Monomer mixture for dental material production

Abstract

The present invention relates to a monomer mixture for producing a dental material comprising: a. at least one base monomer M1 of the following empirical formula 1: K n U m (O-S-PG) o (Formula 1), and b. at least one base monomer of the following formula 4: PG'-S'-A'-S'-PG' (Formula 4), a monomer mixture comprising at least one or two or more base monomers M1 of empirical formula 1, the use of the monomer mixture, a polymerizable dental material comprising such a monomer mixture, a polymerizable dental material for use in a treatment method, and a cured dental material.

Description

Technical Field

[0001] The present invention relates to a monomer mixture for producing dental materials, the use of the monomer mixture, a polymerizable dental material comprising such a monomer mixture, a polymerizable dental material comprising such a monomer mixture for use in a treatment process, and a cured dental material.

Background Art

[0002] Radical polymerizable dental materials mainly comprise (meth)acrylate monomers. For example, restorative and prosthetic dental materials such as dental fillers or dentures generally employ dimethacrylate systems because of their properties such as rapid free radical polymerization, good mechanical properties, and aesthetic appearance. Conventional base monomers are high molecular weight structures containing linear aliphatic or aromatic groups and having terminal methacrylate functional groups, such as 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (bisGMA) and 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diylbis(2-methylacrylate) (UDMA).

[0003] For some time, efforts have been made to discontinue the use of bisGMA and replace it, at least to some extent, with other compounds. Particular attention has been focused on urethane monomers and oligomers. In the field of dental materials, the most widely commercially used substance as at least a partial substitute for bisGMA is UDMA.

[0004] For example, base monomers such as bis-GMA and UDMA are present in a wide range of commercially available radically polymerizable dental materials, but they have several drawbacks. They are generally solids due to their high viscosity. Therefore, mixtures with monomers of significantly lower viscosity, such as triethylene glycol dimethacrylate (TEGDMA), for example, are used. TEGDMA is a very versatile low molecular weight monomer with a low viscosity (0.01 Pa·s) and high mobility during polymerization, making conversion during polymerization easy.

[0005] However, these monomer mixtures and the dental materials obtained therefrom have several problem characteristics that can have an adverse effect on the results of clinical treatment. For example, monomer mixtures of these dimethacrylate monomers exhibit relatively low polymerization conversion rates, substantial polymerization shrinkage, low toughness, and undesirable water absorption. In known systems, the conversion rate of double bonds is often relatively low, resulting in not only insufficient mechanical properties and wear resistance but also being disadvantageous with respect to the toxicity and biocompatibility of the polymerized dental material. In addition, the volume shrinkage of currently used dimethacrylate monomers and the shrinkage stress of dental fillers (or fillings) can cause poor adhesion between the tooth and the filler, leading to microleakage and, consequently, secondary caries, potentially significantly reducing the lifespan of the restoration. Attempting to increase the double bond conversion rate to reduce the unreacted monomer content unfortunately increases the polymerization shrinkage rate and shrinkage stress.

[0006] For example, low molecular weight monomers having oligo(ethyleneoxy) groups such as TEGDMA have some water solubility and thus high bioavailability and are currently being critically evaluated considering their toxicological properties and susceptibility to biodegradation processes. Monomers containing bis-2,2[p-oxyphenyl]propane structural elements, i.e., monomers based on bisphenol A, are similarly critically evaluated, as dental materials comprising monomer mixtures containing these structural elements have been found to release detectable amounts of bisphenol A, and toxicologically important properties are thought to result therefrom.

[0007] There are various approaches to increasing the conversion rate or reducing the volume shrinkage. In dental composites (or dental composite materials) for dental fillings containing fillers in an organic resin matrix, attempts have been made to reduce the volume shrinkage by increasing the filler content. However, if the filler content is too high, it becomes difficult to mix the filler with the organic resin. In addition, there is a limit to the amount of filler that can be used in dental composite materials. Therefore, the option of reducing the polymerization shrinkage by increasing the filler content is basically limited.

[0008] In order to increase the conversion rate and reduce the polymerization shrinkage, the development of novel monomers such as high molecular weight urethane methacrylate monomers, for example, is underway. An increase in molecular weight is usually associated with a decrease in the mechanical properties of the cured dental material for a given monomer functionality. Furthermore, an increase in the viscosity of such monomers means that they need to be used together with a larger amount of low viscosity monomers in order to enable their use in dental composites, which has an adverse effect on shrinkage.

[0009] EP2436365B1 describes a low shrinkage dental composite comprising a monomer mixture in which monomers (b1) and (b2) are present in a ratio of 1:20 to 5:1. The compositions of the examples contain, in each case, 4.8 to 76.6% by weight of bis((meth)acryloyloxymethyl)tricyclo[5.2.1.0 2,6 decane (b1), 90.9 to 19.1% by weight of UDMA (b2), and 4.3% by weight of TEGDMA (b2). These composites exhibit a polymerization shrinkage of about 1.50%, regardless of the ratio of (b1) and (b2). When the filler content is reduced and the proportion of TEGDMA is increased, as in Comparative Example 11, the polymerization shrinkage increases.

[0010] Vaidyanathan et al., "Visible light curing properties of alicyclic polyester dimethacrylate, an 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 wt% and 50 wt% TEGDMA. Investigation of the polymerization conversion rates of these mixtures revealed that the combination of PEM with TEGDMA exhibited higher polymerization conversion rates than the combination of bis-GMA with TEGDMA.

[0011] US4554336 describes a dental orthodontic adhesive based on a trifunctional polyetherurethane(alk)acrylate having a non-linear structure. However, the urethane acrylate having a non-linear structure of U.S. Patent No. 4,554,336 results in a dental composite with a reduced modulus of elasticity, among other things.

Prior Art Documents

Patent Documents

[0012]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0013]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0014] Therefore, in dental materials, particularly dental restorations and filler materials, there is a need for monomers or monomer mixtures that can reduce the potential for toxicity, reduce volumetric shrinkage, and have good mechanical properties, and that can be manufactured from and are readily available.

[0015] Accordingly, an object of the present invention is to overcome the above-mentioned drawbacks of the prior art and to provide a monomer mixture that particularly enables the production of dental materials, particularly dental composites, in which volumetric shrinkage is improved, flexural strength is improved, and a good modulus of elasticity is obtained.

Means for Solving the Problems

[0016] The present invention achieves this object through a monomer mixture for producing a dental material comprising the following: a. The following empirical formula 1:

Chemical formula

Chemical formula

Chemical formula

[0017] Preferred embodiments can be found in the dependent claims.

DETAILED DESCRIPTION OF THE INVENTION

[0018] First, some terms used in the context of the present invention will be explained.

[0019] According to the present invention, a polymerizable dental material is understood to mean a material for (bio)medical use, in particular on dental hard substances such as enamel and dentin, or on bone tissue such as, for example, the jawbone.

[0020] A polymerizable dental material is usually a resin-based material containing a curable mixture of various components. In the context of the present invention, the resin consists essentially of a monomer mixture and further components soluble in the monomer, such as initiators, stabilizers, etc.

[0021] In the context of the present invention, the monomer mixture is a mixture containing base monomers M1 and M2, and optionally base monomers M3 and / or other monomers (OM) of the polymerizable dental material. For example, further components of the polymerizable dental material such as initiators, fillers, conventional dental additives, etc. are not components of the monomer mixture.

[0022] In the context of the present invention, base monomer M1 is a monomer when n = 1 and an oligomer when n = 2 to 9. In this case, the monomers and oligomers with n = 1 to 9 are also referred to as base monomer M1.

[0023] In the context of the present invention, T in formula 3 is a trivalent hydrocarbon group having C3-C7 carbon atoms. In the context of the present invention, trivalent means that three bonds start from group T, and these bonds preferably start from three different carbon atoms. Preferably, T is derived from glycerol, 2-ethyl-2-(hydroxymethyl)propane-1,3-diol, hexanetriol (1,2,6-isomer, 1,3,5-isomer, 1,2,3-isomer, 2,3,5-isomer, and mixtures thereof), butanetriol, 2-(hydroxymethyl)propane-1,3-diol, 2-methylpropane-1,2,3-triol, pentanetriol, 2-(hydroxymethyl)butane-1,4-diol, 2-(hydroxymethyl)butane-1,3-diol, 3-methylpentane-1,3,5-triol, 2-(hydroxymethyl)hexane-1,6-diol, and 3-(hydroxymethyl)hexane-1,6-diol. In addition, the C3-C7 carbon radical can also be derived from other trifunctional alcohols of the prior art. More preferably, T is a trivalent hydrocarbon group having 3 carbon atoms. In a preferred embodiment, T is the following formula 5: [Chemical formula] [In formula 3, The bonding points to the oxygen atoms in formula 3 are represented by the respective bonds (i.e., dashed lines) shown] represented by

[0024] In the context of the present invention, A in formula 2 is a group selected from divalent aromatic or aliphatic C6-C20 hydrocarbon groups. In the context of the present invention, divalent means that two bonds start from group A, and these bonds preferably start from two different carbon atoms. Preferably, A is a divalent aliphatic C6-C13 hydrocarbon group, more preferably a divalent saturated cyclic C6-C13 hydrocarbon group. Preferably, A is a divalent cyclic hydrocarbon group having 10 carbon atoms. In a preferred embodiment, A is the following formula 6: [Chemical formula] [In Formula 6, The two bonds shown (i.e., the dashed lines) each represent a bonding point to the nitrogen atom of Formula 2] are represented by

[0025] The monomer mixture preferably contains a plurality of base monomers M1, more preferably at least two base monomers M1, even more preferably more than 2 base monomers M1, still more preferably more than 3 base monomers M1, still more preferably more than 4 base monomers M1, still more preferably more than 5 base monomers M1, etc. When the monomer mixture contains a plurality of base monomers M1, it is preferably a mixture that also contains base oligomers in addition to the base monomers. According to the present invention, such a mixture is also referred to as a mixture of base monomers M1.

