were performed. TCDDA had an elution volume of 29.8 ml, compound x=1 (structure 33) had an elution volume of 26.3 ml, and compounds x=2 and x=3 had elution volumes of 25.0 ml and 24.0 ml, respectively. TCDDA HPLC content: 48.09% by weight. Content of the compound in formula 31: 50.22% by weight. TIFF2026515966000018.tif39155

[0154] Example 3 Synthesis of a free radical polymerizable compound with the structure of formula 34 7.17 g of H12MDI was slowly added dropwise at room temperature to an initial packing of 30 g of oil according to Example 1 in 30 g of THF in a 250 ml two-necked flask equipped with a magnetic stirrer bar, an internal thermometer, and a dropping funnel with a CaCl2 drying tube. Then, 10 μl of catalyst solution (toluene-t in DMTND, weight ratio 1:1) was added, and the mixture was stirred at 40°C for 4 hours and at room temperature for 19 hours. For the conversion of the remaining isocyanate groups, a further 11.61 g of oil as described in Example 1 in 11.61 g of THF was added in steps (4 steps). After each addition, the mixture was stirred at 45°C for 3 hours and at room temperature for 18 hours. Subsequently, the isocyanate groups were no longer detectable by FT-IR spectroscopy.

[0155] The reaction mixture was transferred to a 250 ml necked flask, and THF was substantially removed using a rotary evaporator at 25 mbar and a water bath temperature of 50°C. Further volatile components were removed under high vacuum at 50°C. The remaining material was a clear, colorless oil. Yield: 42.79g Drying loss (2 hours, 110℃): 2.07%

[0156] HPLC-MS revealed TCDDA(M+H + =305) held for 33.6 minutes, the compound of formula 34 (M+H + (=764) was detected with a retention time of 48.6 minutes. GPC:TCDDA had an elution volume of 29.6 ml, the compound with structure 34 where y=1 had an elution volume of 26.0 ml, and those with y=2 and y=3 had elution volumes of 24.3 ml and 23.2 ml, respectively. TCDDA HPLC content: 47.35% by weight. Content of the compound in formula 32: 50.58% by weight. TIFF2026515966000019.tif20130

[0157] Example 4 Synthesis of the free radical polymerizable compound of formula 35 First, a 250 ml three-necked flask equipped with a magnetic stirrer bar, internal thermometer, reflux condenser, dropping funnel, and CaCl2 drying tube was filled with 11.35 g of TMDI and 50 μl of catalyst solution (DMTND in toluene-t, 50:50 w / w) in 25 ml of THF. A solution of 50.0 g of the oil described in Example 1 in 25 ml of THF was slowly added dropwise at room temperature while stirring. The mixture was then stirred at 45 °C for 5 hours and then at room temperature for a further 18 hours.

[0158] To convert the remaining isocyanate groups, an additional 6.44 g of oil was added in four steps until the isocyanate groups were no longer detectable by FT-IR spectroscopy. After each addition, the mixture was stirred at 45°C for 5 hours and at room temperature for 18 hours.

[0159] The reaction mixture was transferred to a 250 ml necked flask, and 0.01 g of BHT was added. Most of the THF was removed using a rotary evaporator. The solvent and other volatile components were further removed under high vacuum at 50°C. The remaining substance was a clear, colorless oil. Yield: 55.94g Drying loss (2 hours, 110℃): 0.99%

[0160] HPLC-MS revealed TCDDA(M+H + The compound (M+H) of formula 35 was held for 33.7 minutes. + The result (=712) was detectable with a retention time of 45.2 minutes. The elution profiles of the GPCs performed are shown in Figure 2. TCDDA had an elution volume of 29.8 ml, the compound with the structure of Equation 35 with z=1 had an elution volume of 26.5 ml, and the higher-order oligomers (z=2~4) had elution volumes of 24.9, 23.9, and 23.2 ml, respectively. TCDDA HPLC content: 44.97% by weight. Content of compound in formula 35: 54.04% by weight. TIFF2026515966000020.tif25131

[0161] Example 5 Synthesis of a free radical polymerizable compound with the structure of formula 36 6.67 g of TMXDI was slowly added dropwise at room temperature to 30 g of the initial packing of the oil described in Example 1 in 30 g of THF and 0.005 g of BHT in a 250 ml two-necked flask equipped with a magnetic stirrer bar, an internal thermometer, and a dropping funnel with a CaCl2 drying tube. 10 μl of catalyst solution (DMTND in toluene-t, weight ratio 1:1) was added, and the mixture was stirred at 40°C for 4 hours and at room temperature for 18 hours. To convert the remaining isocyanate groups, a further 5.22 g of the oil described in Example 1 and 10 μl of catalyst solution were added, and the mixture was stirred at 40°C for 5.5 hours and at room temperature for 18 hours. Subsequently, the isocyanate groups were no longer detectable by FT-IR spectroscopy.

