DENTAL POLYMERIZABLE COMPOSITION BASED ON CONDENSED SILANES

Description

[0001] The present invention relates to novel dental polymerizable compositions comprising (A) Polysiloxanes, wherein the polysiloxanes comprise a mixture of the condensates of the three silanes (a1), (a2) and (a3) ​​and / or a cocondensate of a mixture of the three silanes (a1), (a2) and (a3) ​​and / or a mixture of at least two of the cocondensates (a1) / (a2), (a1) / (a3) and (a2) / (a3) and / or a mixture of the condensate of one of the three silanes (a1), (a2) or (a3) ​​with the cocondensate of the other two silanes, wherein the silane (a1) corresponds to the formula (R 1< O) a R 2< b Si[-A(-Y{-B[-PG] f} e ) d ] c, where Y = -C(=O)NH-, -NHC(=O)-, -OC(=O)NH-, -NHC(=O)O-, -SC(=O)NH-, -NHC(=O)S-, -NHC(=O)NH-, -OC(=O)N(-C(=O)NH-)-, -SC(=O)N(-C(=O)NH-)-, -NHC(=O)N(-C(=O)NH-)-, -C(=O)NHC(=O)NH-, -NHC(=O)NHC(=O)-, where the bond on the left in the formula is closer to structural element A and the bond on the right is closer to structural element B, PG = polymerizable group,wherein the group PG is selected from the group consisting of -ZC(=O)-CH=CH 2 and -ZC(=O)-C(CH 3 )=CH 2 wherein Z is selected from the group consisting of O and NH, A = an organic linking group that connects Si to Y and has 1 to 20 C atoms, B = an organic linking group that connects Y to PG and has 1 to 20 C atoms, R 1< = H or C1- to C4-alkyl, R 2< = C1- to C4-alkyl, a = 2 or 3, b = 0 or 1, c = 1 or 2, d = 1 to 3, e = 1 or 2, f = 1 to 5, , a + b + c = 4 , and wherein the silane (a2) corresponds to the formula (R 1< O) a R 2< b Si[-A'(-PG) f ] c, where PG = polymerizable group, wherein the polymerizable group PG is selected from the group consisting of -ZC(=O)-CH=CH 2 and -ZC(=O)-C(CH 3 )=CH 2 where Z is selected from the group consisting of O and NH, A' = an organic linking group which links Si to PG and has 1 to 20 C atoms and does not contain any of the groups -C(=O)NH-, -NHC(=O)-, -OC(=O)NH-, -NHC(=O)O-, -SC(=O)NH-, -NHC(=O)S-, -NHC(=O)NH-, -OC(=O)N(-C(=O)NH-)-, -SC(=O)N(-C(=O)NH-)-, -NHC(=O)N(-C(=O)NH-)-, -C(=O)NHC(=O)NH-, or -NHC(=O)NHC(=O)-, contains, R 1< = H or C1- to C4-alkyl, R 2< = C1- to C4-alkyl, a = 2 or 3 b = 0 or 1 c = 1 or 2 f = 1 to 5, a + b + c = 4 , and wherein the silane (a3) ​​corresponds to the formula (R 1< O) a R 2< b SiAr c, where R 1< = H or C1- to C4-alkyl, R 2< = C1- to C4-alkyl, Ar = aryl, where different Ar groups can be the same or different, a = 2 or 3, b = 0 or 1, c = 1 or 2 a + b + c = 4 , (B) fillers and (C) initiators and / or catalysts and / or activators for the polymerization, wherein the proportion of the silanes (a1), (a2) and (a3) ​​in the cocondensate or in the mixture of the condensates or cocondensates (a1) in an amount of 10 to 70 wt.%, (a2) in an amount of 10 to 70 wt.%, and (a3) ​​in an amount of 5 to 60 wt.-%, in each case based on the total amount of silanes (a1), (a2) and (a3), the dental products cured from the dental polymerizable compositions according to the invention, and their respective use as dental material, in particular as flowable or packable, permanent or temporary filling composite, as so-called "bulk fill" material, as core build-up material, as dental luting cement, as dental sealing material, as dental varnish, as dental relining material, as crown or bridge material, as dental adhesive (bonding), as dental primer, as soft or hard relining material, as inlay, onlay and / or overlay, as artificial tooth, as orthodontic material, as prefabricated tooth part, as dental framework, as dental temporary, as dental block material, as partial denture or as full denture.They are also suitable for use in generative dental manufacturing processes, also known as "rapid prototyping," preferably for stereolithography, preferably digital light processing (DLP), selective laser assembling (SLA), microstereolithography, 3D printing, laminated object manufacturing, or film transfer imaging.

[0002] The invention further relates to a method for producing the dental compositions and a method for producing a respective dental product. Kits according to the invention containing the novel polymerizable dental compositions are also claimed.

[0003] The present invention also relates to polymerizable dental compositions comprising components (A), (B) and (C) as defined above and one or more than one compound which is not a polysiloxane compound according to the invention. Optionally, polymerizable dental compositions according to the invention can thus also (D) organic, polymerizable monomers which are not polysiloxanes according to the invention, preferably for reaction with the polysiloxanes according to the invention.

[0004] The present invention also relates to polymerizable dental compositions comprising components (A), (B), (C) and optionally (D) as defined above and one or more than one compound which are not polysiloxanes according to the invention, but polymerizable compounds containing acid groups which do not have a Si atom. Optionally, polymerizable dental compositions according to the invention can thus also (E) organic, acid-containing monomers which do not contain a Si atom.

[0005] Embodiments according to the invention are also polymerizable dental materials as defined above, further comprising one, two, more than two or all substances from the group of additives (F), consisting of: rheological aids, colorants, preferably color pigments, flavors, stabilizers, in particular daylight stabilizers, inhibitors, molecular weight regulators, preservatives, preferably parabens, surface-active substances, preferably surfactants, microbicides, preferably bactericides, organic polymers and oligomers and compounds with high molecular weights, thickeners, dental medicaments and plasticizers.

[0006] Embodiments according to the invention are also polymerizable dental materials as defined above, further comprising one, two, or more than two solvents (G).

[0007] Most preferably, the present invention relates to polymerizable dental compositions and polymerized dental compositions as defined above for specific use in a therapeutic method (a method for therapeutic treatment of the human or animal body, preferably the human body).

[0008] The term "comprise" is used in this application in its usual and generally accepted meaning.

[0009] Thus, of course, polymerizable dental compositions are also claimed according to the invention which contain (A) polysiloxanes, wherein the polysiloxanes contain at least one mixture of the condensates of the three silanes (a1), (a2) and (a3) ​​and / or at least one cocondensate of a mixture of the three silanes (a1), (a2) and (a3) ​​and / or at least one mixture of at least two of the cocondensates (a1) / (a2), (a1) / (a3) and (a2) / (a3) and / or at least one mixture of the condensate of one of the three silanes (a1), (a2) or (a3) ​​with the cocondensate of the other two silanes.

[0010] Also claimed according to the invention are polymerizable dental compositions which contain (A) polysiloxanes, wherein the polysiloxanes contain any mixtures of condensates and cocondensates comprising (a1), (a2) and (a3), for example the mixture of two or three different cocondensates (a1) / (a2) / (a3) or the mixture of a cocondensate (a1) / (a2) / (a3) with the condensate of (a1), etc.

[0011] In other words: A polymerizable dental composition according to the invention comprises homo- and / or cocondensates of at least one of the three silanes (a1), (a2) and (a3).

[0012] Further aspects of the present invention and its preferred embodiments will become apparent from the following description, the exemplary embodiments and the claims.

[0013] Polysiloxane compounds have long been known and are obtainable, for example, by hydrolysis and condensation of silanes with hydrolyzable groups (see, for example, DE 27 58 414 A1) or by hydrosilylation of allyl or vinyl compounds with SiH-containing compounds. Polysiloxane compounds can be further processed into a wide variety of products, such as coatings, membranes, or bulk materials. This further processing is often based on a crosslinking reaction of organically polymerizable groups in the polysiloxane compounds (e.g., (meth)acrylate groups) and the resulting formation of crosslinked polysiloxane compounds.

[0014] In this text, the term "(meth)acrylic" refers to both "acrylic" and "methacrylic".

[0015] In this text, the term "polymerizable groups" refers to functional groups that, as components of molecules, yield solid polymers upon curing, i.e., polymers capable of converting from a liquid-pasty phase to a solid phase. In this process, monomers react to form polymers. These reactions include both chain growth reactions and step-growth reactions, thus including radical chain polymerization, coordinative chain polymerization, cationic chain reaction, anionic chain polymerization, and polyaddition.

[0016] Preferably, the groups polymerize (cure or crosslink) in a chain growth reaction either radically or cationically, most preferably they polymerize radically.

[0017] Polysiloxanes substituted with polymerizable groups, in chain and / or cyclic and / or cage form, are generally synthesized via the sol-gel process through targeted hydrolysis and condensation of appropriately functionalized derivatives of silicon alkoxides or halosilanes. These manufacturing processes are widely described in the literature. Such a synthesis generally starts with a standard silane, such as isocyanatopropyldiethoxymethylsilane, which is then converted in a first step, also in a standard reaction, for example, an isocyanate-alcohol addition, with glycerol-1,3-dimethacrylate to form the corresponding urethane.The resulting compound consists, on the one hand, of a silicon atom equipped with hydrolyzable and condensable groups. This atom, via a so-called spacer consisting of an alkyl group (here a propyl group) and a urethane group as a structural linking element, is transferred to another functional structural segment, in this case two radically polymerizable methacrylate groups. Such a simple synthesis process can be modified in many ways, since the reaction possibilities between appropriately functionalized silanes and suitable reactants appear unlimited. The synthesis proposals in the literature are correspondingly numerous. The starting compound thus comprises an inorganically condensable structural element, a variably designed linking element, and a polymerizable organic backbone.In a catalytically controlled hydrolysis and condensation, the polysiloxane is obtained as an inorganic condensate, substituted, for example, with radically or cationically polymerizable groups. Whether the polycondensate exists in the form of chains, rings, three-dimensional cages, or in the corresponding mixed forms, depends on the precise conditions of the condensation. These include the reaction conditions (pH, amount of solvent and water, type and amount of catalyst, reaction temperature, type of preparation, etc.) as well as the structural forms of the starting silane, whereby the number of alkoxy groups, the number of polymerizable groups, the chemical nature of the connecting element, and the chain length of the spacer are important. Information on this can be found in both scientific and patent literature.

[0018] Examples of possible structural types are given below, where the polymerizable groups here contain radically curable (meth)acrylate groups. Ring-shaped, chain-shaped, and cage-shaped structures are shown, as well as a possible mixed form of ring- and chain-shaped condensates. Depending on the reaction conditions and the structural elements of the reactants, the synthesis of both pure and corresponding mixed-form condensates is possible.

[0019] Polysiloxanes, as a link between inorganic and organic chemistry, possess special material properties. Since they are also physiologically inert, meaning they have no significant toxicity, they are particularly important for medical applications. The basis for the almost nonexistent toxicity of polysiloxanes is the low biological vulnerability of the silicon-carbon bonds and the limited diffusion capacity of the highly hydrophobic polymer chains through cell membranes, which should make them particularly suitable for implantation (in teeth).

[0020] A specific group of polysiloxane compounds contains, in addition to an organically polymerizable group, additional free polar functional groups such as hydroxy or carboxy groups in the organic groups (side chains).

[0021] For example, DE 44 16 857 C1 relates to hydrolyzable and polymerizable silanes, processes for their preparation, and their use in the production of silica (hetero)polycondensates and (hetero)polymers. Hydrolyzable, organically modified silanes are widely used in the production of scratch-resistant coatings for a wide variety of substrates, for the production of fillers, adhesives and sealants, or molded articles.

[0022] DE 44 16 857 C1 discloses the use of silicic acid (hetero)polycondensates (polysiloxane compounds) in curable dental materials. The polysiloxane compounds described here contain free polar functional groups (e.g., carboxy or hydroxy groups) that are capable of complexing suitable metal ions / transition metal ions (e.g., ions of titanium, zirconium, or tin). In curable dental compositions, this can have a positive effect on the radiopacity, contact toxicity, and refractive index of a corresponding curable or cured dental material.

[0023] DE 198 60 364 C2 relates to polymerizable dental materials based on curable siloxane compounds, their use, and their preparation. This document describes the preparation of cyclic polysiloxanes and their use as a basis for polymerizable dental materials. Despite a high density of polymerizable groups, they are said to exhibit a low viscosity, which enables high filler absorption and leads to materials with low polymerization shrinkage. Here, too, the organic side chains of the described polysiloxanes contain free polar functions in addition to the polymerizable units.

[0024] However, the free polar functional groups, e.g., in the aforementioned polysiloxane compounds, also regularly lead to undesirable properties. It has been shown that the hydrophilicity of the polysiloxane compounds caused by the (free) polar functional groups leads to increased water absorption in the presence of moisture, which adversely reduces the wet strength of the curable dental material. Presumably due to the formation of internal hydrogen bonds, this leads to an increase in viscosity. This then negatively impacts the handling during production of the curable dental compositions.

[0025] There is a significant need among dentists and the dental industry to further adapt polysiloxane compounds to the requirements of a modern (curable or cured) dental material and to minimize the aforementioned disadvantages. Such adapted polysiloxane compounds should possess improved physical properties for dental medicine (or lead to improved physical properties for corresponding curable / cured dental materials), e.g., lower polymerization shrinkage during polymerization / crosslinking of the polysiloxane compounds (i.e., during curing), increased strength, and / or limited water absorption while maintaining a comfortable consistency of the curable dental material.

[0026] Initial successes in improving the polysiloxanes were achieved by adding or substituting different substrates to the free polar functionalities of the special polysiloxanes described above.

[0027] EP 1 874 847 B1 relates to a process for producing silanes with two, three, or even more structural units linked to one another via a bridge containing urethane, acid amide, and / or carboxylic acid ester groups, each of which contains at least one organically polymerizable radical and at least one silyl radical. These silanes are said to be particularly suitable for modifying the properties of silicic acid (hetero)polycondensates and silyl-containing organic polymers. The disclosed process is also said to be suitable for bridging precondensed silicic acid (hetero)polycondensates.

[0028] The silicic acid (hetero)polycondensates (polysiloxane compounds) disclosed in EP 1 874 847 B1 possess a free hydroxyl group (i.e., a free polar functional group). These free hydroxyl groups can react with a dicarboxylic acid derivative or diisocyanate such that hydroxyl groups form a linkage (bridge) with a dicarboxylic acid derivative or diisocyanate. Such linked polysiloxane compounds possess a significantly higher molecular weight without significantly reducing the double bond density (due to the organically polymerizable (meth)acrylate groups). Double bond density is understood here as the quotient of the number of polymerizable double bonds in a compound and the molecular weight of this compound. The higher molecular weight has a positive effect on the biocompatibility and polymerization shrinkage during crosslinking of the linked polysiloxane compounds.At the same time, the hydrophobicity of the polysiloxane compounds could be increased. However, it was shown that the higher molecular weight has a detrimental effect on the viscosity of the linked polysiloxane compounds (and thus on the processability during the production of the curable dental material). Viscosity increases significantly with the degree of linkage, i.e., with the molecular weight, so that tolerable processability in the production of a corresponding curable dental material comprising such linked polysiloxane compounds is no longer satisfactory even at a relatively low degree of linkage.

[0029] EP 1 685 182 B1 relates to silanes and silicic acid polycondensates and partial condensates formed therefrom, in which an organic radical is present which is bonded to a silicon atom and which is branched and carries at least one independently organically polymerizable group on each of the two branches, or has such a group on one of the two branches and a radical with a further silicon atom on the other.

[0030] The polysiloxane compounds disclosed in EP 1 685 182 B1 also comprise free polar functional groups in the form of hydroxyl groups. By reacting carboxylic acid or isocyanate derivatives, which in turn also contain polymerizable double bonds (e.g., (meth)acrylate groups), organically polymerizable groups can be linked to free polar functional groups. These reaction products typically possess increased strength, enhanced hydrophobicity, and improved biocompatibility due to the increased molecular weight.

[0031] However, it could also be shown in these cases that the introduction of additional polymerizable double bonds leads to an increased polymerization shrinkage during crosslinking of the polysiloxane compounds, since the double bond density increases significantly, but the increase in molecular weight is only comparatively small.