[0026] In addition to the base monomer M1 where n = 1 (i.e., the monomer), it is preferable that there is also at least one base monomer M1 where n is greater than 1 (i.e., the oligomer). The mass fraction of the base monomer M1 where n is greater than 1, which can be determined by fractionation by gel permeation chromatography (measurement with visible light) using a refractive index detector, is preferably 5 to 70% by weight, more preferably 10 to 60% by weight, and even more preferably 15 to 50% by weight based on the total mass of all base monomers M1 in the monomer / oligomer series of n = 1 to 9.

[0027] The distribution of the base monomer M1 with respect to n can vary within a wide range. The base monomer M1 where n = 2 to 5 or n = 2 to 4 may have the highest mass fraction based on the total mass fraction of the base monomer M1. However, the base monomer M1 where n = 1 may also have the highest mass fraction compared to the individual base monomers M1 present in the monomer mixture of n = 2 to 9.

[0028] A part of the structure of the base monomer M1 for various n is outlined below. When n = 1, if the conditions m = 2n + 1 and o = n + 2 are satisfied, the empirical formula of the base monomer M1 is K1U3(OS-PG)3. The combination of the trivalent group K, the divalent group U, and the monovalent group -O-S-PG gives, for n = 1, the following formula 7: [Chemical formula] yields the structure of the base monomer M1 shown in.

[0029] When n = 2, the empirical formula of the base monomer M1 is K2U5(O-S-PG)4. In this case, the base monomer M1 can be represented by formula 8: [Chemical formula] as shown in the structure.

[0030] When n = 3, the empirical formula of the base monomer is K3U7(O-S-PG)5. In this case, the base monomer M1 can be represented by formula 9: [Chemical formula] as shown in the structure.

[0031] When n = 4, the empirical formula of the base monomer is K4U9(O-S-PG)6. When n = 4, the base monomer M1 can already be represented by two different structures, the following formula 10: [Chemical formula] and the following formula 11: [Chemical formula] as shown in.

[0032] When n = 5, the empirical formula of the base monomer is K5U 11 (O-S-PG)7 is obtained. When n = 5, the base monomer M1 can similarly be represented by two different structures, the following formula 12: [Chemical formula] and formula 13: [Chemical formula] are shown in.

[0033] When n = 6 - 9, the number of possible structures increases as n increases.

[0034] Specifically, within group K, the three carbon atoms of group T are each bonded to the corresponding oxygen atom T( O ) s [((OR) r )O] t or T(O) s [(( O R) r )O] t is bonded. Group K can be bonded to the carbamoyl carbon atom of group U - O ) s [((OR) r )O] t or T(O) s [((OR) r ) O t via. The carbamoyl carbon atom - NH - of group U C O - NH - can be bonded. The carbamoyl carbon atom - NH - C O - of group U can be bonded to either the oxygen atom of the - O - S - PG group and the oxygen atom of group K (T(O) s [((OR) r ) O t or T( O ) s [((OR) r )O] t ), or to two oxygen atoms of different groups K. The oxygen atom of the - O - S - PG group is always bonded to the carbamoyl carbon atom NH - CO - of group U.

[0035] The base monomer M1 where n is greater than 1 exists as a base monomer where n = 2 - 9, preferably n = 2 - 7, more preferably n = 2 - 5.​​

[0036] In one embodiment, all base monomers M1 of the monomer / oligomer system with n = 1 to 9, preferably n = 1 to 7, more preferably n = 1 to 5, may be present adjacent to each other. This means that if at least one compound exists for each n from 1 to 9 in each case, at least 9 compounds (i.e., 1 monomer when n = 1, and 8 oligomers when n = 2, 3, 4, etc.) are present in the monomer mixture (or monomer / oligomer mixture). Thus, when n = 1 to 7, at least 7 compounds (i.e., 1 monomer and 6 oligomers) are present in the monomer mixture, and when n = 1 to 5, at least 5 compounds (i.e., 1 monomer and 4 oligomers) are present.

[0037] In the context of the present invention, r is, in each case, independently, 1 to 12, preferably 1 to 9, even more preferably 1 to 6. Since t can vary in the base monomer M1, i.e., t can be 2 or 3, the number of radicals r present also varies accordingly, i.e., in the context of the present invention, r can correspond to either radical r1 and r2, or radicals r1, r2, and r3. In the context of the present invention, the radicals r1 to r2 or r1 to r3 in the base monomer M1 may be the same as each other or different from each other.

[0038] That is, since the -O-R- groups may be arranged with different stoichiometric exponents r1, r2, r3, the group K may be distributed by molecular weight.

[0039] The sum of the coefficients r1, r2, r3 is preferably greater than 3. In a preferred implementation, r1 + r2 + r3 = 4 to 20.

[0040] The base monomer M2 may be selected from bis(acryloyloxymethyl)tricyclo[5.2.1.0 / 2,6]decane, bis(acryloyloxymethyl)tricyclo[5.2.1.0 / 2,6]decane, and mixtures thereof. More preferably, the base monomer M2 is bis(acryloyloxymethyl)tricyclo[5.2.1.0 / 2,6]decane. The base monomer M2 can be a commercially available monomer such as tricyclo[5.2.1.0 / 2,6]decane dimethanol diacrylate from PolyScience, for example. However, it may also be a monomer obtained by an esterification reaction according to the production examples of, for example, EP0235836B1 or US4131729 / DE2816823. Industrially available base monomers M2 based on tricyclo[5.2.1.0 / 2,6]decane dimethanol di(meth)acrylate generally contain a mixture of isomers in which the exocyclic methylene groups are bonded to different main chain (or backbone) carbon atoms depending on the isomer.

[0041] The monomer mixture may contain a base monomer M3 different from the base monomer M1 of formula 1 and the base monomer M2 of formula 2.

[0042] Preferably, the base monomer M3 is selected from urethane-based monomers.

[0043] Suitable base monomers M3 may be selected from difunctional urethane (meth)acrylates, polyfunctional urethane (meth)acrylates, and mixtures thereof.

[0044] The base monomer M3 is preferably urethane di(meth)acrylate. The urethane di(meth)acrylate is preferably selected from linear or branched alkylene bis(urethane (meth)acrylate) and urethane di(meth)acrylate-functionalized polyethers.

[0045] A difunctional urethane (meth)acrylate having a divalent alkylene group and a difunctional urethane (meth)acrylate selected from those having a divalent cycloaliphatic hydrocarbon group are preferred.

[0046] The difunctional urethane (meth)acrylate having a divalent alkylene group is preferably selected from linear or branched urethane di(meth)acrylates functionalized with a divalent alkylene group such as, for example, bis(methacryloyloxy-2-epoxycarbonylamino)alkylene.

[0047] Thus, the difunctional urethane (meth)acrylate has a group B selected from a divalent linear or branched alkylene group and a divalent cycloaliphatic hydrocarbon group, a group Z selected from linear or branched C2-C8 hydrocarbon radicals in which one or more carbon atoms may be optionally substituted with oxygen, nitrogen or sulfur, and a group X which may independently be a methyl group or H, of the following formula 14: [Chemical formula] and can be a compound of. Examples are bis(methacryloyloxy-2-epoxycarbonylamino)alkylene. The divalent alkylene preferably includes 2,2,4-trimethylhexamethylene and / or 2,4,4-trimethylhexamethylene. Preferably, it is 1,6-bis(methacryloyloxy-2-epoxycarbonylamino)-2,4,4-trimethylhexane. Examples include UDMA and HEMA-TDMI.

[0048] Base monomer M3 can also be a di(meth)acrylate-functionalized polyether having an alkylene group, such as, for example, bis(methacryloyloxy-2-epoxycarbonylamino)substituted polyalkylene ether. Group B from formula 14 is, in these cases, a polyether group. Preferably, it is a compound containing bis(methacryloyloxy-2-epoxycarbonylamino) containing a linear or branched alkylene group having 3 to 20, preferably 3 to 9 carbon atoms or a divalent cycloaliphatic group having 3 to 20, preferably 3 to 9 carbon atoms. This can also be an alkylene substituted with a methyl group or a cyclohexyl group substituted with a methyl group.

[0049] In addition, base monomer M3 can also be HP-UDMA which is a reaction product of 3-hydroxypropyl methacrylate and trimethylhexamethylene diisocyanate, or HP-UDA which is a reaction product of 3-hydroxypropyl acrylate and trimethylhexamethylene diisocyanate.

[0050] The urethane (meth)acrylate having a divalent cycloaliphatic hydrocarbon group is obtained by reacting 2 moles of 2-hydroxyethyl methacrylate (HEMA) or 2 moles of 2-hydroxyethyl acrylate (HEA) with 1 mole of a cycloaliphatic diisocyanate.

[0051] Suitable diisocyanates are isophorone diisocyanate (1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane) or H12-MDI (1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane and other cyclic diisocyanates. Examples include UDA-IPDI which is a reaction product of 2 molecules of 2-hydroxyethyl acrylate (HEA) and 1 molecule of isophorone diisocyanate (IPDI), and UDMA-IPDI which is an addition compound of 2 molecules of 2-hydroxyethyl methacrylate (HEMA) and 1 molecule of isophorone diisocyanate.