[0162] The reaction mixture was transferred to a 250 ml necked flask, and THF was substantially removed using a rotary evaporator at 25 mbar and a water bath temperature of 50°C. Further volatile components were removed under high vacuum at 45°C. The remaining material was a clear, colorless oil. Yield: 33.75g Drying loss (2 hours, 110℃): 1.49%

[0163] HPLC-MS revealed TCDDA(M+H + =305) held for 34.5 minutes, and the compound (M+H) had the structure of formula 36. + The value (=746) was detectable with a retention time of 45.4 minutes. GPC:TCDDA had an elution volume of 29.7 ml, the compound with the structure of formula 36 (l=1) had an elution volume of 26.5 ml, and those with l=2 to l=4 had elution volumes of 24.9, 24.0, and 23.2 ml, respectively. TCDDA HPLC content: 46.06% by weight. Content of compound in formula 36: 52.45% by weight. TIFF2026515966000021.tif24143

[0164] Example 6 Synthesis of Free Radical Polymerizable Compounds Using H6XDI 3.89 g of H6XDI in 15 ml of THF was slowly added dropwise at room temperature to the initial packing of 22 g of oil described in Example 1 in 15 ml of THF in a 100 ml two-necked flask equipped with a magnetic stirrer bar, an internal thermometer, and a dropping funnel with a CaCl2 drying tube. 10 μl of catalyst solution (toluene-t in DMTND, weight ratio 1:1) was added, and the mixture was stirred at 40°C for 5 hours and at room temperature for 18 hours. Subsequently, isocyanate groups were no longer detectable by FT-IR spectroscopy.

[0165] The reaction mixture was transferred to a 100 ml necked flask, a spatula-tip-sized amount of BHT was added, and THF was removed as much as possible using a rotary evaporator. Further volatile components were removed under high vacuum. The remaining substance was a clear, colorless oil. Yield: 21.48g Drying loss (2 hours, 110℃): 1.43%

[0166] By HPLC-MS, TCDDA was detectable with a retention time of 34.0 minutes, and the product (M+H) was detected. + The value (=696) was detectable with a retention time of 43.3 minutes. GPC:TCDDA had an elution volume of 29.7 ml, and product elution volumes of 26.6 ml, 25.1 ml, 24.1 ml, and 23.4 ml.

[0167] Since the isocyanates and / or alcohols used are isomers or mixtures of isomers, it is clear that different isomeric structures will arise in the synthesis of free radical polymerizable compounds. In particular, differences in isomeric structures may arise with respect to the dimethylentricyclodecane groups and the direction in which they are oriented within the polymerizable compound (e.g., in the oligomeric chain). However, each single compound having the structures of formulas 33-34 shown herein is assumed to include all resulting isomeric compounds.

[0168] 5. Characteristics of Free Radical Polymerizable Compositions For the preparation of the composition, the individual components were mixed using a magnetic stirrer until the composition was homogeneous.

[0169] Table 2: Composition, viscosity (η), flexural strength (FS), elastic modulus (ME), conversion rate (C), volume shrinkage (VS), and refractive index (n) of the uncured material for compositions of the present invention (Ex. A, B, C, D) containing polymerizable compounds synthesized by free radical synthesis in Examples 2-5 (Ex. 2-5 oils). D VA), and the refractive index (n) of the cured product. D NA), and comparative compositions (CE A, B) TIFF2026515966000022.tif71140

[0170] Table 3: Composition, flexural strength (FS), elastic modulus (ME), volume shrinkage (VS), refractive index of uncured material (nDVA), and refractive index of cured material (nDNA) of comparative compositions (CE C~F) TIFF2026515966000023.tif75152

[0171] Examples B and D of the present invention exhibit significantly lower volume shrinkage than comparative examples A to F. The conversion rate, flexural strength, and modulus of elasticity of the examples of the present invention are within the range of comparative examples A to F, and in some cases, higher.

[0172] The difference in refractive index (n) between the cured examples B and D of the present invention and the dental glass used. D The difference (=1.53) is comparable to the difference between Comparative Examples A-F and the same dental glass. Thus, the results of Examples B and D of the present invention similarly show low turbidity in the dental composite, which results in very good aesthetic product characteristics.