[0032] WO 2013 / 041723 A1 discloses hydrolyzable and polymerizable silanes (including silicic acid polycondensates, i.e., siloxanes) with adjustable spatial distribution of functional groups, as well as their use. The teaching disclosed in WO 2013 / 041723 A1 relates to a process for chain extension of residues bonded to silicon via carbon in silanes or siloxanes.

[0033] WO 2013 / 053693 A1 discloses silicic acid polycondensates (siloxanes) with cyclic olefin-containing structures, processes for their preparation, and their use. WO 2013 / 053693 A1 discloses that polymer materials with widely adjustable elastic moduli and high elastic elongation (i.e., without brittle behavior) and thus high fracture toughness can be produced from silicic acid (hetero)polycondensates with cyclic olefin-containing structures.

[0034] DE 10 2014 210 432 A1 describes polysiloxane compounds that do not exhibit, or at least only to a lesser extent, the aforementioned disadvantages of the prior art in a curable or cured dental composition. The conceptual approach of these systems involves converting the free functional group in the silane in such a way that no additional polymerizable double bonds are introduced into the system. Instead, high-molecular-weight hydrocarbon radicals with at least 11 carbon atoms are incorporated into the system. Surprisingly, these curable dental compositions showed a good viscosity of the polysiloxane compounds (the viscosity should be 50 Pa*s or less at a temperature of 25°C) and the associated excellent processability in the production of a curable dental material containing the polysiloxane compounds, good hydrophobicity, good strength, in particular good flexural strength, very low polymerization shrinkage during crosslinking of the polysiloxane compounds, i.e. during curing of the curable dental material, good biocompatibility, a refractive index that is almost identical to the refractive index of conventional dental glasses.

[0035] The measures taken in DE 10 2014 210 432 A1 have thus solved several problems: By eliminating polar functional groups, the formation of intermolecular interactions was prevented. Thus, the viscosity of the system was kept at a comparatively low level despite a considerable increase in molecular weight. By incorporating hydrocarbon radicals of relatively high molecular weight, the polysiloxane structural framework was spatially expanded intramolecularly, so that the accessibility of the radically polymerizable groups was increased during curing and thus the conversion rate could be optimized. How else could one explain the fact that in these systems, with a comparatively reduced double bond density, the strength of the materials, for example the flexural strength of the cured dental compositions, remains at a very good level and in many cases is even increased compared to the non-reacted polysiloxanes. By increasing the molecular weight while maintaining functionality, i.e. by effectively reducing the double bond density, it was possible to set the perhaps most clinically important technical parameter of a curable dental composition, namely the volume shrinkage during curing, to an extremely low value. In clinical practice, therapeutic success primarily depends on whether the dental material, for example, seals a cavity prepared by the dentist with a tight margin. Shrinkage of the material during polymerization can lead to marginal gaps forming through which bacteria can penetrate the tooth and thus cause the treatment to fail. By incorporating hydrocarbon residues with a relatively high molecular weight, the polysiloxane structural framework was also made comparatively more hydrophobic, so that the undesirable water absorption now assumes extremely low values.

[0036] The radically curable compositions described in DE 10 2014 210 432 A1 are particularly suitable for use in a therapeutic procedure for the temporary or permanent filling of a dental cavity. Furthermore, the systems are suitable for use in a therapeutic procedure as a base material, as an adhesive (bonding agent), as a flowable composite material (flow material), as a fissure sealant, as a crown and bridge material, as an inlay / onlay, and / or as a core build-up material.

[0037] DE 10 2014 116 389 A1 discloses combinations of polysiloxanes with disiloxanes that are particularly well-suited for the production of flowable, curable dental materials that are applied through an application cannula or a static mixer. In addition to good flow properties in the cannula or mixer and optimal flow onto the tooth substance, these materials exhibit sufficiently high stability, allowing the good physical properties provided by the polysiloxanes to take full effect. Furthermore, the combination of polysiloxanes with disiloxanes surprisingly also increased the Young's modulus. The cured dental material can thus resist deformation more effectively and thus better withstand the constant chewing loads.

[0038] DE 10 2014 116 402 A1 teaches the use of combinations of polysiloxanes with disiloxanes in generative manufacturing processes, wherein the processes include stereolithography, digital light processing, polyjet technology, the galvanometer type scanning method, microstereolithography, multi-jet modeling, selective laser sintering, 3D printing, fused deposition modeling, 3D plotting, laminated object manufacturing or film transfer imaging.

[0039] MEGAN A. COLE ET AL: "Thiol-ene functionalized siloxanes for use as elastomeric dental impression materials" (DENTAL MATERIALS, Vol. 30, No. 4, April 1, 2014 (2014-04-01), pages 449-455, XP055743888, AMSTERDAM, NL ISSN: 0109-5641, DOI: 10.1016 / j.dental.2014.01.011) discloses dental impression materials containing phenyl-substituted polysiloxanes. In addition to the phenyl groups, the polysiloxanes alternatively contain thiol or allyl groups and cure via a thiol-ene reaction.

[0040] JP H08 311115 A (MITSUBISHI RAYON CO) discloses the use of methacrylic and phenyl substituted silanes such as γ-methacryloyloxypropyltrimethoxysilane and phenyltrimethoxysilane for hydrophobizing the surface of colloidal silica.

[0041] The use of polysiloxanes for the production of dental curable compositions has achieved some developmental progress over time, but the mere fact that there are currently only three product families based on polysiloxanes commercially available on the market demonstrates that the major breakthrough for this interesting and biocompatible class of substances has not yet been achieved. The main reason for the current lack of general acceptance of this class of substances is the fact that the polymerized polysiloxanes do not yet achieve the high mechanical values ​​of flexural strength and Young's modulus that conventional systems based on classic dental monomers (Bis-GMA, UDMA, and TEGDMA) exhibit.In addition to the flexural strength, the Young's modulus is a crucial parameter and a key property in the selection of a restorative material, since a high Young's modulus means a high resistance of the material to elastic deformation, which is particularly important in the compensation of occlusal forces and justifies the high clinical relevance of this parameter.

[0042] According to the currently valid ISO standard DIN EN ISO 4049, entitled "Polymer-based Restorative Materials," the limit value for flexural strength for this material class is 80 MPa, assuming the material is also suitable for restoring occlusal surfaces. Polysiloxane-based restorative materials certainly achieve this level of strength, but they fall short of the peak values ​​of conventional composite restorative materials.

[0043] In a large-scale, older study by N. Ilie and R. Hickel (Clin. Oral Invest. (2009), 13, 427-438), entitled "Investigations on mechanical behavior of dental composites," 61 commercially available composite materials were examined and tested according to the standard. The following results were obtained: Flexural strength = BF in MPa, Young's modulus = EM in GPa, the average values ​​are given, see publication, Table 2, page 433 below Hybrid composites: 29 materials tested, BF 116.9, EM 7.3 Packable composites: 9 materials tested, BF 105.9, EM 8.4 Polysiloxane-based composites: 2 materials tested, BF 104.3, EM 7.5 Nano-hybrid composites: 7 materials tested, BF 103.1, EM 5.0 Flowable composites: 10 materials tested, BF 99.8, EM 4.4 Microfilled composites: 4 materials tested, BF 73.5, EM 3.8

[0044] The values ​​demonstrate an acceptable level of mechanical properties of polysiloxane-based restorative materials, taking into account that these early polysiloxane-based restorative materials contain, in addition to polysiloxanes, a larger proportion of conventional dental monomers without Si atoms.

[0045] In a very recent compilation taken from the textbook "Materials Science in Dentistry, Modern Materials and Technologies", edited by M. Rosentritt, N. Illie, U. Lohbauer, 2018, Georg Thieme Verlag, Stuttgart, page 208, Table 7.3, "Mechanical Properties of Various Composite Categories", the following values ​​can be found: Fiber-reinforced composite: BF 132.9, EM 8.2 Microhybrid: BF 127.8, EM 6.8 Bulk-fill (flowable): BF 127.6, EM 5.0 Nanohybrid: BF 125.7, EM 5.9 Bulk-fill (highly viscous): BF 123.4, EM 7.1 flowable: BF 119.3, EM 4.2

[0046] This compilation shows that within the last 10 years the mechanical values ​​of the flexural strength of all restoration materials have been increased by an average of approximately 20 points each and that new composite compositions have been developed (bulk-fill materials).

[0047] In contrast to traditional light-curing filling composites, which are applied in individual, thin layers of approximately 2 mm to ensure sufficient curing of the material and to compensate for volume shrinkage, bulk-fill materials can be photopolymerized in layer thicknesses of up to 5 mm. This capability is achieved through the materials' greater transparency. Bulk-fill composites are divided into two groups, as shown in the table above: low-viscosity, flowable materials and high-viscosity, moldable types.

[0048] The objective of the invention was therefore to significantly improve the mechanical values ​​of flexural strength and Young's modulus of biocompatible polysiloxanes, bringing them close to the outstanding values ​​of conventional dental composite systems, or even exceeding them. At the same time, the clinically relevant values ​​of volume shrinkage were to be reduced. Polymerization creates bonds between the molecules, so that the reactants adhere more closely to one another, and the resulting solid polymers have a denser structure than the liquid starting materials. This volume contraction can lead to stresses within the restorative material and is clinically undesirable. Marginal gap formation and the development of secondary caries are associated with the phenomenon of shrinkage.

[0049] Surprisingly, it has now been found that dental polysiloxane-based composite materials for restoration with extremely good mechanical properties are available - even without having to resort to conventional dental monomers - if the polymerizable matrix comprises polysiloxanes, wherein the polysiloxanes (A) comprise a mixture of the condensates of the three silanes (a1), (a2) and (a3) ​​and / or a co-condensate of a mixture of the three silanes (a1), (a2) and (a3) ​​and / or a mixture of at least two of the condensates (a1) / (a2), (a1) / (a3) and (a2) / (a3) and / or a mixture of the condensate of one of the three silanes (a1), (a2) and (a3) ​​with the co-condensate of the other two silanes.

[0050] According to the invention, the proportion of the silanes (a1), (a2) and (a3) ​​in the cocondensate or in the mixture of the condensates or cocondensates is (a1) in an amount of 10 to 70 wt.%, preferably from 20 to 60 wt.%, (a2) in an amount of 10 to 70 wt.%, preferably from 20 to 50 wt.% and (a3) ​​in an amount of 5 to 60 wt.%, preferably from 10 to 40 wt.%, in each case based on the total amount of the silanes (a1), (a2) and (a3).

[0051] Such mixtures are new and are not suggested by the state of the art. Component (A) - different siloxanes (a1), (a2) and (a3)

[0052] The following describes the structures of silanes (a1), (a2), and (a3) ​​in more detail, along with detailed procedures for their synthesis. Commercially available starting substances are also listed. The CAS numbers mentioned in this context are examples. The same substances may have different CAS numbers. This can be the case, for example, if there are different isomers (constitutional isomers, stereoisomers, conformational isomers, configurational isomers, enantiomers, diastereomers) or if the substance is labeled as a reaction product of its starting substances. These variants are also suitable and can be used. Silane (R 1< O) a R 2< b Si[-A(-Y{-B[-PG] f} e ) d ] c (a1):

[0053] The silane (a1) corresponds to the formula (R 1< O) a R 2< b Si[-A(-Y{-B[-PG] f} e ) d ] c with ​Y = -C(=O)NH-, -NHC(=O)-, -OC(=O)NH-, -NHC(=O)O-, -SC(=O)NH-, -NHC(=O)S-, -NHC(=O)NH-, -OC(=O)N(-C(=O)NH-)-, -SC(=O)N(-C(=O)NH-)-, -NHC(=O)N(-C(=O)NH-)-, -C(=O)NHC(=O)NH-, -NHC(=O)NHC(=O)- where the bond on the left in the formula is closer to structural element A and the bond on the right is closer to structural element B, PG = polymerizable group, where the polymerizable group PG is selected from the group consisting of -ZC(=O)-CH=CH 2 and -ZC(=O)-C(CH 3 )=CH 2 where Z is selected from the group consisting of O and NH, A = an organic linking group that connects Si with Y and has 1 to 20 C atoms, B = an organic linking group that connects Y with PG and has 1 to 20 C atoms, R 1< = H or C1- to C4-alkyl, R 2< = C1- to C4-alkyl, a = 2 or 3, b = 0 or 1, c = 1 or 2, d = 1 to 3, e = 1 or 2, f = 1 to 5 and a + b + c = 4 .

[0054] In a preferred embodiment, the group Y is selected from the group consisting of -(X) x -C(=O)NH-, -NHC(=O)-(X) x - and -(X) x C(=O)N(-C(=O)NH-)- where X is selected from the group consisting of O, S and NH, preferably O and S, and where the index x is either 0 or 1, preferably 1.

[0055] In a preferred embodiment, the polymerizable group PG is selected from the group consisting of -ZC(=O)-CH=CH 2 and -ZC(=O)-C(CH 3 )=CH 2 where Z = O.

[0056] The organic linking group A, which connects the Si atom to the group Y, is a (d+1)-valent, straight-chain, branched or cyclic group which has 1 to 20 C atoms and may optionally have O atoms, S atoms, NR groups, ester groups or thioester groups.

[0057] In a preferred embodiment, the connecting group A is selected from the group consisting of -(CH 2 ) n - with n = 1 to 12, -(CH 2 ) n -N(CH 3 )-(CH 2 ) n - with n = 1 to 4, -(CH 2 ) n N[(CH 2 ) n -] 2 with n = 1 to 4 and -(CH 2 ) n -CH(R)-(CH 2 ) n - with n = 0 to 4 and R = methyl, ethyl, phenyl, where in each case the bond arranged on the left is connected to the Si atom and the bond arranged on the right is connected to the group Y.

[0058] In a very preferred embodiment, the connecting group A is -(CH 2 ) n -with n = 1 to 6.

[0059] The organic linking group B, which connects the group Y with the polymerizable group PG, is an (f+1)-valent, straight-chain, branched or cyclic group which has 1 to 20 C atoms and may optionally have O atoms, S atoms, NR groups, ester groups or thioester groups.

[0060] In a preferred embodiment, the compound group B is selected from the group consisting of -(CH 2 ) n - with n = 1 to 12, -CH 2 CH(CH 3 )-, -CH(CH 3 )CH 2 -, -(CH 2 ) 2 (OCH 2 CH 2 ) n - with n = 1 to 6, -(CH 2 ) n OC(=O)(CH 2 ) m - with n,m = 1 to 6, -(CH 2 ) n C(=O)O(CH 2 ) m - with n,m = 1 to 6, -CH(CH 2 OPh)CH 2 -, where the bond arranged on the left is connected to the group Y and the bond(s) arranged to the right is / are connected to the group(s) PG.

[0061] In a very preferred embodiment, the connecting group B is -(CH 2 ) n -with n = 1 to 6.

[0062] In a preferred embodiment, the radical R 1< is selected from the group consisting of H, methyl and ethyl.

[0063] In a preferred embodiment, the index d = 1 to 2.

[0064] In a preferred embodiment, the index f = 1 to 2.

[0065] Bevorzugte Silane (a1) sind         (R 1< O) a R 2< b Si[-A(-C(=O)-NH-B[-Z-C(=O)C(=CH 2 )R 3< ] f ) d ] c ,         (R 1< O) a R 2< b Si[-A(-NH-C(=O)-B[-Z-C(=O)C(=CH 2 )R 3< ] f ) d ] c ,         (R 1< O) a R 2< b Si[-A(-X-C(=O)-NH-B[-Z-C(=O)C(=CH 2 )R 3< ] f ) d ] c und         (R 1< O) a R 2< b Si[-A(-NH-C(=O)-X-B[-Z-C(=O)C(=CH 2 )R 3< ] f ) d ] c mit A = an organic linking group that connects Si to Y selected from the group consisting of -(CH 2 ) n - with n = 1 to 12, -(CH 2 ) n -N(CH 3 )-(CH 2 ) n - with n = 1 to 4, -(CH 2 ) n N[(CH 2 ) n -] 2 with n = 1 to 4 and -(CH 2 ) n -CH(R)-(CH 2 ) n - with n = 0 to 4 and R = methyl, ethyl, phenyl, preferably -(CH 2 ) n - with n = 1 to 6, B = an organic linking group that connects Y to Z selected from the group consisting of -(CH 2 ) n - with n = 1 to 12, -CH 2 CH(CH 3 )-, -CH(CH 3 )CH 2 -, -(CH 2 ) 2 (OCH 2 CH 2 ) n - with n = 1 to 6, -(CH 2 ) n OC(=O)(CH 2 ) m - with n,m = 1 to 6, -(CH 2 ) n C(=O)O(CH 2 ) m - with n,m = 1 to 6, -CH(CH 2 OPh)CH 2 -, preferably -(CH 2 ) n - with n = 1 to 6, X = O, S, NH; preferably OZ = O, NH; preferably OR 1< = H or C1- to C4-alkyl, preferably H, methyl or ethyl R 2< = C1- to C4-alkyl, R 3< = H, methyl; preferably methyl a = 2 or 3, b = 0 or 1, c = 1 or 2, d = 1 to 3, preferably 1 to 2, e = 1 or 2, f = 1 to 5, preferably 1 to 2 and a + b + c = 4 . Synthesis of silanes with urethane, thiourethane, urea or amide groups starting from isocyanates

[0066] Silanes with urethane, thiourethane or urea groups can be easily prepared by Sn- or Bi-catalyzed reaction of the corresponding silanes with OH, SH or NH 2 groups with (meth)acryl-substituted isocyanates.