[0052] Suitable base monomer M3 is available, for example, under the following trade names or brand names: Ebecryl 230 (aliphatic urethane diacrylate), CN9200 (aliphatic urethane diacrylate), Ebecryl 210 (aromatic urethane diacrylate oligomer), Ebecryl 270 (aliphatic urethane diacrylate oligomer), Photomer 6210 (aliphatic urethane diacrylate), Photomer 6891 (aliphatic urethane) diacrylate), UDMA, Genomer 4256 (aliphatic urethane dimethacrylate, Genomer 4267 (aliphatic urethane diacrylate), Genomer 4259 (aliphatic urethane diacrylate), RCX18-059 (aliphatic urethane diacrylate), CN1963CG (aliphatic urethane methacrylate), CN1993CG (aliphatic urethane methacrylate), PRO21252 (aliphatic urethane acrylate), H1391 (hydroxypropyl urethane dimethacrylate), X851-1066 (urethane dimethacrylate), X726-000 (PEG400 extended urethane dimethacrylate), and urethane methacrylate 14-774 (aliphatic urethane dimethacrylate), Genomer 4277 (aliphatic urethane dimethacrylate).

[0053] Base monomer M3 is preferably selected from 7,7,9-(or 7,9,9-)trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazadecane-1,16-diyl-bis(2-methylacrylate) (UDMA), 7,7,9-(or 7,9,9-)trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazadecane-1,16-diol diacrylate (UDA), the reaction product of two molecules of 2-hydroxyethyl acrylate (HEA) and one molecule of isophorone diisocyanate (IPDI) (UDA-IPDI), and mixtures thereof.

[0054] In a preferred embodiment, base monomer M3 is selected from UDMA, UDA, UDA-IPDI, and mixtures thereof.

[0055] In addition, the monomer mixture may contain other monomers. The other monofunctional monomers are preferably MMA (methyl methacrylate), EMA (ethyl methacrylate), n-BMA (n-butyl methacrylate), IBMA (isobutyl methacrylate), t-BMA (tert-butyl methacrylate), EHMA (2-ethylhexyl methacrylate), LMA (lauryl methacrylate), TDMA (tridecyl methacrylate), SMA (stearyl methacrylate), CHMA (cyclohexyl methacrylate), BZMA (benzyl methacrylate), IBXMA (isobornyl methacrylate), MAA (methacrylic acid), HEMA (2-hydroxyethyl methacrylate), HPMA (2-hydroxypropyl methacrylate), DMMA (dimethylaminoethyl methacrylate), DEMA (diethylaminoethyl methacrylate), GMA (glycidyl methacrylate), THFMA (tetrahydrofurfuryl methacrylate), AMA (allyl methacrylate), ETMA (ethoxyethyl methacrylate), 3FMA (trifluoroethyl methacrylate), 8FMA (octafluoropentyl methacrylate), IBA (isobutyl acrylate), TBA (tert-butyl acrylate), LA (lauryl acrylate), CEA (cetyl acrylate), STA (stearyl acrylate), CHA (cyclohexyl acrylate), BZA (benzyl acrylate), IBXA (isobornyl acrylate), 2-MTA (2-methoxyethyl acrylate), ETA (2-ethoxyethyl acrylate), EETA (ethoxyethoxyethyl acrylate), PEA (2-phenoxyethyl acrylate), THFA (tetrahydrofurfuryl acrylate), HEA (2-hydroxyethyl acrylate), HPA (2-hydroxypropyl acrylate), 4HBA (4-hydroxybutyl acrylate), DMA (dimethylaminoethyl acrylate), 3FA (trifluoroethyl acrylate), 17FA (heptadecafluorodecyl acrylate), 2-PEA (2-phenoxyethyl acrylate), TBCHA (4-tert-butylcyclohexyl acrylate), EHA (2-ethylhexyl acrylate), 3EGMA (triethylene glycol monomethacrylate), isodecyl methacrylate, isodecyl acrylate,Trimethylcyclohexyl methacrylate, trimethylcyclohexyl acrylate, tert-butylcyclohexyl acrylate, SR256 (2-(2-ethoxyethoxy)ethyl acrylate), SR257C (C16-C18 alkyl acrylate), CD278 (diethylene glycol monobutyl ether acrylate), SR440 (isooctyl acrylate), SR484 (octyldecyl acrylate), adamantyl methacrylate (CAS=16887-36-8), dicyclopentanyl methacrylate (CAS=34759-34-7), dicyclopentenyl oxyethyl methacrylate (CAS=68586-19-6), dicyclopentanyl acrylate (CAS=79637-74-4), dicyclopentenyl oxyethyl acrylate (CAS=65983-31-5), and dicyclopentanyl methyl acrylate (CAS=93962-84-6). Other difunctional and polyfunctional monomers are preferably DDDMA (decan-1,10-diol dimethacrylate), DDDA (decan-1,10-diol dimethacrylate), NDDA (nonane-1,9-diol diacrylate), NDDMA (nonane-1,9-diol dimethacrylate), HDDMA (hexane-1,6-diol dimethacrylate), HDDA (hexane-1,6-diol diacrylate), PDDMA (pentane-1,5-diol dimethacrylate), PDDA (pentane-1,5-diol diacrylate), BDDMA (butane-1,4-diol dimethacrylate), BDDA (butane-1,4-diol diacrylate), PRDMA (propane-1,3-diol dimethacrylate), PRDA (propane-1,3-diol acrylate), GDMA (glycerol dimethacrylate), PEG400DA (polyethylene glycol 400 diacrylate), PEG400DMA (polyethylene glycol 400 dimethacrylate), PEG300DA (polyethylene glycol 300 diacrylate), PEG300DMA (polyethylene glycol 300 dimethacrylate), PEG200DA (polyethylene glycol 200 diacrylate), PEG600DA (polyethylene glycol 600 diacrylate),NPG(PO)2DA (Propoxylated(2) Neopentyl Glycol Diacrylate), NPG(PO)2DMA (Propoxylated(2) Neopentyl Glycol Dimethacrylate), EGDMA (Ethylene Glycol Dimethacrylate), EGDA (Ethylene) Glycol Diacrylate), TEGDMA (Triethylene Glycol Dimethacrylate), TEDA (Triethylene Glycol Diacrylate), 4EGDMA (Tetraethylene Glycol Dimethacrylate), 4EGDA (Tetraethylene Glycol Diacrylate), BGDMA (1,3-Butylene Glycol Dimethacrylate), BGDA (1,3-Butylene Glycol Diacrylate), DEGDMA (Diethylene Glycol Dimethacrylate), DEGDA (Diethylene Glycol Diacrylate), NPG-DMA (Neopentyl Glycol Dimethacrylate), NPG-DA (Neopentyl Glycol Diacrylate), TPGDMA (Tripropylene Glycol Dimethacrylate), TPGDA (Tripropylene Glycol Diacrylate), SR341 (3-Methylpentane-1,5-diol Diacrylate), CD536 (Dioxane Glycol Diacrylate), TMPTMA (Trimethylolpropane Trimethacrylate), TMPTA, Trimethylolpropane Triacrylate, DTMPTMA (Ditrimethylolpropane Tetramethacrylate); DTMPTA (Ditrimethylolpropane Tetraacrylate); DiPENTMA (Dipentaerythritol Pentamethacrylate); DiPENTA (Dipentaerythritol Pentaacrylate), DPEHMA (Dipentaerythritol Hexamethacrylate), DPEHA (Dipentaerythritol Hexaacrylate), Miramer M340 (Pentaerythritol Triacrylate), SR494 (Ethoxylated Pentaerythritol Tetraacrylate), Miramer M4004 (Pentaerythritol n-EO Tetraacrylate), SR593 (Ethoxylated Pentaerythritol Triacrylate), Ethoxylated Trimethylolpropane Trimethacrylate, Ethoxylated Trimethylolpropane Triacrylate, Propoxylated Trimethylolpropane Trimethacrylate, Propoxylated Trimethylolpropane Triacrylate,Selected from ethoxylated pentaerythritol trimethacrylate, ethoxylated pentaerythritol triacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated dipentaerythritol trimethacrylate, ethoxylated dipentaerythritol triacrylate, ethoxylated dipentaerythritol tetramethacrylate, ethoxylated dipentaerythritol tetraacrylate, ethoxylated dipentaerythritol pentamethacrylate, ethoxylated dipentaerythritol pentaacrylate, ethoxylated dipentaerythritol hexamethacrylate, ethoxylated dipentaerythritol hexaacrylate, propoxylated pentaerythritol trimethacrylate, propoxylated pentaerythritol triacrylate, propoxylated pentaerythritol tetramethacrylate, propoxylated pentaerythritol tetraacrylate, propoxylated dipentaerythritol trimethacrylate, propoxylated dipentaerythritol triacrylate, propoxylated dipentaerythritol tetramethacrylate, propoxylated dipentaerythritol tetraacrylate, propoxylated dipentaerythritol pentamethacrylate, propoxylated dipentaerythritol pentaacrylate, propoxylated dipentaerythritol hexamethacrylate, propoxylated dipentaerythritol hexaacrylate, Miramer M320 (propoxylated glycerol triacrylate), SR9019 (propoxylated glycerol triacrylate), SR9020 (propoxylated glycerol triacrylate), SR9021 (highly propoxylated glycerol triacrylate), Jenomer 3364 (modified acrylated polyether) polyol), SR9041 (pentaacrylate). Other monofunctional, difunctional, and polyfunctional monomers may be present alone or in a mixture.,

[0056] Other preferred monomers are triethylene glycol dimethacrylate (TEGDMA), tripropylene glycol diacrylate (TPGDA), 2-hydroxyethyl acrylate (HEA), dicyclopentanyl methyl acrylate (TCDA), and mixtures thereof.