[0173] Manufacturing of dental composites First, for the preparation of the dental composite, the components (oil, Ex.3, Ex.5, and bisGM A and TEDMA) were mixed with CQ, EHA, and BHT using a magnetic stirrer until the composition was homogenized. Subsequently, a total of 75% by weight of BaF relative to the total mass of the dental composite was gradually added, and the mixture was homogenized using a Speedmixer DAC400-1 VAC-P (Hauschild, Germany) and degassed at 20 mbar for 3 minutes. The composition and measurement results are shown in Table 4.

[0174] Table 4: Composition, flexural strength (FS), elastic modulus (ME), conversion rate (C), and volume shrinkage (VS) of dental composites (Ex. E, F) containing polymerizable compounds synthesized free radically in Examples 3 and 5 (Ex. 3, Ex. 5) and comparative composition G (CE G). TIFF2026515966000024.tif74117

[0175] Examples E and F, using the compounds of the present invention, exhibit significantly lower volume shrinkage than Comparative Example G, which uses monomer mixtures from the prior art. The conversion rate, flexural strength, and modulus of elasticity of the examples of the present invention are comparable to those of Comparative Example G.

[0176] For comparison, Table 5 shows the properties of commercially available dental composites with higher filler levels, as known from the prior art. Despite the higher filler levels, the shrinkage data for these composites is higher than that of the embodiments of the present invention.

[0177] Table 5: Properties of prior art commercially available dental composites containing BPA-containing polymerizable compositions and 78.5% to 83% by weight of fillers. TIFF2026515966000025.tif46135

Claims

1. Free radical polymerizable compounds represented by the structure of formula 1 below: PG - Sp - PCA - Sp - [OC(O)NH - K - NHC(O)O - Sp - PCA - Sp] ｎ - PG (Formula 1) [Here, PG = Each is independently selected from free radical polymerizable groups, preferably (NR １ ) OC-CR ２ =CH ２ and OOC-CR ２ =CH ２ Selected from, more preferably OOC-CR ２ =CH ２ Selected from, R １ is selected from hydrogen, a C1-C8 alkyl group, an aryl group, and an araliphatic group having 6 to 8 carbon atoms, preferably selected from a C1-C8 alkyl group and a benzyl group, R ２ = Selected from hydrogen, C1-C4 alkyl groups, preferably selected from hydrogen and methyl; Sp = A spacer group independently selected from unbranched and branched alkylenes having C1 to C19 carbon atoms, wherein the alkylene may further have oxygen, sulfur and / or -OOC- in its carbon chain. Or Sp does not exist; PCA = Each is independently a polycyclic group, preferably an aliphatic polycyclic group, preferably an aliphatic bicyclic group or an aliphatic tricyclic group; K = an aliphatic acyclic saturated or unsaturated unit having C1 to C15 carbon atoms, preferably C3 to C13 carbon atoms, more preferably C6 to C9 carbon atoms, which may be substituted by one or more C1 to C3 aliphatic carbon substituents. A polyphatic cyclic saturated or unsaturated unit having C3 to C15 carbon atoms, preferably C5 to C13 carbon atoms, more preferably C6 to C13 carbon atoms, which may be substituted by one or more polyphatic C1 to C3 carbon substituents, or Aromatic or aroliphatic units having C6 to C14 carbon atoms, preferably C6 to C13 carbon atoms, which may be substituted by one or more aliphatic C1 to C3 carbon substituents; n = 1 to 9, preferably 1 to 6.

2. The spacer base Sp is methylene, *CH ２ - (OC ２ H ４ ) ｐ , *CH ２ - (OC ３ H ６ ) ｐ , * (OC ２ H ４ ) ｐ , * (OC ３ H ６ ) ｐ , *CH ２ -(OC(O)-R ５ -) ｐ , *(OC(O)-R ５ -) ｐ and *S-R ５ Selected from, where p = 1 to 5, preferably 1 to 3, R ５ The free radical polymerizable compound according to claim 1, characterized in that it is a C1-C12 alkylene group, preferably a C2-C6 alkylene group.

3. The free radical polymerizable compound according to claim 1 or 2, characterized in that the polycyclic group PCA is selected from the structures of formulas 2 to 13 below in each case: [These may be optionally substituted with one or more C1-C4 alkyl groups.]

4. The free radical polymerizable compound according to any one of claims 1 to 3, characterized in that the polycyclic group PCA is an aliphatic tricyclic group, preferably tricyclo[5.2.1.0 / 2,6]decanylene (TCD) (Formula 2).