[0067] Alternatively, the Sn- or Bi-catalyzed reaction of isocyanate-substituted silanes with the corresponding OH-, SH- or NH 2 -substituted (meth)acrylic compounds is also possible.

[0068] By reacting isocyanate-substituted silanes with carboxyl-substituted (meth)acrylic compounds, the corresponding amides can be produced with CO 2 elimination. Synthesis of (R 1< O) a R 2< b Si[-A(-XC(=O)-NH-B[-ZC(=O)C(=CH 2 )R 3< ] f ) d ] c

[0069] The synthesis of the silanes (R 1< O) a R 2< b Si[-A(-XC(=O)-NH-B[-ZC(=O)C(=CH 2 )R 3< ] f ) d ] c takes place under tin or bismuth catalysis from a silane with an XH group and a (meth)acrylic compound with an isocyanate group. Preferred catalysts are dibutyltin dilaurate and bismuth neodecanoate. With gentle heating, one XH group is reacted with one isocyanate group in an equimolar ratio. The reaction usually proceeds to completion and can be easily followed in the IR spectrum until the isocyanate band (2270 cm -1< ) ​​has completely disappeared. (R 1< O) a R 2< b Si[-A(-XH) d ] c + (cxd) [R 3< -C(=CH 2 )C(=O)-Z-] f B-NCO → (R 1< O) a R 2< b Si[-A(-XC(=O)-NH-B[-ZC(=O)C(=CH 2 )R 3< ] f ) d ] c The following two tables 1 and 2 list a series of commercially available starting compounds. Table 1: (R 1 < O) a R 2 < b Si[-A(-XH) d ] c CAS No. R 1< R 2< XH a b c d -A- 53764-54-8 Me - OH 3 0 1 1 -(CH 2 ) 3 - 53394-61-9 Et - OH 3 0 1 1 -(CH 2 ) 3 - 99697-20-8 Me Me OH 2 1 1 1 -(CH 2 ) 3 - 162781-70-6 Et - OH 3 0 1 1 -CH2- 4420-74-0 Me - SH 3 0 1 1 -(CH 2 ) 3 - 14814-09-6 Et - SH 3 0 1 1 -(CH 2 ) 3 - 31001-77-1 Me Me SH 2 1 1 1 -(CH 2 ) 3 - 30817-94-8 Me - SH 3 0 1 1 -CH2- 60764-83-2 Et - SH 3 0 1 1 -CH2- 877593-17-4 Me - SH 3 0 1 1 -(CH 2 ) 11 - 57765-40-9 Me - SH 2 0 2 1 -(CH 2 ) 3 - 13822-56-5 Me - NH2 3 0 1 1 -(CH 2 ) 3 - 3663-44-3 Me Me NH2 2 1 1 1 -(CH 2 ) 3 - 3179-76-8 Et Me NH2 2 1 1 1 -(CH 2 ) 3 - 71408-48-5 Me - NH2 3 0 1 1 -CH2- 18306-83-7 Et - NH2 3 0 1 1 -CH2- 51749-36-1 Me - NH2 2 0 2 1 -(CH 2 ) 3 - 53746-12-6 Et - NH2 2 0 2 1 -(CH 2 ) 3 - 330457-46-0 Me - OH 3 0 1 1 -(CH 2 ) 3 -N(CH 3 )-(CH 2 ) 2 - 24801-87-4 Me - OH 3 0 1 2 -(CH 2 ) 3 N[(CH 2 ) 2 -] 2 7538-44-5 Et - OH 3 0 1 2 -(CH 2 ) 3 N[(CH 2 ) 2 -] 2 Table 2: [R 3 < -C(=CH 2 )C(=O)-Z-] f B-NCO CAS No. R 3< Z f -B- 30674-80-7 Me O 1 -(CH 2 ) 2 - 130025-29-5 Me O 1 -CH 2 CH(CH 3 )- 86241-25-0 Me O 1 -(CH 2 ) 3 - 93956-19-5 Me O 1 -CH2- 13641-96-8 H O 1 -(CH 2 ) 2 - 223909-47-5 H O 1 -CH 2 CH(CH 3 )- 119096-71-8 H O 1 -(CH 2 ) 3 - 886577-76-0 H O 2 953028-96-1 H NH 1 -(CH 2 ) 3 - 61994-33-0 H NH 1

[0070] In the following, some examples of syntheses of the silanes (R 1< O) a R 2< b Si[-A(-XC(=O)-NH-B[-ZC(=O)C(=CH 2 )R 3< ] f ) d ] c are presented.

[0071] The reaction of 3-(trimethoxysilyl)-1-propanol with 2-isocyanatoethyl methacrylate yields the silane (1).

[0072] The reaction of 3-(methyldimethoxysilyl)-1-propanol with 2-isocyanatoethyl methacrylate yields the silane (2).

[0073] The reaction of 1-(triethoxysilyl)methanol with 2-isocyanatoethyl methacrylate yields the silane (3).

[0074] The reaction of 3-(trimethoxysilyl)-1-propanol with 3-isocyanatopropyl methacrylate yields the silane (4).

[0075] The reaction of 3-(trimethoxysilyl)-1-propanol with 1,1-bis(acryloyloxymethyl)ethyl isocyanate yields the silane (5).

[0076] The reaction of 1-(trimethoxysilyl)methanethiol with 2-isocyanatoethyl methacrylate yields the silane (6).

[0077] The reaction of 3-(trimethoxysilyl)-1-propanethiol with 2-isocyanatoethyl methacrylate yields the silane (7).

[0078] The reaction of 11-(trimethoxysilyl)-1-undecanethiol with 2-isocyanatoethyl methacrylate yields the silane (8).

[0079] The reaction of 3-(methyldimethoxysilyl)-1-propanethiol with 2-isocyanatoethyl methacrylate yields the silane (9).

[0080] The reaction of 1-(trimethoxysilyl)methanamine with 2-isocyanatoethyl methacrylate yields the silane (10).

[0081] The reaction of 3-(trimethoxysilyl)-1-propanamine with 2-isocyanatoethyl methacrylate yields the silane (11).

[0082] The reaction of 3-(methyldimethoxysilyl)-1-propanamine with 2-isocyanatoethyl methacrylate yields the silane (12).

[0083] The reaction of 3,3'-(diethoxysilylene)bis[1-propanamine] with two equivalents of 2-isocyanatoethyl methacrylate yields the silane (13).

[0084] The reaction of 2-[methyl[3-(trimethoxysilyl)propyl]amino]ethanol with 2-isocyanatoethyl methacrylate yields the silane (14).

[0085] The reaction of 2,2'-[[3-(triethoxysilyl)propyl]imino]bis[ethanol] with 2 equivalents of 2-isocyanatoethyl methacrylate gives the silane (15). Synthese von (R 1< O) a R 2< b Si[-A(-X-C(=O)-N(-B[-Z-C(=O)C(=CH 2 )R 3< ] f )-C(=O)-NH-B[-Z-C(=O)C(=CH 2 )R 3< ] f ) d ] c

[0086] The synthesis of the silanes (R 1< O) a R 2< b Si[-A(-XC(=O)-N(-B[-ZC(=O)C(=CH 2 )R 3< ] f )-C(=O)-NH-B[-ZC(=O)C(=CH 2 )R 3< ] f ) d ] c is carried out analogously to the above-described syntheses of the silanes (R 1< O) a R 2< b Si[-A(-XC(=O)-NH-B[-ZC(=O)C(=CH 2 )R 3< ] f ) d ] c . In this case, one equivalent of XH group is reacted with two equivalents of isocyanate compound to give the corresponding allophanates, thioallophanates and biurets. The reactions also proceed under tin or bismuth catalysis. Preferred catalysts are also dibutyltin dilaurate and bismuth neodecanoate. Under gentle heating, one XH group is reacted with two equivalents of isocyanate compound. The reaction usually proceeds to completion and can be easily monitored in the IR spectrum until the isocyanate band (2270 cm -1 ) has completely disappeared.

[0087] However, it is equally possible to react the XH groups with the isocyanate groups in a stoichiometry between 1:1 and 1:2. The second reaction stage can then no longer proceed to completion, resulting in a mixture of urethane and allophanate, or of thiourethane and thioallophanate, or of urea and biuret. Polymerizable dental compositions according to the invention can thus also contain corresponding mixed forms of species (a1). (R 1< O) a R 2< b Si[-A(-XH) d ] c + (2 xcxd) [R 3< -C(=CH 2 )C(=O)-Z-] f B-NCO → (R 1< O) a R 2< 6 Si[-A(-XC(=O)-N(-B[-ZC(=O)C(=CH 2 )R 3< ] f )-C(=O)-NH-B[-ZC(=O)C(=CH 2 )R 3< ] f ) d ] c

[0088] The commercially available compounds listed in Tables 1 and 2 can also be used as starting compounds.

[0089] In the following, some examples of the syntheses of the silanes (R 1< O) a R 2< b Si[-A(-XC(=O)-N(-B[-ZC(=O)C(=CH 2 )R 3< ] f )-C(=O)-NH-B[-ZC(=O)C(=CH 2 )R 3< ] f ) d ] c are presented.

[0090] The reaction of 3-(trimethoxysilyl)-1-propanol with two equivalents of 2-isocyanatoethyl methacrylate yields the allophanate silane (16).

[0091] The reaction of 3-(methyldimethoxysilyl)-1-propanol with two equivalents of 2-isocyanatoethyl methacrylate yields the allophanate silane (17).

[0092] The reaction of 1-(triethoxysilyl)methanol with two equivalents of 2-isocyanatoethyl methacrylate yields the allophanate silane (18).

[0093] The reaction of 3-(trimethoxysilyl)-1-propanethiol with two equivalents of 2-isocyanatoethyl methacrylate yields the thioallophanate silane (19).

[0094] The reaction of 3-(trimethoxysilyl)-1-propanamine with two equivalents of 2-isocyanatoethyl methacrylate yields the biuret silane (20). Synthese von (R 1< O) a R 2< b Si[-A(-NH-C(=O)-X-B[-Z-C(=O)C(=CH 2 )R 3< ] f ) d ] c

[0095] The synthesis of the silanes (R 1< O) a R 2< b Si[-A(-NH-C(=O)-XB[-ZC(=O)C(=CH 2 )R 3< ] f ) d ] c is carried out analogously with tin or bismuth catalysis, whereby in this case the isocyanate group is located on the silane and the XH group on the (meth)acrylic compound. Preferred catalysts here are also dibutyltin dilaurate and bismuth neodecanoate. With slight heating, one XH group is reacted with one isocyanate group in an equimolar ratio. The reaction usually proceeds to completion and can be easily followed in the IR spectrum until the isocyanate band (2270 cm -1< ) ​​has completely disappeared. (R 1< O) a R 2< b Si[-A(-NCO) d ] c + (cxd) [R 3< -C(=CH 2 )C(=O)-Z-] f B-XH → (R 1< O) a R 2< b Si[-A(-NH-C(=O)-XB[-ZC(=O)C(=CH 2 )R 3< ] f ) d] c

[0096] The following two Tables 3 and 4 list a number of commercially available starting compounds. Table 3: (R 1< O) a R 2< b Si[-A(-NCO) d ] c CAS-Nr. R 1< R 2< a b c d -A- 15396-00-6 Me - 3 0 1 1 -(CH 2 ) 3 - 24801-88-5 Et - 3 0 1 1 -(CH 2 ) 3 - 26115-72-0 Me Me 2 1 1 1 -(CH 2 ) 3 - 33491-28-0 Et Me 2 1 1 1 -(CH 2 ) 3 - 78450-75-6 Me - 3 0 1 1 -CH 2 - 132112-76-6 Et - 3 0 1 1 -CH 2 - 406679-89-8 Me Me 2 1 1 1 -CH 2 - 20160-30-9 Et Me 2 1 1 1 -CH 2 - 862546-89-2 Et - 3 0 1 1 -(CH 2 ) 10 - Table 4: [R 3< -C(=CH 2 )C(=O)-Z-] f B-XH CAS-Nr. R 3< Z f XH -B- 868-77-9 Me O 1 OH -(CH 2 ) 2 - 923-26-2 Me O 1 OH -CH 2 CH(CH 3 )- 2761-09-3 Me O 1 OH -(CH 2 ) 3 - 997-46-6 Me O 1 OH -(CH 2 ) 4 - 13092-57-4 Me O 1 OH -(CH 2 ) 6 - 203245-10-7 Me O 1 OH 4855-07-6 Me O 1 OH -(CH 2 ) 8 - 56927-66-3 Me O 1 OH -(CH 2 ) 10 - 115372-36-6 Me O 1 OH 86282-42-0 Me O 1 OH -(CH 2 ) 12 - 2351-43-1 Me O 1 OH -(CH 2 ) 2 O(CH 2 ) 2 - 2351-42-0 Me O 1 OH -(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 - 16926-87-7 Me O 1 OH -CH 2 CH(CH 2 OPh)- 818-61-1 H O 1 OH -(CH 2 ) 2 - 999-61-1 H O 1 OH -CH 2 CH(CH 3 )- 2761-08-2 H O 1 OH -(CH 2 ) 3 - 2478-10-6 H O 1 OH -(CH 2 ) 4 - 57198-94-4 H O 1 OH -(CH 2 ) 5 - 10095-14-4 H O 1 OH -(CH 2 ) 6 - 118915-15-4 H O 1 OH -(CH 2 ) 3 - 23117-38-6 H O 1 OH -(CH 2 ) 10 - 216581-76-9 H O 1 OH 13533-05-6 H O 1 OH -(CH 2 ) 2 O(CH 2 ) 2 - 16695-45-7 H O 1 OH -(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 - 16969-10-1 H O 1 OH -CH 2 CH(CH 2 OPh)- 1830-78-0 Me O 2 OH 101525-90-0 Me O 2 OH 1709-71-3 H / Me O 2 OH 433937-38-3 H / Me O 2 OH 1709-72-4 H O 2 OH 53151-63-6 Me O 2 OH 19727-16-3 Me O 2 OH 37275-47-1 H O 2 OH 3524-66-1 Me O 3 OH 3524-68-3 H O 3 OH 60506-81-2 H O 5 OH 7659-36-1 Me O 1 NH 2 -(CH 2 ) 2 - 7659-38-3 H O 1 NH 2 -(CH 2 ) 2 - 5238-56-2 Me NH 1 OH -(CH 2 ) 2 - 21442-01-3 Me NH 1 OH -CH 2 CH(CH 3 )- 89911-51-3 Me NH 1 OH -(CH 2 ) 2 O(CH 2 ) 2 - 89911-50-2 H NH 1 OH -(CH 2 ) 2 O(CH 2 ) 2 - 96189-83-2 Me NH 1 OH -(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 - 63298-57-7 Me NH 1 NH 2 -(CH 2 ) 2 - 23918-29-8 H NH 1 NH 2 -(CH 2 ) 2 -

[0097] In the following, some examples of syntheses of the silanes (R 1< O) a R 2< b Si[-A(-NH-C(=O)-XB[-ZC(=O)C(=CH 2 )R 3< ] f ) d ] c are presented.

[0098] The reaction of 1-(trimethoxysilyl)methyl isocyanate with 2-hydroxyethyl methacrylate (HEMA) yields the silane (21).

[0099] The reaction of 3-(trimethoxysilyl)propyl isocyanate with 2-hydroxyethyl methacrylate (HEMA) yields the silane (22).