[0057] It is preferred that one or more of the following base monomers be present in the following mass fractions based on the total mass of the monomer mixture: - Base monomer M1 in an amount of 2% to 75% by weight, preferably 5% to 68% by weight, more preferably 13% to 63% by weight, and even more preferably 15% to 52% by weight; - Base monomer M2 in an amount of 5% to 96% by weight, preferably 12% to 65% by weight, more preferably 30% to 63.5% by weight, and even more preferably 30% to 52% by weight; - Base monomer M3 in an amount of 0% to 75% by weight, preferably 0.1% to 65% by weight, more preferably 12% to 65% by weight, and even more preferably 12% to 64% by weight.

[0058] In addition, the other monomers may be present in a mass fraction of 0 to 15% by weight, preferably 0.1 to 15% by weight, more preferably 1 to 10% by weight, more preferably 1 to 4% by weight, and even more preferably 1 to 2% by weight based on the total mass of the monomer mixture.

[0059] The monomer mixture preferably contains base monomers M1 and M2 in a mass fraction of 25% by weight or more, more preferably 30% by weight or more, even more preferably 40% by weight or more, still more preferably 50% by weight or more, still more preferably 60% by weight or more, still more preferably 70% by weight or more, still more preferably 80% by weight or more, and still more preferably 90% by weight or more, based on the monomer mixture or the total mass consisting of the monomer mixture.

[0060] According to the present invention, the mass ratio Y = m(M2) / m(M1) of the base monomer M2 to the base monomer M1 is preferably 0.5 ≦ Y ≦ 20, more preferably 0.6 ≦ Y ≦ 10, still more preferably 0.95 ≦ Y ≦ 5.

[0061] The monomer mixture may contain the base monomers M1, M2, and M3 in a mass fraction of 80% by weight to 100% by weight, preferably 85% by weight to 100% by weight, more preferably 87% by weight to 100% by weight, still more preferably 100% by weight, based on the total mass of the monomer mixture or the monomer mixture.

[0062] According to the present invention, the monomer mixture preferably does not contain a monomer having a bisphenol A structure.

[0063] In particular, 2,2-bis[4-(2-hydroxy-3-(meth)acryloyloxypropoxy)phenyl]propane (bisGMA) and / or ethoxylated bisphenol A di(meth)acrylate (bisEMA) are not present. The same applies to the polymerizable dental material.

[0064] In one embodiment, the monomer mixture preferably does not contain monomers selected from low molecular weight and low viscosity mono- and di(meth)acrylates. In particular, it does not contain monomers having a viscosity of less than 0.05 Pa·s at a temperature of 23°C and / or having partial solubility in water. In particular, the monomer mixture does not contain di(meth)acrylates having an oligo[ethyleneoxy] group or a linear or branched C1-C10 alkylene group. The monomer mixture more preferably does not contain hexanediol diacrylate (HDDA), hexanediol dimethacrylate (HDDMA), triethylene glycol diacrylate (TEGDA) and / or triethylene glycol dimethacrylate (TEGDMA). The same applies to the polymerizable dental material.

[0065] The viscosity of the monomer or organic resin is regularly specified by the manufacturer and can be determined using a viscometer (e.g., Kinexus Pro from Malvern Instruments Ltd.). A plate-plate geometry with an upper plate diameter of 25 mm and a gap width of 0.1 mm was used. The measurement covered a shear stress range of 0.1 Pa to 50 Pa. For the evaluation, the value at a shear stress of 50 Pa was used. The measurement was carried out at a temperature of 23 °C, monitored and kept constant by the internal temperature control of the apparatus.

[0066] At a temperature of 23 °C, the monomer mixture of the present invention preferably has a viscosity of 0.2 to 10 Pa·s, more preferably 1 to 6 Pa·s.

[0067] The present invention has the advantage that the monomer mixture according to the present invention, and thus the polymerizable dental material according to the present invention, overcomes the above-mentioned drawbacks of the prior art. The monomer mixture and the polymerizable dental material are readily available and can additionally be produced from base monomers with reduced potential toxicity. When using the monomer mixture of the present invention in the production of dental materials, the polymerization shrinkage is reduced while obtaining good mechanical properties of the resulting dental material. In particular, the monomer mixture can be used to obtain dental materials, especially dental composites, with improved volume shrinkage rate, improved flexural strength, and good elastic modulus. This is because a decrease in crosslink density and flexural strength was expected considering the molecular size and structure of the base monomer M1.

[0068] Therefore, the monomer mixture and the polymerizable dental material preferably do not contain monomers or other compounds having structural elements derived from bisphenol A, or low molecular weight mono- and di(meth)acrylates having partial solubility in water, especially TEGDMA.

[0069] The present invention further provides a monomer mixture for producing a dental material comprising a and b: a. The following empirical formula 1:

Chemical formula

Chemical formula

[0070] The monomer mixture preferably consists of a plurality of base monomers M1, more preferably more than 2 base monomers M1, even more preferably more than 3 base monomers M1, even more preferably more than 4 base monomers M1, even more preferably more than 5 base monomers M1, and the like. Preferably, the mixture further contains base oligomers in addition to the base monomers. According to the present invention, such a mixture is also referred to as a mixture M1 of base monomers.

[0071] In addition to the base monomer M1 where n = 1 (i.e., the monomer), it is preferable that at least one base monomer M1 where n is greater than 1 (i.e., the oligomer) is also present in the mixture. The mass fraction of the base monomer M1 where n is greater than 1 can be determined by fractionation (or fractionation) by gel permeation chromatography using a refractive index detector (measurement by visible light), and is preferably 5 to 70% by weight, more preferably 10 to 60% by weight, even more preferably 15 to 50% by weight, based on the total mass of all the base monomers M1 in the monomer / oligomer series of n = 1 to 9.

[0072] The distribution of the base monomer M1 with respect to n can vary within a wide range. The basic monomer M1 with n = 2 to 5 or n = 2 to 4 may have the highest mass fraction based on the total mass fraction of the base monomer M1. However, the base monomer M1 where n = 1 may also have the highest mass fraction compared to the individual base monomers M1 present in the monomer mixture where n = 2 to 9.

[0073] The base monomer M1 where n > 1 exists as a base monomer with n = 2 to 9, preferably n = 2 to 7, more preferably n = 2 to 5.

[0074] In one embodiment, all base monomers M1 of the monomer / oligomer series where n = 1 to 9, preferably n = 1 to 7, more preferably n = 1 to 5 may be present side by side. That is, if at least one compound is present in each case for each n from 1 to 9, there will be at least 9 compounds (i.e., a monomer for n = 1, 8 oligomers for n = 2, 3, 4, etc.) in the monomer mixture (or monomer / oligomer mixture). In the case of n = 1 to 7, at least 7 compounds (i.e., 1 monomer and 6 oligomers) are present, and in the case of n = 1 to 5, at least 5 compounds (i.e., 1 monomer and 4 oligomers) are present in the monomer mixture.

[0075] Furthermore, for a monomer mixture for producing a dental material in which the mixture contains at least two or three or more base monomers M1, the same characteristics and conditions as those of the monomer mixture of the present invention for producing a dental material containing at least one base monomer M1 are applied.

[0076] The present invention further provides the use of the monomer mixture of the present invention, preferably for the production of a polymerizable dental material, preferably a dental composite, a core build-up material, a root canal filling material, a filling material, an underfill material, a fixing material, a crown material, a bridge material, a restorative material and / or a prosthetic material, preferably as described in any one of claims 1 to 10.

[0077] In a preferred embodiment, it is a radically polymerizable dental material.

[0078] The present invention also provides a polymerizable dental material comprising: a) the monomer mixture of the present invention, preferably as described in any one of claims 1 to 10, b) optionally, at least one initiator or initiator system for polymerization, c) optionally, a filler, d) optionally, conventional dental additives.

[0079] The coincident dental material may take the form of a kit. The kit may contain a single component or multiple components thereof. In the case of a multi-component kit or system, the production of the dental material is carried out by mixing the components at a specified mixing ratio immediately before applying the dental material and then curing it.

[0080] B) Initiator A suitable initiator or initiator system can initiate a polymerization reaction, preferably a free radical polymerization reaction. Such initiators and initiator systems are known to those skilled in the art.

[0081] The polymerization initiator system consists of at least one polymerization initiator and at least one additional compound such as a co-polymerization initiator. These may be dispersed in different components of the polymerizable dental material. The dental material according to the present invention can be cured thermally, chemically, or photochemically, i.e., by irradiation with ultraviolet and / or visible light.

[0082] Suitable initiators may be, for example, photoinitiators. These are characterized by causing 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, optionally through an additional reaction with one or more co-initiators. Preferably, phosphine oxide, acylphosphine oxide, bisacylphosphine oxide and their derivatives, such as acylgermanane, benzoin ether, benzyl ketal, acetophenone, benzophenone, thioxanthone, bisimidazole, metallocene, fluorone, α-dicarbonyl compound, aryldiazonium salt, arylsulfonium salt, aryliodonium salt, ferrocenium salt, phenylphosphonium salt, or a mixture of the above compounds as described in EP2649981A1, WO2017 / 055209A1 and EP3153150A1.

[0083] Particularly preferred are diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, benzoin, benzoin alkyl ether, benzyldialkyl ketal, α-hydroxyacetophenone, dialkoxyacetophenone, α-aminoacetophenone, isopropylthioxanthone, camphorquinone, phenylpropanedione, 5,7-diiodo-3-butoxy-6-fluorone, (η 6 -cumene)(η 5 -cyclopentadienyl)iron hexafluorophosphate, (η 6 -cumene)(η 5 -cyclopentadienyl)iron tetrafluoroborate, (η 6 -cumene)(η 5 -cyclopentadienyl)iron hexafluoroantimonate, a substituted diaryliodonium salt, a triarylsulfonium salt, or a mixture of the above compounds.