5. A free radical polymerizable compound according to any one of claims 1 to 4, characterized in that K is selected from the following structures of formulas 14 to 26, preferably from the structures of formulas 14, 15, 16, 17, 18, 19 and 20:

6. The free radical polymerizable compound according to any one of claims 1 to 5, characterized in that the free radical polymerizable compound is represented by the structure of the following formula 27: (Formula 27) [Here, R ２ = Hydrogen or methyl group; Sp = A spacer group independently selected from unbranched and branched alkylenes having C1 to C19 carbon atoms, wherein the alkylene may further have oxygen, sulfur and / or -OOC- in its carbon chain. Or Sp does not exist; PCA = Each is independently a polycyclic group, preferably an aliphatic polycyclic group, preferably an aliphatic bicyclic or aliphatic tricyclic group, more preferably a tricyclic group, most preferably tricyclo[5.2.1.0 / 2,6]decanylene; K = an aliphatic acyclic saturated or unsaturated unit having C1 to C15 carbon atoms, preferably C3 to C13 carbon atoms, more preferably C6 to C9 carbon atoms, which may be substituted by one or more C1 to C3 aliphatic carbon substituents. A polyphatic cyclic saturated or unsaturated unit having C3 to C15 carbon atoms, preferably C5 to C13 carbon atoms, more preferably C6 to C13 carbon atoms, which may be substituted by one or more polyphatic C1 to C3 carbon substituents, or Aromatic or aromatic aliphatic unit having C6 to C14 carbon atoms, preferably C6 to C13 carbon atoms, which may be substituted by one or more aliphatic C1 to C3 carbon substituents; r = 1 to 9, preferably 1 to 6.

7. The free radical polymerizable compound according to any one of claims 1 to 6, characterized in that the free radical polymerizable compound is represented by a structure selected from the following formulas 28 to 31: (Formula 28) (Formula 29) (Formula 30) (Formula 31) [Here, t, u, v, and w are each independently 1 to 9, preferably 1 to 6; and R ２ = Selected from hydrogen and C1-C4 alkyl groups, preferably selected from hydrogen and a methyl group.

8. A method for preparing a free radical polymerizable compound, comprising the following steps: a) A step of reacting a diol of a polycyclic group PCA with a (meth)acrylic acid ester to obtain a PCA mono(meth)acrylate having a hydroxyl group by enzyme catalytic action, b) A step of reacting the PCA mono(meth)acrylate containing a hydroxyl group from step a) with a diisocyanate compound, preferably using a catalyst.

9. Free radical polymerizable compositions including the following: a) One or more free radical polymerizable compounds according to any one of claims 1 to 7; b) Optionally, one or more further free radical polymerizable monomers or oligomers not covered by at least one compound of Formula 1; c) Optionally, at least one initiator or initiator system for polymerization; d) One or more stabilizers, at the discretion of the party; e) One or more fillers, at the discretion of the party; f) Optionally, conventional dental additives.

10. The free radical polymerizable composition according to claim 9, characterized in that the free radical polymerizable composition contains one or more free radical polymerizable compounds of formula 1 in a mass ratio of 1 to 100% by weight, preferably 2 to 80% by weight, preferably 2 to 65% by weight, and more preferably 10 to 65% by weight, based on the total mass of all free radical polymerizable monomers and oligomers in the polymerizable composition.

11. The free radical polymerizable composition according to claim 9 or 10, characterized in that it contains a plurality of compounds of formula 1 selected from monomers (n=1) and / or oligomers (n=2 to 9).

12. The free radical polymerizable composition according to any one of claims 9 to 11, characterized in that the free radical polymerizable composition is a free radical polymerizable dental material.

13. Use of a free radical polymerizable compound according to any one of claims 1 to 7, or a free radical polymerizable composition according to any one of claims 9 to 12, for manufacturing polymerizable dental materials, preferably dental composites, dental cements, self-adhesive dental cements, dental lacquers, core build-up materials, root canal filling materials, filling materials, lining materials, luting materials, crown materials, bridge materials, restorative materials, orthodontic materials and / or prosthetic materials.

14. The use according to claim 13, wherein the polymerizable dental material is used as a 3D printing material, wherein the polymerizable dental material is used by 3D printing to manufacture, preferably, orthodontic materials, aligners, rail materials, prosthesis base materials, modeling materials, crown and bridge materials, drilling templates, gingival masks, spoon materials, mouthguards or veneers.

15. A hardened dental material manufactured from a polymerizable composition according to any one of claims 9 to 12.

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