[0100] The reaction of 10-(triethoxysilyl)decylisocyanate with 2-hydroxyethyl methacrylate (HEMA) yields the silane (23).

[0101] The reaction of 3-(methyldimethoxysilyl)propyl isocyanate with 2-hydroxyethyl methacrylate (HEMA) yields the silane (24).

[0102] The reaction of 1-(trimethoxysilyl)methyl isocyanate with 4-hydroxybutyl methacrylate yields the silane (25).

[0103] The reaction of 1-(trimethoxysilyl)methyl isocyanate with 6-hydroxyhexyl methacrylate yields the silane (26).

[0104] The reaction of 1-(trimethoxysilyl)methyl isocyanate with 4-hydroxycyclohexyl methacrylate yields the silane (27).

[0105] The reaction of 1-(trimethoxysilyl)methyl isocyanate with 3-hydroxy-adamantan-1-yl methacrylate yields the silane (28).

[0106] The reaction of 1-(trimethoxysilyl)methyl isocyanate with 2-(2-hydroxyethoxy)ethyl methacrylate yields the silane (29).

[0107] The reaction of 1-(trimethoxysilyl)methyl isocyanate with 2-[2-(2-hydroxyethoxy)ethoxy]ethyl methacrylate yields the silane (30).

[0108] The reaction of 1-(trimethoxysilyl)methyl isocyanate with 2-hydroxy-3-phenoxy-1-propyl methacrylate yields the silane (31).

[0109] The reaction of 1-(trimethoxysilyl)methyl isocyanate with glycerol-1,3-dimethacrylate yields the silane (32).

[0110] The reaction of 1-(trimethoxysilyl)methyl isocyanate with pentaerythritol trimethacrylate yields the silane (33).

[0111] The reaction of 1-(trimethoxysilyl)methyl isocyanate with 2-aminoethyl methacrylate yields the silane (34).

[0112] The reaction of 1-(trimethoxysilyl)methyl isocyanate with (2-hydroxyethyl)methacrylamide yields the silane (35). Synthese von (R 1< O) a R 2< b Si[-A(-NH-C(=O)-B[-Z-C(=O)C(=CH 2 )R 3< ] f ) d ] c

[0113] The synthesis of the silanes (R 1< O) a R 2< b Si[-A(-NH-C(=O)-B[-ZC(=O)C(=CH 2 )R 3< ] f ) d ] c is tin- or bismuth-catalyzed with elimination of carbon dioxide from a silane with an isocyanate group and a carboxyl-substituted (meth)acrylic compound. Preferred catalysts are dibutyltin dilaurate and bismuth neodecanoate. With gentle heating, one carboxyl group is reacted with one isocyanate group in an equimolar ratio. The reaction usually proceeds to completion and can be easily followed in the IR spectrum until the isocyanate band (2270 cm -1< ) ​​has completely disappeared. (R 1< O) a R 2< b Si[-A(-NCO) d ] c + (cxd)[R 3< -C(=CH 2 )C(=O)-Z-] f B-COOH → (R 1< O) a R 2< b Si[-A(-NH-C(=O)-B[-ZC(=O)C(=CH 2 )R 3< ] f ) d ] c

[0114] A number of commercially available carboxyl(meth)acrylic compounds are listed in Table 5 below. Suitable isocyanate-substituted silanes are the commercially available compounds listed above in Table 3. Table 5: [R 3< -C(=CH 2 )C(=O)-Z-] f B-COOH CAS-Nr. R 3< Z f -B- 141681-03-0 H O 1 -(CH 2 ) 3 - 59178-90-4 Me NH 1 -(CH 2 ) 2 - 16753-07-4 H NH 1 -(CH 2 ) 2 - 59178-91-5 Me NH 1 -(CH 2 ) 3 - 59178-91-5 H NH 1 -(CH 2 ) 3 - 20882-04-6 Me O 1 -(CH 2 ) 2 OC(=O)-(CH 2 ) 2 - 112241-32-4 Me O 1 -(CH 2 ) 3 OC(=O)-(CH 2 ) 2 - 51252-88-1 Me O 1 27697-00-3 Me O 1 65859-45-2 Me O 1

[0115] In the following, some examples of syntheses of the silanes (R 1< O) a R 2< b Si[-A(-NH-C(=O)-B[-ZC(=O)C(=CH 2 )R 3< ] f ) d ] c are presented.

[0116] The reaction of 3-(trimethoxysilyl)propyl isocyanate with mono[2-(methacryloyloxy)ethyl]succinate yields the silane (36).

[0117] The reaction of 1-(trimethoxysilyl)methyl isocyanate with mono[2-(methacryloyloxy)ethyl]succinate yields the silane (37).

[0118] The reaction of 1-(trimethoxysilyl)methyl isocyanate with butanedioic acid 1-[3-[(2-methyl-1-oxo-2-propen-1-yl)oxy]propyl] ester yields the silane (38).

[0119] The reaction of 1-(trimethoxysilyl)methyl isocyanate with 1,2-cyclohexanedicarboxylic acid 1-[2-[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl] ester yields the silane (39).

[0120] The reaction of 1-(trimethoxysilyl)methyl isocyanate with mono[2-(methacryloyloxy)ethyl]phthalate yields the silane (40). Synthese von Silanen mit Urethan-, Thiourethan-, Harnstoff- oder Amidgruppen ausgehend von Hydrosilanen

[0121] Silanes with urethane, thiourethane, urea, or amide groups can be prepared in a multistep synthesis by platinum-catalyzed reaction of vinyl compounds with hydrosilanes. Corresponding syntheses are disclosed in US 2015 / 0299469 A1. Synthese von (R 1< O) a R 2< b Si[-(CH 2 ) 2 -CH(R 4< )-NH-C(=O)-B[-Z-C(=O)C(=CH 2 )R 3< ] f ] c

[0122] In a two-step synthesis, a carboxyl-(meth)acrylic compound is first reacted with an allylamine. [R 3< -C(=CH 2 )C(=O)-Z-] f B-COOH + H 2 C=CHCH(R 4< )-NH 2 → [R 3< -C(=CH 2 )C(=O)-Z-] f BC(=O)-NH-CH(R 4< )-CH=CH 2

[0123] Commercially available carboxyl (meth)acrylic compounds are listed above in Table 5. Commercially available allylamines are listed in Table 6 below. Table 6: H 2 C=CHCH(R 4< )-NH 2 CAS-Nr. R 4< 107-11-9 H 34375-90-1 Me 70267-50-4 Et 4181-11-7 n -Pr 127209-34-1 i< Pr 5963-71-3 n -This 36024-39-2 t< This 4393-21-9 Ph 1186139-06-9

[0124] In the second synthesis step, the resulting vinyl compound is reacted with a hydrosilane (R 1< O) a R 2< b SiH c under platinum catalysis. Commercially available hydrosilanes are listed in Table 7. Further trialkoxysilanes HSi(OR 1< ) 3 can be prepared according to EP 0 285 133 A2 by copper(II) hydroxide-catalyzed reaction of silicon with alcohols. c [R 3< -C(=CH 2 )C(=O)-Z-] f BC(=O)-NH-CH(R 4< )-CH=CH 2 + (R 1< O) a R 2< b SiH c → (R 1< O) a R 2< b Si[-(CH 2 ) 2 -CH(R 4< )-NH-C(=O)-B[-ZC(=O)C(=CH 2 )R 3< ] f ] c Table 7: (R 1< O) a R 2< b SiH c CAS-Nr. R 1< R 2< a b c 2487-90-3 Me - 3 0 1 998-30-1 Et - 3 0 1 6485-85-4 n -Pr - 3 0 1 6675-79-2 i< Pr - 3 0 1 6485-86-5 n -This - 3 0 1 16881-77-9 Me Me 2 1 1 2031-62-1 Et Me 2 1 1 54010-11-6 i< Pr Me 2 1 1 2487-91-4 n -This Me 2 1 1 19753-84-5 Me Et 2 1 1 13175-88-7 Et Et 2 1 1 18132-62-2 n -This Et 2 1 1 163215-58-5 Me i< Pr 2 1 1 5314-52-3 Me - 2 0 2 18165-68-9 Et - 2 0 2

[0125] In the following, some examples of syntheses of the silanes (R 1< O) a R 2< b Si[-(CH 2 ) 2 -CH(R 4< )-NH-C(=O)-B[-ZC(=O)C(=CH 2 )R 3< ] f ] c are presented.

[0126] Reaction of mono[2-(methacryloyloxy)ethyl]succinate with allylamine initially yields the vinyl compound (41). Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (42).

[0127] By reacting 3-methacryloylaminopropanoic acid with allylamine, the vinyl compound (43) is initially obtained. Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (44).

[0128] By reacting 3-methacryloylaminopropanoic acid with allylamine, the vinyl compound (45) is initially obtained. Further platinum-catalyzed reaction with methyldimethoxysilane finally yields the silane (46). Synthese von (R 1< O) a R 2< b Si[-(CH 2 ) 2 -C(=O)-NH-B[-Z-C(=O)C(=CH 2 )R 3< ] f ] c

[0129] In a two-step synthesis, an amino(meth)acrylic compound is first reacted with acryloyl chloride (CAS No. 814-68-6). Preferably, R 3< is a methyl group, since in this case the subsequent reaction with (R 1< O) a R 2< b SiH c occurs selectively at the acrylamide function. Commercially available amino(meth)acrylic compounds are listed in Table 4 (for XH = NH 2 ). [R 3< -C(=CH 2 )C(=O)-Z-] f B-NH 2 + H 2 C=CHCOCl → [R 3< -C(=CH 2 )C(=O)-Z-] f B-NH-C(=O)-CH=CH 2

[0130] In the second synthesis step, the resulting vinyl compound is reacted with a hydrosilane (R 1< O) a R 2< b SiH c under platinum catalysis. Commercially available hydrosilanes are listed in Table 7. c [R 3< -C(=CH 2 )C(=O)-Z-] f B-NH-C(=O)-CH=CH 2 + (R 1< O) a R 2< b SiH c → (R 1< O) a R 2< b Si[-(CH 2 ) 2 -C(=O)-NH-B[-ZC(=O)C(=CH 2 )R 3< ] f ] c

[0131] Reaction of 2-aminoethyl methacrylate with acryloyl chloride yields the vinyl compound (47). Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (48). Synthese von (R 1< O) a R 2< b Si[-(CH 2 ) 2 -CH(R 4< )-X-C(=O)-NH-B[-Z-C(=O)C(=CH 2 )R 3< ] f ] c

[0132] In a two-step synthesis, the isocyanate-substituted (meth)acrylic compound is first reacted with an XH compound under tin or bismuth catalysis. Preferred catalysts here are also dibutyltin dilaurate and bismuth neodecanoate. With gentle heating, one XH group is reacted with one isocyanate group in an equimolar ratio. The reaction usually proceeds to completion and can be easily monitored in the IR spectrum until the isocyanate band (2270 cm -1 ) has completely disappeared. Commercially available isocyanate-substituted (meth)acrylic compounds are listed above in Table 2. Commercially available XH compounds are listed in Table 8 below. [R 3< -C(=CH 2 )C(=O)-Z-] f B-NCO + H 2 C=CHCH(R 4< )-XH → [R 3< -C(=CH 2 )C(=O)-Z-] f B-NH-C(=O)-X-CH(R 4< )-CH=CH 2 Table 8: H 2 C=CHCH(R 4< )-XH CAS-Nr. XH R 4< 107-18-6 OH H 598-32-3 OH Me 616-25-1 OH Et 4798-44-1 OH n -Pr 4798-45-2 OH i< Pr 4938-52-7 OH n -This 24580-44-7 OH t< This 3391-86-4 OH n -Pentyl 21964-44-3 OH n -Hexyl 51100-54-0 OH n -Heptyl 35329-42-1 OH n -Octyl 4393-06-0 OH Ph 61619-02-1 OH 870-23-5 SH H 5937-82-6 SH Me 61758-08-5 SH n -Pentyl 39707-48-7 SH Ph 107-11-9 NH 2 H 34375-90-1 NH 2 Me 70267-50-4 NH 2 Et 4181-11-7 NH 2 n -Pr 127209-34-1 NH 2 i< Pr 5963-71-3 NH 2 n -This 36024-39-2 NH 2 t< This 4393-21-9 NH 2 Ph 1186139-06-9 NH 2

[0133] In the second synthesis step, the resulting vinyl compound is reacted with a hydrosilane (R 1< O) a R 2< b SiH c under platinum catalysis. Commercially available hydrosilanes are listed in Table 7. c [R 3< -C(=CH 2 )C(=O)-Z-] f B-NH-C(=O)-X-CH(R 4< )-CH=CH 2 + (R 1< O) a R 2< b SiH c → (R 1< O) a R 2< b Si[-(CH 2 ) 2 -CH(R 4< )-XC(=O)-NH-B[-ZC(=O)C(=CH 2 )R 3< ] f ] c

[0134] In the following, some examples of the syntheses of the silanes (R 1< O) a R 2< b Si[-(CH 2 ) 2 -CH(R 4< )-XC(=O)-NH-B[-ZC(=O)C(=CH 2 )R 3< ] f ] c are presented.

[0135] Reaction of 2-isocyanatoethyl methacrylate with 2-propen-1-ol yields the vinyl compound (49). Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (50).

[0136] Reaction of 2-isocyanatoethyl methacrylate with 2-propene-1-thiol yields the vinyl compound (51). Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (52).

[0137] Reaction of 2-isocyanatoethyl methacrylate with 3-amino-1-propene yields the vinyl compound (53). Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (54). Synthese von (R 1< O) a R 2< b Si[-(CH 2 ) 2 -CH(R 4< )-X-C(=O)-N(-B[-Z-C(=O)C(=CH 2 )R 3< ] f )-C(=O)-NH-B[-Z-C(=O)C(=CH 2 )R 3< ] f ] c

[0138] Analogous to the synthesis of [R 3< -C(=CH 2 )C(=O)-Z-] f B-NH-C(=O)-X-CH(R 4< )-CH=CH 2 , the silanes (R 1< O) a R 2< b Si[-(CH 2 ) 2 -CH(R 4< )-XC(=O)-N(-B[-ZC(=O)C(=CH 2 )R 3< ] f )-C(=O)-NH-B[-ZC(=O)C(=CH 2 )R 3< ] f ] c can also be prepared in a two-step synthesis from an XH compound and an isocyanate-substituted (meth)acrylic compound. Two equivalents of the isocyanate-substituted (meth)acrylic compound are first reacted with one equivalent of an X-H compound under tin or bismuth catalysis, yielding the corresponding allophanates, thioallophanates, or biurets. Preferred catalysts here are also dibutyltin dilaurate and bismuth neodecanoate. The reaction proceeds with slight heating, is usually complete, and can be easily monitored in the IR spectrum until the isocyanate band (2270 cm -1 ) has completely disappeared. Commercially available isocyanate-substituted (meth)acrylic compounds are listed above in Table 2.Commercially available XH compounds are listed in Table 8 below. Here, too, it is possible to react the XH groups with the isocyanate groups in a stoichiometry between 1:1 and 1:2, so that the second reaction step is then incomplete, resulting in a mixture of urethane and allophanate, or of thiourethane and thioallophanate, or of urea and biuret. In the second synthesis step, the resulting vinyl compounds are again reacted with a hydrosilane (R 1< O) a R 2< b SiH c under platinum catalysis. Commercially available hydrosilanes are listed in Table 7.

[0139] Reaction of two equivalents of 2-isocyanatoethyl methacrylate with 2-propen-1-ol yields the vinyl compound (55). Further platinum-catalyzed reaction with triethoxysilane finally yields the allophanate silane (56).

[0140] Reaction of two equivalents of 2-isocyanatoethyl methacrylate with 2-propene-1-thiol yields the vinyl compound (57). Further platinum-catalyzed reaction with triethoxysilane finally yields the thioallophanate silane (58).