[0084] The co-initiator used for photochemical curing is preferably a tertiary amine, a borate, an organic phosphite, a diaryliodonium compound, a thioxanthone, a xanthene, a fluorene, a fluorone, an α-dicarbonyl compound, a dicarbonyl-based, condensed polyaromatic described in WO2021 / 048313A1, or a mixture of the above compounds. Particularly preferred are N,N-dimethyl-p-toluidine, N,N-dialkylalkylaniline, N,N-dihydroxyethyl-p-toluidine, 2-ethylhexyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, butyrylcholine triphenylbutyl borate, or a mixture of the above compounds.

[0085] It is also possible to use as the initiator those known as heat initiators that can cause the curing of materials by absorbing thermal energy at high temperatures. It is preferable to use inorganic and / or organic peroxides, inorganic and / or organic hydroperoxides, diethyl α,α'-azobisisobutyrate, α,α'-azobisisobutyronitrile, benzopinacol or a mixture of the above compounds. Particularly preferred are diacyl peroxides such as benzoyl peroxide or lauroyl peroxide, cumene hydroperoxide, benzopinacol, 2,2'-dimethylbenzopinacol or a mixture of the above compounds.

[0086] For chemical curing at room temperature, generally, a redox initiator system consisting of one or more initiators and one or more co-initiators that function as activators is used. For reasons of storage stability, the individual components of the initiator system are incorporated into spatially separated components of the dental material according to the invention, i.e., there are multi-component, preferably two-component materials. As the initiator, it is preferable to use inorganic and / or organic peroxides, inorganic and / or organic hydroperoxides, barbituric acid derivatives, malonylsulfamide, protonic acids, Lewis acids or Bronsted acids, or compounds that release such acids, for example, carbocation donors such as methyl triflate or triethyl perchlorate, or a mixture of the above compounds. As the co-initiator, it is preferable to use tertiary amines, heavy metal compounds, particularly compounds of Groups 8 and 9 of the Periodic Table ("iron group and copper group"), compounds containing an ionic bond halogen or pseudohalogen, for example, quaternary ammonium halides, weak Bronsted acids, for example, alcohols and water, or a mixture of the above compounds.

[0087] The dental material according to the invention may also contain any possible combination of the above initiators and co-initiators. As an example, there is a dual-curing dental material known that contains both a photoinitiator for photochemical curing and any corresponding co-initiator, and an initiator for chemical curing at room temperature and its corresponding co-initiator.

[0088] The polymerizable dental material according to the present invention is preferably photocurable. In a preferred embodiment, camphorquinone (CQ) is present as an initiator, and 2-ethylhexyl p-dimethylaminobenzoate (EHA) or ethyl p-dimethylaminobenzoate is present as a co-initiator.

[0089] C) Filler The polymerizable dental material according to the present invention may further contain conventional dental additives. The filler particles are not defined as having a specific particle shape. Rather, fillers (or fillers) having a spherical, flaky, plate-like, needle-like, leaf-like or irregular shape can be very easily used. The filler particles preferably have an average particle size of 5 nm to 100 μm, more preferably 5 nm to 50 μm.

[0090] Suitable fillers can be selected from a variety of materials commonly used in dental products. By selecting the filler, it is possible to adjust, for example, the fluidity, viscosity, consistency, color tone, radiation transparency, and mechanical stability of the dental material. Fillers are roughly classified into three types: inorganic fillers, organic fillers, and organic-inorganic composite fillers according to their chemical properties. Fillers can be used not only alone but also in combination with each other.

[0091] The inorganic filler used may be a ground powder of natural or synthetic glass or crystalline inorganic substances of various sizes and states (monodisperse, polydisperse). Suitable materials include quartz, cristobalite, glass ceramics, feldspar, barium silicate glass (e.g., those available under the trade names Kimble Ray-Sorb T3000, Schott 8235, Schott GM27884, Schott G018-053, and Schott GM39923), barium fluosilicate glass, strontium silicate glass, strontium borosilicate glass (e.g., those 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, fluoroaluminosilicate glass (e.g., those available under the trade names Schott G018-091 and Schott G018-117), zirconium or cesium borosilicate glass (e.g., available under the trade names Schott G018-307, G018-308, and G018-310), zeolite, and apatite. The filler preferably has a median particle size d50 of 0.01 to 15 μm, preferably has a median particle size d50 of 0.2 to 5 μm, and more preferably has a median particle size (or median particle diameter or median particle size or central particle diameter or central particle size; median particle size) of 0.2 to 1.5 μm. In some cases, it may be preferable for the median particle size d50 to be 0.1 to 0.5 μm. In such cases, it is particularly preferable for the median particle size d90 to be less than 1.0 μm. In addition, discrete, non-agglomerated, non-aggregated, organically surface-modified nanoparticles may be used to achieve more uniform filling of the dental material and enhance hardness and wear resistance.

[0092] In this context, nanoparticles are understood to mean 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 the voids between coarse particles. The material of the nanoparticles is preferably an oxide or a mixed oxide, preferably selected from the group consisting of oxides and mixed oxides of silicon, titanium, yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, ytterbium, lanthanum, cerium, aluminum, and mixtures thereof. The preferred oxide nanoparticles are non-aggregated. In order to enable good incorporation of the nanoparticles into the polymer matrix of the composite material, the surface of the nanoparticles is organically modified. The surface treatment of the filler is preferably carried out using a silanizing agent. A particularly suitable adhesion promoter is methacryloyloxypropyltrimethoxysilane. Commercially available usable nanoscale non-agglomerated and non-aggregated silica sols are marketed, for example, under the names "Nalco Colloidal Silicas" (Nalco Chemical Co.), "Ludox colloidal silica" (Grace), or "Highlink OG" (Clariant).

[0093] Submicron fillers or micro fillers consisting of aggregated nanoscale particles, especially those having a specific surface area (determined by the Brunauer, Emmet, and Teller method) of 100 - 400 m 2If it is within the range of / g, it may be used similarly. Fumed silica or wet precipitated silica is preferred. Suitable non-surface-treated silicon dioxide filler products that can be used are commercially available as Aerosil (trademark) ("OX50", "90", "130", "150", "200", "300", "380", "R8200" from Evonik Industries AG, Essen, Germany), Cab-O-Sil ("LM-150", "M-5", "H-5", "EH-5" from Cabot Corp, Tuscola, Illinois), HDK (trademark) ("S13", "V15", "N20", "T30", "T40", Wacker-Chemie AG, Munich, Germany), and Orisil (trademark) ("200", "300", "380", Orisil, Lviv, Ukraine).

[0094] By using aggregated nanoscale particles based on a mixed oxide of silicon dioxide and zirconium dioxide, particularly advantageous wear resistance and gloss resistance can be achieved in dental materials. Suitable fillers can be produced, for example, by the process described in US6730156 (Example A). The fillers thus produced can be surface-treated according to a method such as that described in US6730156 (for example, Production Example B).

[0095] Preferably, the aggregated filler has a median secondary size (or median secondary particle size or median secondary particle diameter or central secondary particle size or central secondary diameter; median secondary particle size) of 1 to 15 μm, preferably a median secondary particle size of 1 to 10 μm, more preferably a median secondary particle size of 2 to 5 μm.

[0096] In order to achieve a high filler content while having good aesthetics and wear stability, it may be particularly advantageous to use spherical submicron particles based on a silicon-zirconium mixed oxide as described in DE19524362A1 or US2020 / 0121564A1.

[0097] There may further be present a large amount of selected radiopaque fillers. The addition of radiopaque particles to dental materials is advantageous as it enables the distinction between healthy dental hard substances and restorations. Suitable radiopaque fillers include particles of metal oxides, metal fluorides or barium sulfate. Oxides and fluorides of heavy metals with an atomic number greater than 28 are preferred. The metal oxides and fluorides should be selected so as to affect the color of the restoration as little as possible. Metal oxides and metal fluorides with an atomic number greater than 30 are more suitable. Suitable metal oxides are oxides of yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, lanthanides (elements with atomic numbers 57 to 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 size of 40 nm to 1.5 μm, more preferably a core-shell combination product having a YF3 or YbF3 core and a SiO2 shell, and most particularly preferably, the surface of the SiO2 shell is silanized. In particular, such a core-shell combination product has a refractive index of 1.48 to 1.54 and a measured median particle size of agglomerated particles of 0.5 to 5 μm.

[0098] Examples of suitable organic fillers include filled and unfilled powder polymers or copolymers based on polymethyl methacrylate (PMMA), polyethylene methacrylate, polypropylene methacrylate, polybutyl methacrylate (PBMA), polyvinyl acetate (PVAc), polyethylene glycol (PEG), polypropylene glycol (PPG), polyvinyl alcohol (PVA), polyurethane (PU), polyurea, methyl methacrylate-ethyl methacrylate copolymer, ethylene-vinyl acetate copolymer, and styrene-butadiene copolymer. In addition, the organic filler may contain biologically active ingredients, specific pigments, polymerization initiators, stabilizers, etc. added during the manufacturing process. The organic filler can be used alone or as a mixture.

[0099] When using what is called an organic-inorganic composite filler, in dental materials, it is possible to achieve a higher filler content and at the same time advantageous polishing properties. These fillers can be produced by processing a polymerizable monomer and an inorganic filler into a paste, curing this by polymerization, and finely pulverizing it before using it as a filler. Here, it is preferable to use microfillers as the inorganic filler. After pulverization, the filler preferably has a median particle size of 0.05 to 100 μm, preferably a median particle size of 0.5 to 50 μm, more preferably a median particle size of 1 to 30 μm.

[0100] The filler in the dental material is preferably surface-modified. This is done, for example, by subjecting the described inorganic or organic-inorganic composite filler to surface treatment before use in order to improve the compatibility, affinity, and incorporation into the resin mixture of the filler. By this treatment, the surface of the inorganic particles is organically modified, that is, the surface has organic structural elements. Here, any method known to those skilled in the art can be adopted. A silanizing agent is preferred for the inorganic filler having surface OH groups. Examples here include γ-methacryloyloxyalkyltrimethoxysilane (the number of carbon atoms between the methacryloyloxy group and the silicon atom: 3 to 12), γ-methacryloyloxyalkyltriethoxysilane (the 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 silanizing agent is particularly preferably methacryloyloxypropyltrimethoxysilane.