[0141] Reaction of two equivalents of 2-isocyanatoethyl methacrylate with 3-amino-1-propene yields the vinyl compound (59). Further platinum-catalyzed reaction with triethoxysilane finally yields the biuret silane (60). Synthese von (R 1< O) a R 2< b Si[-(CH 2 ) 2 -CH(R 4< )-NH-C(=O)-X-B[-Z-C(=O)C(=CH 2 )R 3< ] f ] c

[0142] In a two-step synthesis, an OH-, SH-, or NH2-substituted (meth)acrylic compound is first reacted with an isocyanate-substituted vinyl compound under tin or bismuth catalysis. Preferred catalysts here are also dibutyltin dilaurate and bismuth neodecanoate. With gentle heating, one XH group is reacted with one isocyanate group in an equimolar ratio. The reaction usually proceeds to completion and can be easily monitored in the IR spectrum until the isocyanate band (2270 cm-1) has completely disappeared. Commercially available XH-substituted (meth)acrylic compounds are listed above in Table 4. Commercially available isocyanate-substituted vinyl compounds are listed in Table 9 below. [R 3< -C(=CH 2 )C(=O)-Z-] f B-XH + H 2 C=CHCH(R 4< )-NCO → [R 3< -C(=CH 2 )C(=O)-Z-] f BXC(=O)-NH-CH(R 4< )CH=CH 2 Table 9: H 2 C=CHCH(R 4< )-NCO CAS-Nr. R 4< 1476-23-9 H 155469-99-1 Me 55887-59-7 Ph

[0143] In the second synthesis step, the resulting vinyl compound is reacted with a hydrosilane (R 1< O) a R 2< b SiH c under platinum catalysis. Commercially available hydrosilanes are listed in Table 7. c [R 3< -C(=CH 2 )C(=O)-Z-] f BXC(=O)-NH-CH(R 4< )-CH=CH 2 + (R 1< O) a R 2< b SiH c → (R 1< O) a R 2< b Si[-(CH 2 ) 2 -CH(R 4< )-NH-C(=O)-XB[-ZC(=O)C(=CH 2 )R 3< ] f ] c

[0144] In the following, some examples of syntheses of the silanes (R 1< O) a R 2< b Si[-(CH 2 ) 2 -CH(R 4< )-NH-C(=O)-XB[-ZC(=O)C(=CH 2 )R 3< ] f ] c are presented.

[0145] Reaction of 2-hydroxyethyl methacrylate (HEMA) with 3-isocyanato-1-propene yields the vinyl compound (61). Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (62).

[0146] Reaction of 1,3-glycerol dimethacrylate with 3-isocyanato-1-propene yields the vinyl compound (63). Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (64).

[0147] Reaction of 2-hydroxypropyl methacrylate with 3-isocyanato-3-phenyl-1-propene yields the vinyl compound (65). Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (66).

[0148] Reaction of 2-aminoethyl methacrylate with 3-isocyanato-1-propene yields the vinyl compound (67). Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (68). Synthese von (R 1< O) a R 2< b Si[-A(-C(=O)NHC(=O)NH{-B[-Z-C(=O)C(=CH 2 )R 3< ] f} e ) d ] c :

[0149] Acylurea silanes, for example, can be prepared in a two-step synthesis starting from vinyl-functionalized amides by reaction with isocyanate-substituted (meth)acrylates. First, the amide is reacted with an isocyanate-substituted vinyl compound under tin or bismuth catalysis. Preferred catalysts here are also dibutyltin dilaurate and bismuth neodecanoate. With gentle heating, one amide group is reacted with one isocyanate group in an equimolar ratio. The reaction usually proceeds to completion and can be easily monitored in the IR spectrum until the isocyanate band (2270 cm -1 ) has completely disappeared. Commercially available isocyanate-substituted vinyl compounds are listed in Table 2. Hydrosilylation then follows. Commercially available hydrosilanes are listed in Table 7.

[0150] For example, the reaction of 3-butenamide (CAS No. 28446-58-4) with 2-isocyanatoethyl methacrylate and subsequent hydrosilylation with triethoxysilane yields the corresponding acylurea silane. Synthese von (R 1< O) a R 2< b Si[-A(-NHC(=O)NHC(=O){-B[-Z-C(=O)C(=CH 2 )R 3< ] f} e ) d ] c :

[0151] Acylurea silanes can be prepared, for example, in a two-step synthesis starting from amide-functionalized (meth)acrylates by reaction with vinyl-substituted isocyanates. First, the amide is reacted with a vinyl-substituted isocyanate compound under tin or bismuth catalysis. Preferred catalysts here are also dibutyltin dilaurate and bismuth neodecanoate. With gentle heating, one amide group is reacted with one isocyanate group in an equimolar ratio. The reaction usually proceeds to completion and can be easily monitored in the IR spectrum until the isocyanate band (2270 cm -1 ) has completely disappeared. Commercially available vinyl-substituted isocyanates are listed in Table 9. Hydrosilylation then follows. Commercially available hydrosilanes are listed in Table 7.

[0152] For example, the reaction of 2-carbamoylethyl methacrylate (CAS No. 160031-60-7) with 3-isocyanato-1-propene and subsequent hydrosilylation with triethoxysilane yields the corresponding acylurea silane. Silan (R 1< O) a R 2< b Si[-A'(-PG) f ] c (a2):

[0153] The silane (a2) corresponds to the formula (R 1< O) a R 2< b Si[-A'(-PG) f ] c with PG = polymerizable group, wherein the polymerizable group PG is selected from the group consisting of -ZC(=O)-CH=CH 2 and -ZC(=O)-C(CH 3 )=CH 2 where Z is selected from the group consisting of O and NH, A' = an organic linking group that connects Si to PG and has 1 to 20 C atoms and none of the groups -C(=O)NH-, -NHC(=O)-, -OC(=O)NH-, -NHC(=O)O-, -SC(=O)NH-, -NHC(=O)S-, -NHC(=O)NH-, -OC(=O)N(-C(=O)NH-)-, -SC(=O)N(-C(=O)NH-)-, -NHC(=O)N(-C(=O)NH-)- -C(=O)NHC(=O)NH-, or -NHC(=O)NHC(=O)-, R 1< = H or C1- to C4-alkyl, R 2< = C1- to C4-alkyl, a = 2 or 3 b = 0 or 1 c = 1 or 2 f = 1 to 5 and a + b + c = 4 .

[0154] In a preferred embodiment, the polymerizable group PG is selected from the group consisting of -ZC(=O)-CH=CH 2 and -ZC(=O)-C(CH 3 )=CH 2 where Z = O.

[0155] The organic linking group A', which connects the Si atom to the polymerizable group PG, is an (f+1)-valent, straight-chain, branched or cyclic group which has 1 to 20 C atoms and may optionally have O atoms, S atoms, NR groups, ester groups or thioester groups.

[0156] In a preferred embodiment, the connecting group A' is selected from the group consisting of -(CH 2 ) n - with n = 1 to 12, -(CH 2 ) n -N(CH 3 )-(CH 2 ) n -with n = 1 to 4, -(CH 2 ) n N[(CH 2 ) n -] 2 with n = 1 to 4 and -(CH 2 ) n -CH(R)-(CH 2 ) n - with n = 0 to 4 and R = methyl, ethyl, phenyl and with n = 1 to 6, where the bond on the left is connected to the Si atom and the bond(s) on the right is / are connected to the group(s) PG.

[0157] In a very preferred embodiment, the connecting group A' is -(CH 2 ) n - with n = 1 to 6.

[0158] In a preferred embodiment, the radical R 1< is selected from the group consisting of H, methyl and ethyl.

[0159] In a preferred embodiment, the index f = 1 or 2.

[0160] A number of suitable silanes (R 1< O) a R 2< b Si[-A'(-ZC(=O)C(=CH 2 )R 3< ) f ] c are commercially available (see Table 10). Furthermore, the silanes can be prepared by common synthetic methods. Some synthesis routes are disclosed, for example, in US 2015 / 0299469 A1. Table 10: (R 1< O) a R 2< b Si [A'(-Z-C(=O)C(=CH 2 )R 3< ) f ] c CAS-Nr. R 1< R 2< R 3< Z a b c f -A'- 21134-38-3 Me - H O 3 0 1 1 -(CH 2 )- 54586-78-6 Me - Me O 3 0 1 1 -(CH 2 )- 78884-71-6 Et - H O 3 0 1 1 -(CH 2 )- 5577-72-0 Et - Me O 3 0 1 1 -(CH 2 )- 121177-93-3 Me Me Me O 2 1 1 1 -(CH 2 )- 3978-58-3 Et Me Me O 2 1 1 1 -(CH 2 )- 4369-14-6 Me - H O 3 0 1 1 -(CH 2 ) 3 - 2530-85-0 Me - Me O 3 0 1 1 -(CH 2 ) 3 - 57577-96-5 Me - H NH 3 0 1 1 -(CH 2 ) 3 - 10310-41-5 Me - Me NH 3 0 1 1 -(CH 2 ) 3 - 20208-39-3 Et - H O 3 0 1 1 -(CH 2 ) 3 - 21142-29-0 Et - Me O 3 0 1 1 -(CH 2 ) 3 - 80750-05-6 i< Pr - Me O 3 0 1 1 -(CH 2 ) 3 - 13732-00-8 Me Me H O 2 1 1 1 -(CH 2 ) 3 - 14513-34-9 Me Me Me O 2 1 1 1 -(CH 2 ) 3 - 146666-71-9 Et Me H O 2 1 1 1 -(CH 2 ) 3 - 65100-04-1 Et Me Me O 2 1 1 1 -(CH 2 ) 3 - Synthese von (R 1< O) a R 2< b Si[-A'(-Z-C(=O)C(=CH 2 )R 3< ) f ] c

[0161] Suitable silanes are obtained by reacting OH-, SH-, or NH 2 -functionalized silanes with (meth)acryloyl chloride. The synthesis is generally simple and quantitative. Alternatively, (meth)acrylic acid or other (meth)acrylic acid derivatives can be used in the usual processes. Suitable commercial ZH-functionalized silanes are listed in Table 11. (R 1< O) a R 2< b Si[-A'(-ZH) f ] c + (cxe) R 3< C(=CH 2 )C(=O)Cl → (R 1< O) a R 2< b Si[-A'(-ZC(=O)C(=CH 2 )R 3< ) f ] c Table 11: (R 1< O) a R 2< b Si[-A'(-ZH) f ] c CAS-Nr. R 1< R 2< ZH a b c f -A'- 53764-54-8 Me - OH 3 0 1 1 -(CH 2 ) 3 - 53394-61-9 Et - OH 3 0 1 1 -(CH 2 ) 3 - 99697-20-8 Me Me OH 2 1 1 1 -(CH 2 ) 3 - 162781-70-6 Et - OH 3 0 1 1 -(CH2) 1 - 13822-56-5 Me - NH 2 3 0 1 1 -(CH 2 ) 3 - 3663-44-3 Me Me NH 2 2 1 1 1 -(CH 2 ) 3 - 3179-76-8 Et Me NH 2 2 1 1 1 -(CH 2 ) 3 - 71408-48-5 Me - NH 2 3 0 1 1 -(CH2) 1 - 18306-83-7 Et - NH 2 3 0 1 1 -(CH 2 ) 1 - 51749-36-1 Me - NH 2 2 0 2 1 -(CH 2 ) 3 - 53746-12-6 Et - NH 2 2 0 2 1 -(CH 2 ) 3 - 330457-46-0 Me - OH 3 0 1 1 -(CH 2 ) 3 -N(CH 3 )-(CH 2 ) 2 - 24801-87-4 Me - OH 3 0 1 2 -(CH 2 ) 3 N[(CH 2 ) 2 -] 2 7538-44-5 Et - OH 3 0 1 2 -(CH 2 ) 3 N[(CH 2 ) 2 -] 2

[0162] In the following, some examples of syntheses of the silanes (R 1< O) a R 2< b Si[-A'(-ZC(=O)C(=CH 2 )R 3< ) f ] c are presented.

[0163] The silane (69) is obtained by reacting 3-(trimethoxysilyl)-1-propanol with methacryloyl chloride.

[0164] The silane (70) is obtained by reacting 3-(methyldimethoxysilyl)-1-propanol with methacryloyl chloride.

[0165] The silane (71) is obtained by reacting 1-(trimethoxysilyl)methanol with methacryloyl chloride.

[0166] The silane (72) is obtained by reacting 1-(methyldimethoxysilyl)-methanol with methacryloyl chloride.

[0167] The reaction of 2,2'-[[3-(triethoxysilyl)propyl]imino]bis[ethanol] with 2 equivalents of methacryloyl chloride yields the silane (73). Synthese von Silanen ausgehend von Hydrosilanen

[0168] Suitable silanes can be prepared in a multi-step synthesis by platinum-catalyzed reaction of vinyl compounds with hydrosilanes. Corresponding syntheses are disclosed in US 2015 / 0299469 A1. Synthese von (R 1< O) a R 2< b Si[-(CH 2 ) (n+2) -Z-C(=O)C(=CH 2 )R 3< ] c

[0169] In a two-step synthesis, (meth)acryloyl chloride is first reacted with an OH- or NH 2 -functionalized terminal vinyl compound. Alternatively, (meth)acrylic acid or other (meth)acrylic acid derivatives can be used in the usual procedures. R 3< C(=CH 2 )C(=O)Cl + H 2 C=CH(CH 2 ) n -ZH → R 3< C(=CH 2 )C(=O)-Z-(CH 2 ) n CH=CH 2 Table 12: H 2 C=CH(CH 2 ) n -ZH CAS-Nr. n ZH 107-18-6 1 OH 627-27-0 2 OH 821-09-0 3 OH 821-41-0 4 OH 4117-10-6 5 OH 13175-44-5 6 OH 107-11-9 1 NH 2 2524-49-4 2 NH 2 22537-07-1 3 NH 2 34825-70-2 4 NH 2 151626-26-5 5 NH 2 82223-49-2 6 NH 2

[0170] In the second synthesis step, the resulting vinyl compound is reacted with a hydrosilane (R 1< O) a R 2< b SiH c under platinum catalysis. Commercially available hydrosilanes are listed above in Table 7. c R 3< C(=CH 2 )C(=O)-Z-(CH 2 ) n CH=CH 2 + (R 1< O) a R 2< b SiH c → (R 1< O) a R 2< b Si[-(CH 2 ) (n+2) -ZC(=O)C(=CH 2 )R 3< ] c

[0171] In the following, some examples of syntheses of the silanes (R 1< O) a R 2< b Si[-(CH 2 ) (n+2) -ZC(=O)C(=CH 2 )R 3< ] c are presented.

[0172] By reacting methacryloyl chloride with 2-propen-1-ol, the vinyl compound (74) is initially obtained. Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (75).

[0173] By reacting methacryloyl chloride with 2-propen-1-ol, the vinyl compound (74) is initially obtained. Further platinum-catalyzed reaction with methyldimethoxysilane finally yields the silane (76).

[0174] By reacting methacryloyl chloride with 4-penten-1-ol, the vinyl compound (77) is initially obtained. Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (78).

[0175] By reacting methacryloyl chloride with allylamine, the vinyl compound (79) is initially obtained. Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (80).

[0176] By reacting methacryloyl chloride with allylamine, the vinyl compound (79) is initially obtained. Further platinum-catalyzed reaction with methyldimethoxysilane finally yields the silane (81).