[0101] The inorganic filler having few or no surface OH groups is preferably used together with different surface modifiers surface-treated with, for example, titanate, aluminate, zirconaluminate, surfactant, fatty acid, organic acid, inorganic acid, or metal alkoxide. The surface modifiers of salts of barium, strontium, and rare earth metals are particularly preferably organic compounds having N-, P-, S-, and / or O-containing functional groups (for example, polyol, sulfoxide, phosphinate ester, phosphonate ester, trialkylphosphine, carboxylic acid, and carboxylic acid ester). Particularly suitable here is 10-methacryloyloxydecyl dihydrogen phosphate.

[0102] In the case of particularly aggregated silicon dioxide-based nanofillers, the surface modification can consist of groups reactive towards free radicals, such as the above-mentioned methacryloyloxyalkyl groups, or groups non-reactive towards free radicals. Suitable non-reactive groups are, for example, trimethylsilyl groups, dimethylsilylene groups or methylsilylidene groups and can be applied to the surface by silanization, for example with hexamethyldisilazane, dimethyldimethoxysilane or methyltrimethoxysilane. Suitable non-reactive 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 can be modified with groups reactive in a free radical process, such as methacryloyl groups. Commercially available aggregated nanofiller products modified to react with free radicals are available under the name Aerosil R7200 (Evonik Industries AG, Essen, Germany).

[0103] The aggregated nanofillers preferably exist in a mostly deaggregated form, as described, for example, in EP1720206.

[0104] The dental material according to the present invention may contain filler particles in a proportion of 0 wt% to 95 wt%, preferably 1 wt% to 95 wt% based on the total mass of the polymerizable dental material. The amount of the filler fraction is selected according to the indication of the dental product. For example, for dental compositions for producing stable moldable filling composites, inlays, onlays, or overlays, and compositions for producing dental CAD-CAM materials to be subtractive processed, the highest possible amount of filler is used. These compositions generally have a filler content of 75 wt% to 92 wt% based on the total composition. Flowable dental composites, luting composites, core build-up materials, crown materials, bridge materials, and dental materials processed by stereolithography generally have an average filler content in the range of 40 wt% to 80 wt% based on the total composition, while dental varnishes, dental sealants, dental infiltrants, low-viscosity dental materials processed by stereolithography, and dental adhesives use fillers in an amount in the range of 1 wt% to 40 wt% based on the total composition. The above ranges of filler content should be understood only as a guide value and it is possible to deviate from this depending on the filler selected.

[0105] d) Conventional dental additives The polymerizable dental material according to the present invention may further contain conventional dental additives. Conventional dental additives are known to those skilled in the art; preferred additives are inhibitors, stabilizers, accelerators, dyes, fluorinating agents, remineralizing agents, radiopaque agents, and film formers.

[0106] Inhibitors and stabilizers are used especially to prevent premature polymerization. These are substances that react with reactive radicals to form more stable capture products. Adding an inhibitor or stabilizer can improve the storage stability of the uncured composition. An inhibitor can also be used to adjust the processing time of the curing system within an appropriate range. Suitable inhibitors are, for example, phenolic derivatives such as hydroquinone monomethyl ether (HQME) or 2,6-di-tert-butyl-4-methylphenol (BHT). Further inhibitors, such as tert-butylhydroxyanisole (BHA), 2,2-diphenyl-1-picrylhydrazyl radical, galvinoxyl radical, triphenylmethyl radical, 2,3,6,6,-tetramethylpiperidinyloxy radical (TEMPO), TEMPO derivatives, and phenothiazine and derivatives of this compound are described in EP0783880B1. Alternative inhibitors can be found in DE10119831A1 or EP1563821A1.

[0107] As a stabilizer, the polymerizable dental material may especially contain 2,6-di-tert-butyl-4-methylphenol (BHT).

[0108] Conventional dental additives present in the dental material according to the invention may include UV stabilizers. UV stabilizers are used especially to stabilize the dental material against degradation or discoloration by UV radiation. Examples of UV absorbers are 2-hydroxy-4-methoxybenzophenone, phenyl salicylate, 3-(2'-hydroxy-5'-methylphenyl)benzotriazole or diethyl 2,5-dihydroxyterephthalate.

[0109] Conventional dental additives present in the dental material according to the invention may include one or more fluoride-releasing substances in particulate form. The fluoride-releasing substances can be, for example, water-soluble fluorides such as sodium fluoride or amine fluoride. Other suitable fluoride-releasing substances are the sparingly soluble fluorides of main group 2. Fluoride-containing glasses are also suitable fluoride sources.

[0110] Other suitable additives are particulate substances that release calcium and / or phosphates and thus have a remineralizing effect. Suitable remineralizing substances are, for example, calcium phosphate compounds such as hydroxyapatite, brushite, monocalcium phosphate, fluoroapatite, and bioactive glasses as described in DE10111449A1, DE102005053954A1 or US9517186B2.

[0111] The dental material according to the invention may contain a colorant or a mixture of colorants selected from fluorescent dyes, fluorescent pigments, organic coloring pigments, inorganic coloring pigments, and mixtures thereof.

[0112] The fluorescent colorant or pigment is preferably an organic fluorescent dye or an organic fluorescent pigment, in particular a non-polymerizable organic fluorescent colorant optionally containing esters of aryl carboxylic acids such as, for example, diethyl 2,5-dihydroxyterephthalate, aryl carboxylic acids, coumarin, rhodamine, naphthalimide or derivatives thereof. Examples of inorganic fluorescent pigments are CaAl4O7:Mn 2+ (Ba0.98Eu0.02)MgAl 10 O 17 , BaMgF4:Eu 2+ , and Y(1.995)Ce(0.005)SiO5. As coloring pigments, the dental material according to the invention may include organic pigments, and further, for example, N,N'-bis(3,5 xylyl)perylene-3,4:9,10-bis(dicarboximide), copper phthalocyanine and titanate pigments, in particular chromium antimony titanate (rutile structure), spinel black, in particular pigments based on iron black (Fe3O4) in which iron is partially substituted by chromium and copper or nickel and chromium or manganese, other iron oxide-based pigments, zinc iron chromite brown spinel, ((Zn,Fe)(Fe,Cr)2O4) cobalt zinc aluminate blue spinel and / or inorganic pigments such as titanium oxide.

[0113] The components in the dental material may be present in the following mass fractions based on the total mass of the dental material according to the present invention: - A monomer mixture of 5% to 99% by weight, preferably 10% to 95% by weight, more preferably 15% to 85% by weight; - At least one polymerization initiator or polymerization initiator system of 0% to 5% by weight, preferably 0.01% to 5% by weight; - A filler of 0% to 95% by weight, preferably 1% to 95% by weight, more preferably 5% to 90% by weight, even more preferably 15% to 85% by weight. - Conventional dental additives of 0% to 5% by weight, preferably 0.001% to 5% by weight.

[0114] Preferably, the dental material does not contain a compound having a bisphenol A-based structural element.

[0115] The present invention further provides the dental material according to any one of claims 12 or 13 for use in a treatment process as the dental material according to the present invention, preferably a dental composite, filling material, underfill material, fixing material, core build-up material, root canal filling material, crown material, bridge material, restoration material and / or prosthetic material.

[0116] The present invention further provides a cured dental material produced from the polymerizable dental material of the present invention, particularly according to any one of claims 12 or 13.

[0117] The present invention can further provide a method for producing at least one, preferably at least two or three or more base monomers M1, the method comprising the following steps: a) The following formula 15:

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0118] The reaction in step a) is preferably carried out at a molar ratio of hydroxyl groups x1(OH) to isocyanate groups x1(NCO) of x1(NCO) / x1(OH), where x1(NCO) / x1(OH) > 1, more preferably x1(NCO) / x1(OH) is 1.5 to 10, and even more preferably x1(NCO) / x1(OH) is 3 to 5.

[0119] Preferably, the reaction in step a) is carried out by forming urethane groups up to a conversion of at least 95%, more preferably at least 99% of all OH groups.

[0120] The reaction in step b) is preferably carried out at a molar ratio of hydroxyl groups x2(OH) to isocyanate groups x2(NCO) of x2(OH) / x2(NCO), where x2(OH) / x2(NCO) ≥ 1, more preferably x2(OH) / x2(NCO) is 1.0 to 1.4, and even more preferably x2(OH) / x2(NCO) is 1.0 to 1.2. By the selection of the ratio x1(NCO) / x1(OH), it is possible to adjust, in particular, the ratio of the weight fraction of base monomer M1 (n = 1) to the weight fraction of base monomer M1 (n ≥ 2).

[0121] The reaction in step a) and / or b) can be carried out in a solvent or without a solvent. The solvent may be a low-viscosity resin that does not interfere with the reaction. Suitable low-viscosity resins may be those described as monomer M2 and / or other monomers, provided that they do not react under the reaction conditions used.

[0122] The reaction product from step b) (i.e., the base monomer M1 or a mixture of base monomers M1) may preferably be mixed with further monomers of the monomer mixture of the present invention immediately after completion of the reaction. Further monomers in the context of the present invention include monomers M2 and M3, as well as other monomers. In this case, for example, volatile components such as solvents are preferably removed only after addition of the further monomers. Such a procedure has the advantage that the monomer mixture still has a low viscosity and remains stirrable.

[0123] However, it may also be preferable to dry the reaction product from step b) before adding further monomers of the monomer mixture of the present invention. This can be advantageous since an excessive proportion of the compound of formula 17 can be significantly reduced by the drying process. Drying can be carried out, for example, using a thin-film evaporator. Thus, at the end of the drying process, the monomer mixture of the present invention can be produced by adding and mixing further monomers.

[0124] The present invention may further provide a monomer mixture for producing a dental material, which is produced by such a method and contains at least one, preferably at least two or three or more base monomers M1.

[0125] Next, the present invention will be described by way of example with reference to some advantageous embodiments.

Examples

[0126] Examples In the following examples, the compounds used in particular in Table 1 below were used.

[0127]

Table 1

[0128] Examples of oligourethane acrylate (OPUA) A preferred example of the base monomer M1 according to the present invention is oligourethane acrylate (OPUA), which will be explained in more detail below. The oligourethane acrylate (OPUA) according to the present invention can be obtained, for example, by reacting glycerol propoxylate having a number average propoxylation degree of 9 per molecule of glycerol with an excess of isophorone diisocyanate, and then reacting the excess isocyanate groups with HEA, to obtain a mixture having UDA-IPDI (base monomer M3). The monomer mixture thus obtained contains various OPUA (as base monomer M1), as well as UDA-IPDI (as base monomer M3) and the HEA used in excess (as other monomers). It is also possible to add TPGDA (as other monomers) to this mixture, which can function as a thinner resin.

[0129] The OPUA (as base monomer M1) prepared in this way has the following empirical formula 1:

Chemical formula

Chemical formula

[0130] The bonds shown (i.e., the dashed lines) each represent the bonding point of the group to the corresponding partner group. Therefore, the three carbon atoms of group T are each bonded to the corresponding oxygen atom of T[(( O R) r1-r3 )O] t of group K. The carbamoyl carbon atom -NH- C O- of group U is - O- The oxygen atom of the -S-PG group and the group K(T[((OR) r1-r3 ) O t The oxygen atom of (T[(OR) r1-r3 ) O t may be attached to either the oxygen atom of the -S-PG group or to one of the two oxygen atoms of different groups K. - O The oxygen atom of the -S-PG group is always attached to the carbamoyl carbon atom of the U group NH- C O-.

[0131] As an example of the molecular segment T-((OR) r2 )-O-U-O-S-PG, the bonding situation is as follows:

Chemical formula

[0132] Synthesis example: Preparation of OPUA in a mixture with UDA-IPDI Described herein is a method by which OPUA can be prepared as the base monomer M1 in a mixture with UDA-IPDI.

[0133] 60 g of glycerol propoxylate 9 is dissolved in 100 ml of toluene and completely concentrated on a rotary evaporator. Glycerol propoxylate 9 with a residual toluene content of about 11.6 wt% is obtained, which is considered an inert component for all further synthetic purposes. The weights below refer to pure glycerol propoxylate 9.

[0134] ​​In a three-necked flask equipped with a dropping funnel and a reflux condenser, attach a drying tube filled with CaCl₂, and first charge 15 ml of dry THF from which moisture has been removed. Add isophorone diisocyanate of Ag and dissolve it while stirring at room temperature. Add 9 of glycerol propoxylate of Bg at room temperature. Then, add 87.2 μl of a 51.5 g / L solution of Sn-Kat in dry toluene while cooling in a water bath, and stir the mixture for an additional 10 minutes while cooling with water. Next, stir the mixture at a bath temperature of 40 °C for 3.5 hours. Dropwise add HEA of Cg, and stir the batch at 40 °C for an additional 0.5 hour and then at room temperature for 62 hours. Residual isocyanate groups were not detected by IR spectroscopy. Thereafter, spread the reaction mixture thinly on an evaporating dish and first dry it in air at room temperature for 2 days. Remove the residual solvent from the mixture over 2 days at 60 °C in a heated cabinet with forced ventilation. A colorless to pale yellowish transparent viscous substance is obtained almost quantitatively.

[0135] Batch 1 and 2 shown in Table 3 are obtained from Mixture 1 and 2 of Table 2 below.

[0136]

Table 2

[0137] Add an appropriate amount of TPGDA to Batch 1.

[0138] Formulation Example Batches 1 to 3 employed in the examples were characterized by HPLC-MS and MALDI-TOF. For Mixture 1 and 2, and isolated OPUA 1 from Batch 3, the weight fractions shown in Table 3 were obtained by GPC measurement.

[0139]

Table 3

[0140] Isolation of Oligomer Mixture OPUA 1 The oligomer mixture OPUA 1 is obtained by filtering mixture 1 through a silica gel column. In a typical procedure, 33 g of mixture 1 in 12 ml of eluent consisting of n-heptane / ethyl acetate 60:40 (volume / volume) is loaded onto a silica gel column (diameter 4.8 cm, length 22 cm) filled with the eluent. Components other than OPUA 1 are eluted with 3.5 L of the same eluent. Next, OPUA 1 is washed from the column with 1.2 L of ethyl acetate. The product solution is carefully concentrated on a rotary evaporator while introducing air. The fluid solution is thinly applied and left in air at room temperature to remove the residual solvent over 17 days.

[0141] Manufacture of Resin To manufacture the resin, monomer mixtures were prepared according to Tables 4 - 6 below, and an initiator system was added (all values are in wt%, and in each case are based on the total mass of the polymerizable dental material). The initiator system consisted of the same amount of camphorquinone (CQ) and 2-ethylhexyl p-dimethylaminobenzoate (EHA) as a co-initiator in all examples. In all mixtures, 2,6-di-tert-butyl-4-methylphenol (BHT) was used at the same concentration as a stabilizer. The resulting resin was homogenized overnight using a stirrer.

[0142] Examples 1 - 8 in Tables 4 and 5 represent non-inventive monomer mixtures and show the characteristics of prior art monomer mixtures and polymerizable dental materials. In Comparative Examples 3 - 8, the base monomer bis-GMA was replaced with other non-inventive difunctional urethane (meth)acrylates. In Comparative Examples 7 and 8, good volume shrinkage values were obtained, but the flexural strength values were significantly inferior. In Comparative Examples 3, 4, 5, and 6, neither the flexural strength nor the volume shrinkage rate was improved.

[0143]

Table 4

[0144]

Table 5

[0145] Examples 9 to 14 in Table 6 correspond to the monomer mixture according to the present invention, and thus to the polymerizable dental material according to the present invention. In all examples, the volume shrinkage rate is significantly improved compared to the bis-GMA-TEGDMA resin mixture (Comparative Examples 1 and 2) and the UDMA-TEGDMA resin mixture (Comparative Example 3). The measured flexural strength values of Examples 9 to 14 of the present invention are at least equivalent, and in some cases even partially improved, compared to Examples 1 to 3, despite the significant decrease in the shrinkage value.

[0146] [Table 6]

[0147] Manufacture of dental composites Dental compositions were manufactured according to Table 7 below. In Examples 15 to 19, the monomer mixture of the present invention was used. In Comparative Example 20, a corresponding dental composite was manufactured using a monomer mixture containing bis-GMA. For the manufacture of the dental composition, a total of 75% by weight of dental glass G018-053 (median particle size 0.7 μm, 6% by weight of silane) manufactured by Schott AG was gradually added to the resin mixture (dental composition) obtained above while homogenizing using a SpeedMixer DAC 400-1 VAC-P (Hauschild, Germany). Thereafter, while further stirring, the mixture was degassed at 20 mbar for 3 minutes.

[0148] [Table 7]

[0149] [Table 8]

[0150] Determination of flexural strength and modulus of elasticity The flexural strength and modulus of elasticity were determined. Test specimens for this purpose were prepared according to ISO 4049:2009. Different from this, the test specimens were prepared by irradiating with a HiLite (registered trademark) power photopolymerization device (manufactured by Heraeus). Therefore, dental composites with a test specimen shape (40 mm × 2 mm × 2 mm) were irradiated from both sides for 90 seconds each. The test specimens were stored in distilled water at 37°C for 24 hours. The flexural strength and modulus of elasticity were determined using a Zwick universal testing machine (model Z010 or Z2.5, Zwick-Roell, Germany). The average value and standard deviation of six individual measurements are reported.

[0151] Volume shrinkage The volume shrinkage rate was calculated from the density difference ρ of the dental composite before curing (VA) and 24 hours after curing (NA). Three samples were measured for one composite, and the average value was used as the density. To measure the density of the composite after curing, cylindrical test specimens (diameter 8 mm, height 2 mm) were prepared by irradiating with a HiLite power photopolymerization device (manufactured by Heraeus). The irradiation was performed for 90 seconds from both sides of the test specimens. These were stored in dry condition at 23°C for 24 hours. The densities of the cured and uncured composites were measured using a helium gas pycnometer (AccuPyc III 1340, Micromeritics Instrument Corporation, USA, GA).

[0152] The volume shrinkage rate VS is given by the following formula: VS = 100% × (ρ NA - ρ VA ) / ρ NA and was determined from.

[0153] GPC measurement The measurements were carried out using a GPC system (PSS SECcurity GPC system, manufactured by PSS Polymer Standards Service GmbH, Germany) equipped with a column oven and an RI detector.

[0154] The following column combinations were used for the separation of components: guard column VA50 / 7.7 Nucleogel GP5P, separation columns VA 300 / 7.7 Nucleogel GPC104-5, VA 300 / 7.7 Nucleogel GPC500-5 (all from Macherey & Nagel). The columns were temperature-controlled at 20 °C.

[0155] The sample concentration was approximately 1%. 20 μl of each sample was injected, and THF ((Merck 109731)) was used as the mobile phase. The flow rate of the mobile phase was 0.5 ml / min.