[0177] By reacting methacryloyl chloride with 4-penten-1-amine, the vinyl compound (82) is initially obtained. Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (83). Synthese von (R 1< O) a R 2< b Si[-A'(-Z-C(=O)C(=CH 2 )R 3< ) f ] c

[0178] Suitable OH-functionalized silanes are obtained by reacting glycidoxy-functionalized silanes with (meth)acrylic acid. The synthesis is generally simple and quantitative. Further reaction with (meth)acryloyl chloride or another (meth)acrylic acid derivative can yield suitable silanes containing two (meth)acrylic groups. Suitable commercial glycidoxy-functionalized silanes are listed in Table 13. Table 13: CAS-Nr. R 1< R 2< a b c -A"- 215301-24-9 Et Me 2 1 1 -CH 2 - 2530-83-8 Me - 3 0 1 -(CH 2 ) 3 - 2602-34-8 Et - 3 0 1 -(CH 2 ) 3 - 98899-94-6 n-Pr - 3 0 1 -(CH 2 ) 3 - 252255-95-1 i< Pr - 3 0 1 -(CH 2 ) 3 - 65799-47-5 Me Me 2 1 1 -(CH 2 ) 3 - 2897-60-1 Et Me 2 1 1 -(CH 2 ) 3 - 131535-64-3 n -Pr n -Pr 2 1 1 -(CH 2 ) 2 - 233765-90-7 Me - 3 0 1 -CH(CH 3 )CH 2 - 139485-54-4 Et - 3 0 1 -CH(CH 3 )CH 2 - 70187-33-6 Me - 3 0 1 -CH 2 CH(CH 3 )- 20411-24-1 Me - 2 0 2 -(CH 2 ) 3 -

[0179] In addition, suitable glycidoxy-functionalized silanes can be obtained by reacting glycidoxy-functionalized vinyl compounds with (R 1 < O) a R 2 < b SiH c (see Table 7) under platinum catalysis. 1,2-Epoxy-3-allyloxypropane (CAS No. 106-92-3) is preferably used as the glycidoxy-functionalized vinyl compound. However, suitable glycidoxy-functionalized vinyl compounds can also be prepared by known syntheses. For example, glycidol (CAS No. 556-52-5) can be reacted with 3-butenoyl chloride (CAS No. 1470-91-3), 4-pentenoyl chloride (CAS No. 39716-58-0), or 5-hexenoyl chloride (CAS No. 36394-07-7). Substituted glycidol derivatives can also be used instead of glycidol. Commercially available glycidol derivatives are listed in Table 14. Table 14: CAS-Nr. R 556-52-5 H 765-44-6 Me 4798-48-5 Et 33143-44-1 Ph

[0180] Reaction of (3-glycidoxypropyl)trimethoxysilane with methacrylic acid yields silane (84). Further reaction with methacryloyl chloride yields silane (85). Synthese von (R 1< O) a R 2< b Si[-(CH 2 )( n+2) -X'-C(=O)-B'[-Z-C(=O)C(=CH 2 )R 3< ] f ] c

[0181] In a two-step synthesis, a carboxyl-(meth)acrylic compound is first reacted with an OH- or SH-functionalized terminal vinyl compound. Suitable commercial carboxyl-(meth)acrylic compounds are listed in Table 15. Suitable OH- or SH-functionalized terminal vinyl compounds are listed in Table 16. The use of allyl alcohol or allyl mercaptan is preferred. [R 3< C(=CH 2 )C(=O)-Z-] f B'-COOH + H 2 C=CH(CH 2 ) n -X'H → [R 3< C(=CH 2 )C(=O)-Z-] r B'-C(=O)-X'-(CH 2 ) n CH=CH 2 Table 15: [R 3< -C(=CH 2 )C(=O)-Z-] f B'-COOH CAS-Nr. R 3< Z f -B'- 141681-03-0 H O 1 -(CH 2 ) 3 - 59178-90-4 Me NH 1 -(CH 2 ) 2 - 16753-07-4 H NH 1 -(CH 2 ) 2 - 59178-91-5 Me NH 1 -(CH 2 ) 3 - 59178-91-5 H NH 1 -(CH 2 ) 3 - 20882-04-6 Me O 1 -(CH 2 ) 2 OC(=O)-(CH 2 ) 2 - 112241-32-4 Me O 1 -(CH 2 ) 3 OC(=O)-(CH 2 ) 2 - 51252-88-1 Me O 1 27697-00-3 Me O 1 65859-45-2 Me O 1 Table 16: H 2 C=CH(CH 2 ) n -X'H CAS-Nr. n X'H 107-18-6 1 OH 627-27-0 2 OH 821-09-0 3 OH 821-41-0 4 OH 4117-10-6 5 OH 13175-44-5 6 OH 870-23-5 1 SH 5954-70-1 2 SH 17651-37-5 3 SH 17651-39-7 4 SH 173777-16-7 5 SH 178561-30-3 9 SH

[0182] In the second synthesis step, the resulting vinyl compound is reacted with a hydrosilane (R 1< O) a R 2< b SiH c under platinum catalysis. Commercially available hydrosilanes are listed above in Table 7. c [R 3< C(=CH 2 )C(=O)-Z-] f B'-C(=O)-X'-(CH2) n CH=CH 2 + (R 1< O) a R 2< s SiH c → (R 1< O) a R 2< b Si[-(CH 2 ) (n+2) -X'-C(=O)-B'[-ZC(=O)C(=CH 2 )R 3< ] r ] c

[0183] In the following, some examples of syntheses of the silanes (R 1< O) a R 2< b Si[-(CH 2 ) (n+2) -X'-C(=O)-B'[-ZC(=O)C(=CH 2 )R 3< ] f ] c are presented.

[0184] Reaction of 3-[(2-methyl-1-oxo-2-propen-1-yl)amino]propanoic acid with 2-propen-1-ol initially yields the vinyl compound (86). Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (87).

[0185] Reaction of 4-[(2-methyl-1-oxo-2-propen-1-yl)amino]butanoic acid with 2-propen-1-ol initially yields the vinyl compound (88). Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (89).

[0186] Reaction of 3-[(2-methyl-1-oxo-2-propen-1-yl)amino]propanoic acid with 2-propene-1-thiol initially yields the vinyl compound (90). Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (91).

[0187] Reaction of 4-[(2-methyl-1-oxo-2-propen-1-yl)amino]butanoic acid with 2-propene-1-thiol initially yields the vinyl compound (92). Further platinum-catalyzed reaction with methyldimethoxysilane finally yields the silane (93).

[0188] Reaction of mono[2-(methacryloyloxy)ethyl]succinate with 2-propen-1-ol initially yields the vinyl compound (94). Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (95).

[0189] Reaction of mono[2-(methacryloyloxy)ethyl]succinate with 2-propen-1-ol initially yields the vinyl compound (94). Further platinum-catalyzed reaction with methyldimethoxysilane finally yields the silane (96).

[0190] Reaction of mono[2-(methacryloyloxy)ethyl]succinate with 2-propene-1-thiol initially yields the vinyl compound (97). Further platinum-catalyzed reaction with triethoxysilane finally yields the silane (98). Silane (R 1 < O) a R 2 < b SiAr c (a3):

[0191] The silane (a3) ​​corresponds to the formula (R 1< O) a R 2< b SiAr c with R 1< = H or C1- to C4-alkyl, R 2< = C1- to C4-alkyl, Ar = aryl where different groups Ar can be the same or different, a = 2 or 3, b = 0 or 1, c = 1 or 2 and a + b + c = 4 .

[0192] In a preferred embodiment, the radical R 1< is selected from the group consisting of H, methyl and ethyl.

[0193] In a further preferred embodiment, the radical Ar is a - optionally substituted - phenyl group.

[0194] A number of suitable aromatic silanes are commercially available. Table 17 lists silanes (R 1< O) a R 2< b SiAr with one aryl group, and Table 18 lists silanes (R 1< O) 2 SiAr 2 with two aryl groups. Table 17: (R 1< O) a R 2< b SiAr CAS No. R 1< R 2< a b Ar 2996-92-1 Me - 3 0 Ph 780-69-8 Et - 3 0 Ph 17903-00-3 i< Pr - 3 0 Ph 10581-02-9 n -This - 3 0 Ph 3027-21-2 Me Me 2 1 Ph 775-56-4 Et Me 2 1 Ph 223668-64-2 Me - 3 0 17043-05-9 Me - 3 0 35692-33-2 Me - 3 0 17995-18-5 Et - 3 0 17938-34-0 Et Me 2 1 18052-76-1 Me - 3 0 17938-06-6 Et - 3 0 17938-33-9 Et Me 2 1 912576-47-7 Et - 3 0 21591-53-7 Et - 3 0 212609-47-7 Et - 3 0 21591-51-5 Et - 3 0 135251-76-2 Me - 3 0 18056-97-8 Et - 3 0 91309-02-3 Me Me 2 1 Table 18: (R 1< O) a SiAr 1< Ar 2< CAS No. R 1< a Ar 1< Ar 2< 6843-66-9 Me 2 Ph Ph 2553-19-7 Et 2 Ph Ph 92779-72-1 Me 2 52897-51-5 Et 2 223668-68-6 Me 2 36147-17-8 Me 2 Ph 21591-48-0 Me 2 144677-99-6 Me 2

[0195] Furthermore, the silanes (R 1< O) a R 2< b SiAr c can also be prepared by catalyzed reaction of arylchlorosilanes or arylsilanes with alcohols. An example is the synthesis of trimethoxyphenylsilane (99) by reaction of trichlorophenylsilane or phenylsilane with methanol.

[0196] WO 2012 / 091154 A1 discloses the Lewis acid-catalyzed synthesis of arylalkoxysilanes by reacting arylchlorosilanes with ethers. Bismuth(III) chloride, for example, is used as a catalyst.

[0197] Suitable commercially available chlorosilanes are listed in Tables 19 and 20. Table 19: Cl a R 2< b SiAr CAS No. R 2< a b Ar 98-13-5 - 3 0 Ph 149-74-6 Me 2 1 Ph 1125-27-5 Et 2 1 Ph 790234-74-1 i< Pr 2 1 Ph 17887-41-1 t< This 2 1 Ph 701-35-9 - 3 0 18236-57-2 Me 2 1 20083-38-9 - 3 0 21980-43-8 Me 2 1 18164-08-4 - 3 0 18141-19-0 Me 2 1 1521-07-9 - 3 0 17998-61-7 Me 2 1 17995-31-2 Et 2 1 1521-08-0 - 3 0 17998-62-8 Me 2 1 17950-78-6 Et 2 1 1187327-65-6 - 3 0 136687-79-1 - 3 0 18030-61-0 - 3 0 51840-45-0 Me 2 1 18557-48-7 Et 2 1 Table 20: Cl a SiA 1< Ar 2< CAS No. a Ar 1< Ar 2< 80-10-4 2 Ph Ph 13788-41-5 2 Ph 18414-38-5 2 20160-53-6 2 Ph 20160-45-6 2 18030-58-5 2 7751-39-5 2 Ph 18557-48-7 2 Ph

[0198] In the following, some examples of the syntheses of the silanes (R 1< O) 3 SiAr and (R 1< O) 2 SiAr 1< Ar 2< are presented.

[0199] The bismuth(III) chloride-catalyzed conversion of 2-(trichlorosilyl)naphthalene in tert-butyl methyl ether yields 2-(trimethoxysilyl)naphthalene (100).

[0200] The bismuth(II) chloride-catalyzed conversion of 1-(trichlorosilyl)naphthalene in tert-butyl methyl ether yields 1-(trimethoxysilyl)naphthalene (101).

[0201] The bismuth(III) chloride-catalyzed reaction of 4-(trichlorosilyl)-1,1'-biphenyl in tert-butyl methyl ether yields 4-(trimethoxysilyl)-1,1'-biphenyl (102).

[0202] The bismuth(III) chloride-catalyzed conversion of 9,9-dichloro-9 H -9-silafluorene in tert-butyl methyl ether yields 9,9-dimethoxy-9 H -9-silafluorene (103).

[0203] The bismuth(III) chloride-catalyzed conversion of 4-(dichlorophenylsilyl)-1,1'-biphenyl into tert -Butyl methyl ether provides 4-(dimethoxyphenylsilyl)-1,1'-biphenyl (104).

[0204] JP 2016-34912 A discloses syntheses of (R 1< O) a R 2< b SiAr c by reacting tetraalkoxysilanes with diarylmanganese compounds. By appropriate choice of reaction conditions, either the monoarylsilanes (R 1< O) 3 SiAr or the diarylsilanes (R 1< O) 2 SiAr 2 can be predominantly obtained.

[0205] Aryl radicals bearing one or more halogen atoms are particularly preferred. Such halogen-substituted aryl radicals allow the refractive index n A of the polysiloxanes to be adjusted even more precisely within the desired range.

[0206] A polymerizable dental composition according to the invention contains, in addition to component (A), component (B), a proportion of filler particles of 0.3 to 92 wt.%, based on the total mass of the polymerizable dental composition according to the invention.

[0207] The amount of filler fraction is determined depending on the indication of a dental product. For example, the highest possible filler quantities are used for stable filling composites, for dental compositions for the production of inlays, onlays, or overlays, and for compositions for the production of dental block materials. These compositions typically have filler contents of 80% to 92% by weight, based on the total composition. Flowable dental composites, luting composites, core build-up materials, crown and bridge materials generally have an average filler content of 50 to 80% by weight, based on the total composition, while dental varnishes, dental sealants, or dental adhesives contain fillers in the range of 0.3 to 50% by weight, based on the total composition.

[0208] The filler ranges listed above should always be considered guidelines only, as there are also special polymerizable compositions that, for example, use larger amounts of nanoscale fillers (20 wt%), so that they can be used as fissure sealants with a filler content of 70 wt% based on the total composition. These sealants could also be used as flowable composite materials. Component (B) - organic and / or inorganic fillers.

[0209] Organic filler particles comprise or consist of, for example, one or more compounds selected from the group consisting of polyvinyl acetate and copolymers of polyvinyl acetate with one or more polymerizable compounds, polystyrene, polyethylene, polypropylene, waxes such as polyethylene wax, polybutylene, polybutadiene, copolymers of butadiene and styrene, polyacrylonitrile, resins such as rosin resin or hydrocarbon resins, poly(meth)acrylate esters, ieReaction products of poly(meth)acrylic acid with linear or branched aliphatic, aromatic, or cycloaliphatic alcohols such as methanol, ethanol, propanol, isopropanol, the isomeric butanols and higher homologues of the aforementioned alcohols with up to 22 carbon atoms, cyclohexanol, benzyl alcohol, and the like; polydialkyl maleates such as dibutyl maleate and their copolymers; and silyl-containing polymers such as polyvinylsilanes or copolymers of vinylsilane with one or more of the aforementioned monomers. The organic fillers can be used alone or as mixtures.

[0210] The inorganic fillers can also be used alone or as mixtures. To optimize product properties, the inorganic fillers can be incorporated into the formulations in different grain sizes. The fillers can have a unimodal or polymodal, for example, bimodal, distribution.

[0211] Compact glasses and different silicas in different sizes and states (monodisperse, polydisperse) can be used as inorganic fillers.

[0212] Suitable inorganic components are, for example, amorphous materials based on mixed oxides of SiO 2 , ZrO 2 and / or TiO 2 as well as fillers such as quartz glass ceramics or glass powder, barium silicate glasses, barium fluorosilicate glasses, strontium silicate glasses, strontium borosilicate, Li / Al silicate glasses, barium glasses, calcium silicates, sodium aluminum silicates, fluoroaluminum silicate glasses, oxides of aluminum or silicon, zeolites, apatite, zirconium silicates, sparingly soluble metal salts such as barium sulfate or calcium fluoride as well as X-ray opaque fillers such as ytterbium fluoride.

[0213] For better incorporation into the polymer matrix, the fillers can be organically surface-modified. One example is the surface treatment of the fillers with a silane. Methacryloxypropyltrimethoxysilane is particularly suitable as an adhesion promoter.

[0214] To adjust the rheology, the polymerizable dental compositions can contain different silicas, preferably pyrogenic silicas.

[0215] The polymerizable compositions according to the invention preferably contain nanoscale solid particles. The nanoscale solid particles are particles with an average particle size of not more than 200 nm, preferably not more than 100 nm, and in particular not more than 70 nm. The nanoscale inorganic solid particles are preferably those of oxides, sulfides, selenides, and tellurides of metals, mixed metals, and mixtures thereof. Particular preference is given to nanoscale particles of SiO 2 , TiO 2 , ZrO 2 , ZnO, SnO 2 , and Al 2 O 3 and mixtures thereof. The nanoscale solid particles are produced in a known manner, e.g., by flame pyrolysis, plasma processes, gas-phase condensation, colloid techniques, precipitation processes, sol-gel processes, etc.

[0216] In a preferred embodiment, the nanoscale particles are present in non-agglomerated and / or non-aggregated form, for example dispersed in a medium, preferably in monodisperse form.

[0217] To ensure good integration of the nanoparticles into the polymer matrix of a polymerizable dental composition according to the invention, the surfaces of the nanoparticles are also organically surface-modified, i.e., their surfaces contain organic structural elements. One example is the surface treatment of the fillers with a silane. Methacryloxypropyltrimethoxysilane is particularly suitable as an adhesion promoter here.

[0218] In a further preferred embodiment, the nanoscale particles are thus non-agglomerated and / or non-aggregated, organically surface-modified nanoparticles with an average particle size of less than 200 nm, preferably less than 100 nm, particularly preferably less than 70 nm, which in turn are preferably silanized.

[0219] Commercially available nanoscale, non-agglomerated and non-aggregated silica sols that can be used according to the invention are available, for example, under the name "NALCO COLLOIDAL SILICAS" (Nalco Chemical Co.), "Ludox colloidal silica" (Grace) or "Highlink OG" (Clariant).

[0220] In a preferred embodiment, the filler portion of a polymerizable dental composition according to the invention comprises a mixture of a first filler (b1) in the form of non-agglomerated, non-aggregated, organically surface-modified nanoparticles with an average particle size of less than 200 nm and a second filler (b2) in the form of macroscopic microparticles with an average particle size in the range of 0.4 µm to 10 µm. The combination of (b1) nanoparticles and (b2) microparticles in a polymerizable dental composition according to the invention achieves complete and uniform volume filling of the composite material. This reduces both the shrinkage of the polymerizable composition during curing of the polymer matrix and the sensitivity of the composition according to the invention to abrasion.

[0221] The proportion of organically surface-modified nanoparticles in a preferred polymerizable dental composition according to the invention with an average particle size of less than 200 nm is greater than 1 wt. %, preferably greater than 2 wt. % and particularly preferably greater than 3 wt. %. Our own investigations have shown that with a content of 1 wt. % or less of non-agglomerated and / or non-aggregated, organically surface-modified nanoparticles with an average particle size of less than 200 nm, the radically curable dental composition is no longer sufficiently abrasion-resistant in individual cases. This is probably due, among other things, to the fact that with a content of 1 wt. % or less of the said nanoparticles, the areas between the microparticles with an average particle size of 0.4 µm to 10 µm are no longer sufficiently filled. On the other hand, it has been shown that with a content of more than 20 wt.-% of non-agglomerated and / or aggregated, organically surface-modified nanoparticles with an average particle size of less than 200 nm, the composition's processability is no longer sufficient. Due to the high solids content, its viscosity becomes too high.

[0222] The materials for the nanoparticles to be used according to the invention are preferably oxides or mixed oxides and are 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, aluminum, and mixtures thereof. The preferred oxide nanoparticles are, as explained, non-agglomerated and / or non-aggregated and organically surface-treated.

[0223] Within a polymerizable dental composition according to the invention, the microparticles effect a largely uniform filling of the volume, wherein the remaining voids between the microparticles are at least partially filled by the above-described nanoparticles (component (b1)). In the context of the present invention, microparticles are understood to mean particles with an average particle size of 400 nm to 10 µm. The average particle size is preferably less than 5 µm. It has been shown that the volume filling of the polymerizable dental composition achievable with the microparticles is more complete and uniform the smaller the microparticles are.

[0224] The microparticles of component (b2) can have a monomodal or polymodal, for example, a bimodal, particle size distribution. Microparticles with a bimodal or multimodal particle size distribution are preferred according to the invention, since they achieve a more complete volume filling than with the general use of microparticles with a monomodal particle size distribution. In the case of a bimodal or multimodal particle size distribution, the particles of the larger-sized fractions cause a rough filling of the volume, while the particles of the smaller-sized fraction will, as far as possible, fill the areas between the particles of the larger-sized fractions. The remaining voids are filled with nanoparticles as described above.

[0225] Thus, in a polymerizable dental composition according to the invention, a component (b2) is very particularly preferably used which contains two or more fractions of microparticles, wherein the mean particle sizes of the fractions differ.

[0226] Component (b2) preferably contains at least two microparticle fractions, the average particle sizes of which differ from one another by at least 0.5 µm, preferably by at least 0.7 µm. In some embodiments, the difference between the average particle sizes of the microparticle fractions is at least 1.0 µm.

[0227] The microparticles of different fractions may consist of the same or different materials; there may also be several fractions of microparticles whose average particle size is approximately the same or lies within a certain range, whereby the materials of the particles differ between the fractions.

[0228] Particularly preferably, a polymerizable dental composition according to the invention comprises a component (b2) which comprises one or more first microparticle fractions, each having an average particle size in the range from 1 µm to 10 µm, preferably 1 µm to 5 µm, and one or more second microparticle fractions, each having an average particle size in the range from > 0.4 µm to < 1 µm (ie greater than 0.4 µm but less than 1 µm), preferably 0.5 µm to 0.8 µm.

[0229] Preferably, the ratio of the total mass of the first microparticle fractions to the total mass of the second microparticle fractions is in the range from 1:1 to 12:1, preferably in the range from 1.5:1 to 8:1.

[0230] Preferably, the ratio of the average grain size of the or a first microparticle fraction to the average grain size of the or a second microparticle fraction of component (b2) is in the range from 1.5:1 to 10:1, preferably in the range from 2:1 to 5:1.

[0231] In a particularly preferred polymerizable dental composition according to the invention, component (b2) comprises one or more first microparticle fractions, each having an average particle size in the range from 1 µm to 10 µm, preferably 1 µm to 5 µm, and one or more second microparticle fractions, each having an average particle size in the range from > 0.4 µm to < 1 µm, preferably 0.5 µm to 0.8 µm; wherein the ratio of the total mass of the first microparticle fractions to the total mass of the second microparticle fractions is in the range from 1:1 to 12:1, preferably 1.5:1 to 8:1 and / or the ratio of the average grain size of the or a first microparticle fraction to the average grain size of the or a second microparticle fraction of component (b2) is in the range from 1.5:1 to 10:1, preferably 2:1 to 5:1.

[0232] In a particularly preferred polymerizable dental composition according to the invention, at least a portion of the microparticles of component (b2) are formed by organically surface-modified particles, preferably silanized particles, and / or at least a portion of the microparticles of component (b2) are formed by dental glass particles; preferably, at least a portion of the microparticles of component (b2) are organically surface-modified dental glass particles, preferably silanized dental glass particles.

[0233] In these cases, component (b2) is preferably characterized by a bi- or multimodal particle size distribution, in particular a bi- or multimodal particle size distribution with the preferred features described above.

[0234] In addition to components (b1) and (b2), the polymerizable dental composition may additionally comprise further fillers as component (b3) in addition to the mixture of filler particles.

[0235] For example, reinforcing filler materials such as glass fibers, polyamide, or carbon fibers can be used. A polymerizable dental composition according to the invention can also contain finely divided chip or bead polymers, wherein the bead polymers can be homopolymers or copolymers of organic curable monomers.

[0236] In a particularly preferred embodiment, a polymerizable dental composition according to the invention contains a radiopaque filler. Most preferably, the composition according to the invention contains nanoscale YbF 3 and / or BaSO 4 .

[0237] Our own investigations have shown that a refractive index n A of the total amount of polymerizable monomers (A) and (D) in the range of 1.45 to 1.55 very often leads to very good translucency values, since the refractive indices of the one, two, three, or more than three fillers that make up the total amount (B) of fillers in the curable dental material can be relatively easily matched to such a refractive index n A. This good matching means that during light-induced polymerization of polymerizable monomers in the curable dental material, the light used achieves a high penetration depth and thus causes uniform polymerization. This leads to a high-quality, cured dental material with very good mechanical properties.

[0238] If the refractive index n A is less than 1.45 or greater than 1.55, the aforementioned adjustment becomes more complex in many cases (especially with a refractive index less than 1.45), and the light penetration depth is only acceptable in a few cases or hardly acceptable at all (since particularly intense light scattering is to be expected in most cases). This increases the risk of unpolymerized, polymerizable monomers escaping from a (partially) cured dental material and migrating into the oral cavity. In addition, such (partially) cured dental materials have significantly reduced strength. Such curable dental materials must then be laboriously applied in very thin layers, and each layer must be cured individually to minimize the disadvantages mentioned above.If the refractive index is greater than 1.45 but less than 1.48, a sufficiently good match is achieved in most cases, resulting in a sufficiently good light penetration depth. The application of such a curable dental material (and subsequent curing) can then be carried out without great effort. If the refractive index is in the range of 1.48 to 1.55, very good results are regularly achieved with the conventional use of radiopaque dental glasses.

[0239] Particularly preferred is a curable dental material according to the invention (as described above, preferably as defined above as preferred), wherein the total amount of the particulate fillers (B) has a refractive index n B in the range from 1.50 to 1.55.

[0240] Particularly preferred is a curable dental material according to the invention (as described above, preferably as defined above as preferred), wherein the absolute value of the difference |n A - n B | between the refractive index of the total amount of polymerizable monomers ((A) and (D)) n A and the refractive index of the total amount of fillers n B is less than 0.05, preferably less than 0.03, particularly preferably less than 0.02, and most preferably less than 0.01. Such dental materials particularly exhibit the described high translucency and, associated with this, good curing properties.

[0241] During polymerization, the density of the resin matrix increases due to the shrinkage that occurs. This increase in density also leads to an increase in the refractive index during polymerization. In contrast, the refractive index of the fillers does not change during polymerization. This can lead to a decrease in translucency and curing properties during polymerization. The compositions according to the invention are characterized by very low shrinkage, so that only a slight change in density and refractive index occurs during polymerization. Thus, translucency and curing properties also change only slightly during polymerization, ensuring reliable curing.

[0242] Therefore, a curable dental material according to the invention (as described above, preferably as defined above as preferred) is preferred, in which the difference n P - n A of the refractive index n P of the polymerized resin matrix (from (A) and (D)) and the refractive index n A of the total amount of the polymerizable monomers (A) and (D) before polymerization is less than 0.03 and preferably less than 0.02.

[0243] Qualitative and quantitative characterization of the filler particles: The steps described below in the qualitative and quantitative characterization of the filler particles (in particular nanoscale filler particles) are well known to the person skilled in the art and are comprehensively described in the literature.

[0244] Resin / filler separation: In a first step, 1 g of a polymerizable dental composition according to the invention (hereinafter also referred to as composite material) is suspended in 10 ml of acetone, and the resulting suspension is then centrifuged for 10 minutes at 5000 rpm. The supernatant (hereinafter referred to as the resin phase) is decanted into a collecting tube, and the residue is suspended in 5 ml of acetone. Centrifugation is continued for 10 minutes at 5000 rpm, decanted, and the residue is suspended again in 5 ml of acetone. The centrifugation, decanting, and suspension steps are repeated two more times under identical conditions. The total amount of residue separated from the resin phases is dried, and the total amount of resin phases is freed of acetone using a rotary evaporator.

[0245] After completing the first step, the dried total residue regularly comprises filler particles with a particle size of approximately 400 nm or greater (hereinafter referred to as macroscopic filler particles). The total resin phase freed from acetone (hereinafter referred to as resin fraction) regularly comprises, in addition to polymerizable monomers, filler particles with a particle size of approximately 400 nm or, in particular, less than 400 nm (hereinafter referred to as nanoscale particles). This process thus ensures that the dental composite material is completely separated by centrifugation into (i) a fraction of macroscopic filler particles, with particular reference to dental glasses in the size range from greater than 400 nm up to the high micrometer range, and (ii) a resin fraction comprising nanoscale particles.

[0246] The mean particle size d 50 of the macroscopic filler particles of the filler component (b2) of a composition according to the invention to be used according to the invention is determined by means of light scattering (laser diffraction), preferably with a Beckman Coulter LS 13320 particle size measuring device.

[0247] The nanoscale particles which are present in the resin portion can, for example, be non-aggregated and / or non-agglomerated, for example X-ray opaque particles, for example YbF 3 or BaSO 4 with particle sizes in a range of approximately 3 nm to 200 nm, as well as non-X-ray opaque silicas which, for example, are present as pyrogenic silicas in the form of aggregates and / or agglomerates with a particle size in a range of approximately 150 nm to approximately 300 nm or also silicas which are synthesized by the sol-gel process (or from water glass) and which are also non-aggregated and / or non-agglomerated and have particle sizes in a range of approximately 3 nm to 200 nm.

[0248] The total mass fraction of inorganic particles in the resin portion is determined gravimetrically by differential weighing after incineration of a corresponding resin portion.

[0249] TEM in combination with EELS: In a second step, the filler particles in the resin portion are subjected to qualitative and quantitative characterization. TEM (transmission electron microscopy) is used in conjunction with EELS (electron energy loss spectroscopy).

[0250] The particle sizes and number of individual particles are determined using TEM; elemental determination of individual particles is carried out using EELS.

[0251] To perform combined TEM / EELS characterization, the concentration of nanoscale particles in the resin portion is initially reduced by dilution with polymerizable resin. This largely eliminates the possibility of an "overlay" of nanoscale particles being observed in the subsequent images. Such an "overlay" would distort the particle characterization. Our own investigations have shown that the optimal particle concentration (i.e., the volume fraction of filler particles) for such investigations is 1 vol.%, based on the total mass of the diluted sample.

[0252] In a second step, the diluted resin fractions obtained by dilution with polymerizable resin are cured to produce rods. Several 300 nm thick ultrathin sections are then cut from these rods using an ultradiamond knife (e.g., an ULTRCAT UCT ultramicrotome, LEICA, Wetzlar). The ultrathin sections are transferred to copper TEM grids for stabilization. This results in thin-section specimens. These thin-section specimens are then examined in a TEM using bright-field imaging at an accelerating voltage of 120 kV.

[0253] A TEM examination of the thin film preparations described above allows to distinguish non-aggregated and non-agglomerated nanoscale particles from aggregated and / or agglomerated particles (e.g. silicas such as Aerosilene) (for identification of the chemical composition see the following explanations).

[0254] If high-resolution images are to be examined, ultra-thin sections with layer thicknesses of less than 100 nm can be produced and examined.

[0255] In a third step, the filler particles in the ultrathin sections or thin section preparations are chemically characterized using EELS point analyses so that the chemical composition of individual particles becomes known (for the determination of the surface modification of particles, see the following points).

[0256] The volume or weight-related proportions of (or possibly several) particle fractions are determined from a TEM image in a fourth step as follows: The image section of a TEM image viewed under the microscope represents an area whose edge lengths a and b are determined using the legend. Multiplied by the thickness c of the ultra-thin section, this results in a total volume V total for the area viewed in the TEM. This total volume V total is the sum of the resin volume V resin and the volume of all particles V particles within this volume (the volume of all particles may comprise several groups of particles, e.g. sorted according to different criteria such as size). V total = a * b * c = V resin + V particles .

[0257] The volume of individual particles (and thus the volume of all particles in the volume under consideration) can be calculated using the spherical volume of the individual particles. For this purpose, the diameter or radius of a corresponding particle is determined in the TEM image. The resulting spherical volume, multiplied by the density of the corresponding material from which the particle is made (material identifiable using EELS), yields the mass of the particle. The resin volume, obtained from the total volume minus the particle volume, multiplied by the resin density, yields the resin mass. The resin density is largely determined from the density of the resin used for dilution and, if applicable, the density of the diluted resin portion (the latter can be neglected when calculating the resin density if the proportion of diluted resin is negligible).The proportion of particles (or a group of particles) in weight percent is calculated as m P * 100 / (m particles + m resin), where m P is the mass of the particle fraction in question in the volume under consideration, m particles is the mass of all particles in the volume under consideration, and m resin is the mass of the resin in the volume under consideration. The dilution factor is taken into account accordingly in the final calculation of the weight proportion of the particle fraction under consideration.

[0258] Determination of organic surface modifications: Preliminary consideration: Many known radiopaque filler materials (such as ytterbium fluoride or barium sulfate) have the disadvantage that they are difficult to incorporate into the matrix (resin matrix) of polymerizable monomers (the so-called organic resin phase) because they do not form sufficient chemical bonds (bonding options) with the hydrophobic groups of the medium. Glass-like fillers, for example, can be excellently incorporated into the resin matrix of dental composite materials by silanization via Si-OH groups. In the case of ytterbium fluoride and barium sulfate, such groups are not present on the surfaces; thus, they cannot be silanized and lead to insufficient physical and chemical resistance in a cured dental material (see WO 2005 / 011621 A1, page 2 bottom).

[0259] The radiopaque nanoscale particles used in a curable dental material according to the invention will therefore not have any silanes on their surfaces. Instead, the linkage occurs via nitrogen, oxygen, sulfur, and / or phosphorus atoms (see again WO 2005 / 011621 A1 and our comments above).

[0260] Separation of polymerizable monomers from nanoscale particles: "Cross-flow" process: The separation of polymerizable monomers from nanoscale particles is carried out, for example, in a "cross-flow" process known to those skilled in the art using ultrafiltration membranes.

[0261] In this process, a resin component containing nanoscale particles, polymerizable monomers and, if necessary, a suitable diluent is pumped from a container into a circuit of specific membranes by means of a pump, whereby the polymerizable monomers pass through the pores of the membranes and are separated as filtrate, while the nanoscale particles remain within the circuit (and thus in the container).

[0262] For this separation process, the "Vivaflow 50" system from Sartorius Stedim Biotech GmbH, Göttingen, Germany, is suitable. The pump drive (7554-95) and pump head are from the "Masterflex L / S" series from Cole-Palmer Instrument Co., Illinois, USA. The pump is set to 2.5 bar during filtration. Two 50,000 MWCO (PES) separation membranes are connected in series. The MWCO (Molecular Weight Cut-Off) indicates the cut-off value, i.e., the size of the molecules that can still efficiently pass through the membrane. This value is expressed in Daltons. The resulting fractions are then analyzed as described below.