[0156] The ratios of oligomers and monomers were determined by integrating the respective areas under the measurement curves of the refractive index detector; when peaks overlapped, a perpendicular line was dropped onto the volume axis at the local minimum of the curve between the peaks and at the intersection of the perpendicular line with the volume axis used as the integration limit.

Claims

1. A monomer mixture for manufacturing dental materials, a. The following empirical formula 1: 【Chemistry 1】 [In the above empirical formula 1, PG is -OOC-CH=CH ２ and -OOC-C(CH ３ ) = CH ２ A polymerizable group selected from, S is a spacer group selected from unbranched and branched alkylenes having 1 to 10 carbon atoms, which may further contain oxygen and / or -OOC- in the carbon chain, and is preferably ethylene. O is oxygen, U is given by the following equation 2: 【Chemistry 2】 (In the above equation 2, A is a group selected from divalent aromatic or aliphatic C6-C20 hydrocarbon groups, preferably divalent C6-C13 aliphatic hydrocarbon groups, and more preferably divalent saturated cyclic C6-C13 hydrocarbon groups. It is a base represented by, K is given by the following equation 3: 【Transformation 3】 (In the above formula 3, T is a trivalent hydrocarbon group having 3 to 7 carbon atoms. O is oxygen, In each case, R is independently selected from an ethylene group, a 1,2-propylene group, a 1,3-propylene group, and a mixture thereof, preferably a 1,2-propylene group. r is independently 1 to 12, preferably 1 to 9, and more preferably 1 to 6 in each case. s is 0 or 1, preferably 0. t is 2 or 3, preferably 3. (The condition s + t = 3 must be satisfied.) n is 1 to 9, preferably 1 to 7, more preferably 1 to 5. The conditions m = 2n + 1 and o = n + 2 must be satisfied. At least one base monomer M1, b. Equation 4 below: 【Chemistry 4】 [In the above formula 4, PG' is -OOC-CH=CH ２ and -OOC-C(CH ３ ) = CH ２ A polymerizable group selected from, S' is a spacer group selected from unbranched and branched alkylenes having 1 to 10 carbon atoms, which may further contain oxygen and / or -OOC- in the carbon chain, preferably methylene, or S' does not exist. A' is an aliphatic polycyclic group, preferably an aliphatic tricyclic hydrocarbon group, in which one or more hydrogen atoms may be independently substituted with a C1-C4 alkyl radical, a C1-C4 alkoxy radical, a fluorine atom, a chlorine atom, or a trifluoromethyl group, more preferably tricyclodecanylene, and even more preferably tricyclo[5.2.1.0 / 2,6]decanylene. at least one base monomer M2 and A monomer mixture comprising [the specified substance].

2. T is a trivalent hydrocarbon group having three carbon atoms, preferably the following formula 5: 【Transformation 5】 (In the above formula 5, The bonds shown each represent the bonding points to the oxygen atom in Equation 3. The monomer mixture according to claim 1, characterized by being represented as follows.

3. A is a divalent hydrocarbon group having 10 carbon atoms, preferably the following formula 6: 【Transformation 6】 (In the above formula 6, The two bonds shown represent the bonding points to the nitrogen atom in Equation 2. A monomer mixture according to claim 1 or 2, characterized by being represented as such.

4. The monomer mixture according to claim 1, characterized in that the monomer mixture contains a plurality of base monomers M1, preferably at least two base monomers M1, more preferably more than two base monomers M1, even more preferably more than three base monomers M1, and even more preferably more than four base monomers M1.

5. The monomer mixture according to claim 1, wherein the base monomer M2 is selected from bis(methacryloyloxymethyl)tricyclo[5.2.1.0 / 2,6]decane, bis(acryloyloxymethyl)tricyclo[5.2.1.0 / 2,6]decane, and mixtures thereof, preferably characterized in that the base monomer M2 is bis(acryloyloxymethyl)tricyclo[5.2.1.0 / 2,6]decane.

6. The monomer mixture according to claim 1, wherein the monomer mixture comprises a base monomer M3 different from the base monomer M1 of formula 1 and the base monomer M2 of formula 2, the base monomer M3 is preferably selected from urethane monomers, and more preferably the base monomer M3 is selected from UDMA, UDA, UDA-IPDI, and mixtures thereof.

7. One or more of the following base monomers, based on the total mass of the monomer mixture, are as follows: - Base monomer M1 in an amount of 2% to 75% by weight, preferably 5% to 68% by weight, more preferably 13% to 63% by weight, and even more preferably 15% to 52% by weight. - Base monomer M2 in an amount of 5% to 96% by weight, preferably 12% to 65% by weight, more preferably 30% to 63.5% by weight, and even more preferably 30% to 52% by weight. - Base monomer M3 in an amount of 0% to 75% by weight, preferably 0.1% to 65% by weight, more preferably 12% to 65% by weight, and even more preferably 12% to 64% by weight. The monomer mixture according to claim 1, characterized in that it exists in a mass fraction of the specified amount.

8. The monomer mixture according to claim 1, characterized in that the monomer mixture does not contain monomers having a bisphenol A structure, and preferably does not contain 2,2-bis[4-(2-hydroxy-3-(meth)acryloyloxypropoxy)phenyl]propane (bis-GMA) and ethoxylated bisphenol A di(meth)acrylate (bis-EMA).

9. The monomer mixture according to claim 1, characterized in that the monomer mixture does not contain monomers selected from mono- and di(meth)acrylates with low molecular weight and low viscosity, monomers having a viscosity of less than 0.05 Pa·s at a temperature of 23°C and / or partial solubility in water, and / or monomers selected from hexanediol diacrylate (HDDA), hexanediol dimethacrylate (HDDMA), triethylene glycol diacrylate (TEGDA), and triethylene glycol dimethacrylate (TEGDMA).

10. A monomer mixture for manufacturing dental materials, a. The following empirical formula 1: 【Transformation 7】 [In the above empirical formula 1, PG is a polymerizable group selected from -OOC-CH=CH ２ and -OOC-C(CH ３ )=CH ２ and is a polymerizable group selected therefrom, S is a spacer group selected from unbranched and branched alkylenes having 1 to 10 carbon atoms, which may further contain oxygen and / or -OOC- in the carbon chain, and is preferably ethylene. O is oxygen, U is given by the following equation 2: 【Transformation 8】 (In the above equation 2, A is given by the following equation 6: 【Chemistry 9】 <In the above formula 6, The two bonds shown represent the bond points to the nitrogen atom in Equation 2. (A group selected from divalent aromatic or aliphatic C6-C20 hydrocarbon groups, preferably divalent C6-C13 aliphatic hydrocarbon groups, represented by ) It is a base represented by, K is given by the following equation 3: 【Chemistry 10】 (In the above formula 3, T is a trivalent hydrocarbon group having 3 to 7 carbon atoms, preferably the following formula 5: 【Chemistry 11】 <In the above formula 5, The three bonds shown each represent the bond points to the oxygen atom in Equation 3. (This is a trivalent hydrocarbon group represented by ) O is oxygen, In each case, R is independently selected from an ethylene group, a 1,2-propylene group, a 1,3-propylene group, and a mixture thereof, preferably a 1,2-propylene group. r is independently 1 to 12, preferably 1 to 9, and more preferably 1 to 6 in each case. s is 0 or 1, preferably 0. t is 2 or 3, preferably 3. (The condition s + t = 3 must be satisfied.) n is 1 to 9, preferably 1 to 7, more preferably 1 to 5. The conditions m = 2n + 1 and o = n + 2 must be satisfied. It is a base represented by At least two or three base monomers M1 represented by, b. Optionally, use the following formula 4: 【Chemistry 12】 [In the above formula 4, PG' is -OOC-CH=CH ２ and -OOC-C(CH ３ ) = CH ２ A polymerizable group selected from, S' is a spacer group selected from unbranched and branched alkylenes having 1 to 10 carbon atoms, which may further contain oxygen and / or -OOC- in the carbon chain, preferably methylene, or S' does not exist. A' is an aliphatic polycyclic group, preferably an aliphatic tricyclic hydrocarbon group, in which one or more hydrogen atoms may be independently substituted with a C1-C4 alkyl radical, a C1-C4 alkoxy radical, a fluorine atom, a chlorine atom, or a trifluoromethyl group, more preferably tricyclodecanylene, and even more preferably tricyclo[5.2.1.0 ２，６ It is decanilene. at least one base monomer M2 and A monomer mixture comprising [the specified substance].

11. Use of the monomer mixture according to claim 1 for the manufacture of polymerizable dental materials, preferably dental composites, core build-up materials, root canal filling materials, filler materials, underfill materials, fixation materials, crown materials, bridge materials, restorative materials and / or prosthetic materials.

12. a) The monomer mixture according to claim 1, b) Optionally, at least one polymerization initiator or polymerization initiator system, c) Optionally, fillers, d) Optionally, conventional dental additives A polymerizable dental material comprising [the specified substance].

13. The dental material according to claim 12, characterized in that one or more of the following components are present in the dental material in the following mass fractions based on the total mass of the dental material: a) 5% to 99% by weight, preferably 10% to 95% by weight, more preferably 15% to 85% by weight of the monomer mixture, b) At least one polymerization initiator or polymerization initiator system in an amount of 0% to 5% by weight, preferably 0.01% to 5% by weight, c) The filler in an amount of 0% to 95% by weight, preferably 1% to 95% by weight, more preferably 5% to 90% by weight, and even more preferably 15% to 85% by weight. d) The conventional dental additive in an amount of 0% to 5% by weight, preferably 0.001% to 5% by weight.

14. The dental material according to claim 12 or 13, which is intended for use in the treatment process as a dental composite, filler material, underfill material, fixation material, core build-up material, root canal filling material, crown material, bridge material, restorative material and / or prosthetic material.

15. A hardened dental material manufactured from a polymerizable dental material according to claim 12 or 13.

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