[0263] Sedimentation field flow fractionation (SF3): Even better than the cross-flow process is the implementation of sedimentation field flow fractionation (SF3). This method allows different particle fractions to be separated from each other and also from the resin content. The prerequisite for this is that the different particle fractions differ sufficiently in size and / or density.

[0264] Appropriate devices containing the necessary separation column are available from Postnova Analytics GmbH, Landsberg, Germany. The module containing the separation column is called the CF2000 Centrifugal FFF and is complemented by the additional modules PN7140 (Eluent Organizer), PN1130 (Isocratic Pump), PN5300 (Autosampler), PN3621 MALS (21-Multi-Angle Light Scattering Detector), and PN8050 (Fraction Collector). In this combination, the Centrifugal FFF system allows not only the analytical but also the preparative separation of particle fractions. The resulting fractions are then analyzed as described below.

[0265] Characterization of the surface modification: A sample prepared as above and subsequently freed from solvents, containing nanoscale particles in the form of a powder, is then investigated by spectroscopic methods (e.g. by 1< H-NMR, 13< C-NMR, 15< N-NMR, 29< Si-NMR and 31< P-NMR as well as IR).

[0266] Signals that cannot be assigned to a silane, for example the gamma-methacryloxypropylsilyl residue, are assigned to organic surface modifications that are not based on silanes, e.g. surface modifications using organic compounds on surfaces of ytterbium fluoride or barium sulfate particles.

[0267] The proportions of organically surface-modified particles or non-organically surface-modified particles can also be determined by evaluating the intensities of corresponding vibrational bands in the IR spectrum. Reference vibrational bands (reference curves) of organically surface-modified or non-organically surface-modified particles with the corresponding chemical compositions are typically used for this purpose.

[0268] Characterization by Image Analysis and Raman Spectroscopy: Those skilled in the art are familiar with additional methods or combinations of methods that allow for the qualitative and quantitative characterization of filler particles. In this regard, reference is made, for example, to the article "Chemical Identity of Individual Particles" by Deborah Huck-Jones and Renate Hessemann in "Nachrichten aus der Chemie," Volume 62, September 2014, pages 886 and 887. The combination of image analysis and Raman spectroscopy disclosed therein is also generally suitable for characterizing filler particles within the scope of the present invention. This applies in particular to samples obtained after the resin-filler separation described above. A suitable image analysis method is, for example, the TEM analysis described above. Component (C) - Initiators and / or catalysts and / or activators for polymerization

[0269] A polymerizable dental composition according to the invention is preferably radically light-curable and / or radically chemically curable or cationically curable.

[0270] A polymerizable dental composition according to the invention is preferred, wherein component (C) comprises or consists of one or more light-curing initiators and / or one or more initiators for chemical or cationic polymerization.

[0271] Preferred polymerizable dental compositions according to the invention are light-curable (photocurable) and comprise light-curing initiators. Examples of light-curing initiators include substances that only have a photosensitizing effect, as well as combinations of sensitizer and accelerator.

[0272] Examples of photosensitizers include alpha-diketones, benzoin alkyl ethers, thioxanthones, benzophenones, acylphosphine oxides, acylgermanium compounds, acetophenones, ketals, titanocenes, sensitizing dyes, etc. The sensitizers can be used alone or in combination. Specific examples of substances from the different classes can be found, for example, in DE 10 2006 019 092 A1 or DE 39 41 629 C2.

[0273] Examples of accelerators used in conjunction with sensitizers include tertiary amines, secondary amines, barbituric acids, tin compounds, aldehydes, and sulfur compounds. Specific examples of substances from the different classes can be found in DE 10 2006 019 092 A1 or DE 39 41 629 C2.

[0274] Further suitable initiators and initiator combinations are described in DE 601 16 142 T2.

[0275] The photoinitiators which can be used in the context of the present invention are characterized in that they can effect the curing of a polymerizable dental composition according to the invention by absorbing light in the wavelength range from 300 nm to 700 nm, preferably from 350 nm to 600 nm and particularly preferably from 380 nm to 500 nm, optionally in combination with one or more coinitiators.

[0276] The absorption maximum of camphorquinone (CQ) is approximately 470 nm, which is in the blue light range. Camphorquinone (CQ) is a PI 2 initiator and is frequently used in conjunction with a coinitiator.

[0277] Preferably, a composite material according to the invention contains the combination of an alpha-diketone and an aromatic tertiary amine, preferably the combination of camphorquinone (CQ) and ethyl- p - N,N -dimethylaminobenzoate (DABE).

[0278] Also preferred is the further combination of the "alpha-diketone / aromatic tertiary amine" system with a phosphine oxide, in particular with phenyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide and / or 2,4,6-trimethylbenzoyldiphenylphosphine oxide. With regard to the structures of suitable phosphine oxides for use in a radically curable dental composition according to the invention, reference is made to the documents DE 38 01 511 C2, DE 10 2006 050 153 A1, EP 0 184 095 B1, DE 42 31 579 C2, EP 0 366 977 B1, US 7,081,485 B2, DE 32 36 026 A1, US 2007 / 0027229 A1, EP 0 262 629 B1, EP 0 073 413, US 7,148,382 B2, US 5,761,169, DE 197 08 294 A1, EP 0 057 474, EP 0 047 902 A, EP 0 007 508, DE 600 29 481 T2, EP 0 980 682 B1, EP 0 948 955 B1, EP 1 236 459 B1 and EP 0 173 567 A2 referenced.

[0279] The phosphine oxides specified in these publications are particularly suitable alone or in combination with the "alpha-diketone / amine" system as a photopolymerization initiator system in a polymerizable dental composition according to the invention.

[0280] EP 1 905 415 A1 describes polymerizable dental compositions with acylgermanium compounds as initiators, which are also suitable for the polymerizable dental compositions according to the invention.

[0281] Alternatively, borate salts, such as those described in US 4,772,530, US 4,954,414, US 4,874,450, US 5,055,372 and US 5,057,393, can also be used as photoinitiators.

[0282] Other suitable photoinitiators are described in J.-P. Fouassier, Photoinitiation, Photopolymerization and Photocuring, Hanser Publishers, Munich, Vienna, New York 1995 and in J.F. Rabek (ed.), Radiation Curing in Polymer Science and Technology, Vol. II, Elsevier Applied Science, London, New York 1993.

[0283] Various initiators for chemical curing are known to those skilled in the art. Reference is made to EP 1 720 506 as an example. Initiators for chemical curing are also described in the aforementioned publications DE 10 2006 019 092 and DE 39 41 629.

[0284] Preferred initiators for chemical curing are benzoyl peroxide, lauroyl peroxide, especially dibenzoyl peroxide in combination with amines such as N,N- Dimethyl- p -toluidine, N,N- Dihydroxyethyl- p -toluidine and structurally related amines.

[0285] The peroxides and amines are distributed between two different components of the dental material. When the amine-containing component (the so-called base paste) is mixed with the peroxide-containing component (the so-called initiator or catalyst paste), polymerization is initiated by the reaction of the amine and peroxide (redox reaction).

[0286] In addition to peroxides and amines, hydroperoxides can also be used in combination with thioureas.

[0287] Dual-curing systems include a combination of photoinitiators and chemical curing initiators.

[0288] For example, the base paste can additionally contain a photoinitiator, so that the base paste can be used either alone as a light-curing dental composition or together with the initiator paste as a light- and self-curing dental composition.

[0289] In addition to the oxidatively active organic peroxide compounds, barbituric acids or barbituric acid derivatives as well as malonyl sulfamides can also be used as redox systems.

[0290] Among the barbituric acid systems, the so-called "Bredereck systems" are of great importance. Examples of suitable "Bredereck systems" and references to the corresponding patent literature can be found in EP 1 839 640, DE 1495520, WO 02 / 092021, and WO 02 / 092023.

[0291] Instead of barbituric acids, their salts can also be used. Examples can be found in the following documents: EP 1 872 767, EP 2 070 506, EP 1 881 010, DE 10 2007 050 763, US 6,288,138, DE 11 2006 001 049, US 7,214,726, and EP 2 070 935.

[0292] Suitable malonyl sulfamides are described in EP 0 059 451. Preferred compounds are 2,6-dimethyl-4-isobutylmalonyl sulfamide, 2,6-diisobutyl-4-propylmalonyl sulfamide, 2,6-dibutyl-4-propylmalonyl sulfamide, 2,6-dimethyl-4-ethylmalonyl sulfamide and 2,6-diocytyl-4-isobutylmalonyl sulfamide.

[0293] Furthermore, sulfur compounds in the oxidation state +2 or +4 such as sodium benzenesulfinate or sodium paratoluenesulfinate can be used.

[0294] To accelerate curing, polymerization can be carried out in the presence of activators in the form of heavy metal compounds such as Ce, Fe, Cu, Mn, Co, Sn, or Zn, with copper compounds being particularly preferred. The heavy metal compounds are preferably used in the form of soluble organic compounds. Preferred copper compounds are copper benzoate, copper acetate, copper ethylhexanoate, copper di(methacrylate), copper acetylacetonate, and copper naphthenate.

[0295] Cationic polymerization can be photoinduced or thermal. Cationic polymerization is preferably photoinduced, as this application achieves a higher crosslinking conversion, as thermal polymerization can lead to a significant degree of side reactions. Cationic ring-opening polymerization of epoxides is further preferred. In this process, the epoxy-containing monomer reacts with the protic acid formed from the decomposition of a photoinitiator to form an open-chain intermediate, which, as a reactive cation, attacks another epoxide, opens it, and continues the polymerization. The driving force of ring-opening polymerization is the gain in ring strain energy, which is further increased in the bifunctional monomers used due to the greater ring distortion. Cationic photoinitiators include, for example, ionic iodonium or sulfonium derivatives.Examples of commercially available cationic photoinitiators are (4-phenylthiophenyl)diphenylsulfonium triflate, [4(2-hydroxytetradecyl)oxy]phenyliodonium hexafluoroantimonate, or p-octyloxyphenylphenyliodonium hexafluoroantimonate. Irradiation of, for example, an onium salt causes the onium-benzene bond to be cleaved homolytically, forming a phenyl radical and a radical cation, the latter of which reacts with RH to form a radical, the onium benzene, and an acid. The mechanisms for other phenacyl-based photoinitiation systems are analogous.

[0296] A preferred system for cationic crosslinking comprises three components: camphorquinone, which is also used for the classic radical polymerization of dental materials, as a light-absorbing agent, an electron donor such as an amine, for example the ethyl- pN,N-dimethylaminobenzoate (DABE), as well as an iodonium salt. The camphorquinone is excited and reacts with the amine, which converts the iodonium salt into an acidic cation in a redox process. This initiates the ring-opening process of the oxiranes.

[0297] A wealth of initiator systems for cationic ring-opening polymerization, especially for use in dental composite materials, are described in the patent literature. Suitable systems for the dental composite materials according to the invention can be found in the publications EP 2 133 064 A1, titled "Initiator system containing a diarylalkylamine derivative, hardenable composition and use thereof," EP 0 897 710 A2, titled "Light-induced cationically curing compositions and their use," WO 2005 / 051332 A1, titled "Photoinitiator systems with anthracene-based electron donors for curing cationically polymerizable resins," US Pat. No. 9,770,528 B2, titled "Biomaterial compositions," and the published patent application DE 196 48 283 A1, titled "Polymerizable compositions based on epoxides."

[0298] Experts will also find numerous other suitable initiators in the scientific literature. In this regard, we refer to the publication "Photoinduced Electron Transfer Reactions for Macromolecular Synthesis" by SD Silab, S. Doran, and Y. Yagci, Chem. Rev. 116, 10212–10275, 2016. Component (D) - organic, polymerizable monomers which are not polysiloxanes according to the invention, preferably for reaction with the polysiloxanes according to the invention

[0299] The polymerizable monomers are monomers which - in the case of radical polymerization - are preferably substances containing one, two or more ethylenic groups, such as, for example, but not limited to, the (meth)acrylate monomers commonly used in dental chemistry.

[0300] The (meth)acrylate monomers can be monofunctional or polyfunctional.

[0301] Preferably used monofunctional (meth)acrylate monomers are the esters of (meth)acrylic acid with alkyl groups of 1 to 12 C atoms and esters of (meth)acrylic acid containing aromatic groups of 6 to 12 C atoms, wherein the alkyl groups and aromatic groups forming the esters may contain substituents such as hydroxyl groups and ether bonds.

[0302] A large number of other compounds are mentioned in the patent literature (for example in DE 39 41 629 A1), all of which are esters of acrylic or methacrylic acid and are suitable for use in a curable mixture.

[0303] The polymerizable monomers can also be hydroxyl compounds containing at least one ethylenic double bond. Preferably, the hydroxyl compounds of (meth)acrylates commonly used in dental chemistry can be used.

[0304] Examples of polyfunctional (meth)acrylate monomers that can also be mentioned are di(meth)acrylates of alkylene glycol having 2 to 20 C atoms, di(meth)acrylates of oligomers of alkylene glycol, polyalkylene glycol di(meth)acrylate, di(meth)acrylates of bisphenol A or of the diglycidyl ether of bisphenol A.

[0305] Particularly preferred are also polymerizable compounds which are based on a central polyalicyclic structural element, such as, for example, 3(4), 8(9)-bis((meth)acryloyloxymethyl)tricyclo[5.2.1.0 2,6< ]decane, alkoxylated 3(4), 8(9)-bis((meth)acryloyloxymethyl)tricyclo[5.2.1.0 2,6< ]decane, 2,3-bis((meth)acryloyloxymethyl)bicyclo[2.2.1]heptane, alkoxylated 2,3-bis((meth)acryloyloxymethyl)bicyclo[2.2.1]heptane, 1,3,5-tri(meth)acryloyloxytricyclo[3.3.1.1 3,7< ]decane, alkoxylated tri(meth)acryloyloxytricyclo-[3.3.1.1 3,7< ]decane and (meth)acrylic acid esters of tricyclo[5.2.1.0 2,6< ]decane-3(4),8(9)-dimethanol, alkoxylated tricyclo-[5.2.1.0 2,6< ]decane-3(4),8(9)-dimethanol, bicyclo[2.2.1]heptane-2,3-dimethanol, alkoxylated bicyclo[2.2.1]heptane-2,3-dimethanol, 1,3,5-adamantanetriol, alkoxylated 1,3,5-adamantanetriol, wherein urethane, urea, amide, allophanate, acylurea or biuret groups are arranged between the polyalicyclic structural element and the (meth)acrylic acid esters.

[0306] Information on the preparation of these substituted (meth)acrylic acid esters can be found in patent applications EP 11 183 333, EP 11 183 328, EP 11 183 345, EP 11 183 338, EP 11 183 342 and EP 11 188 086 and in the documents cited in these documents.

[0307] Also preferred are urethane (meth)acrylate esters, reaction products of 2 moles of a (meth)acrylate with a hydroxyl group and one mole of a diisocyanate.

[0308] Weiter bevorzugt sind die klassischen Dentalmonomeren Ethylenglycoldi(meth)acrylat, Diethylenglycoldi(meth)acrylat, 1,6-Hexandiol-di(meth)acrylat (HEDMA), Triethylenglycoldi(meth)acrylat (TEGDMA), 1,12-Dodecandioldi(meth)acrylat, Bisphenol-A-di(meth)acrylat, alkoxyliertes Bisphenol-A-di(meth)acrylat, Bisphenol-B-di(meth)acrylat, alkoxyliertes Bisphenol-B-di(meth)acrylat, Bisphenol-C-di(meth)acrylat, alkoxyliertes Bisphenol-C-di(meth)acrylat, Bisphenol-F-di(meth)acrylat, alkoxyliertes Bisphenol-F-di(meth)acrylat, Polyethylenglycoldi(meth)acrylat, 7,7,9-Trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecan-1,16-dioxydi(meth)acrylat (UDMA), Butandioldi(meth)acrylat, Tetraethylenglycoldi(meth)acrylat, Neopentylglycol-di(meth)acrylat, 2-Hydroxypropyl-1,3-di(meth)acrylat, 3-Hydroxypropyl-1,2-di(meth)acrylat, Pentaerythritoldi(meth)acrylat, Di(meth)acrylaten des Dihydroxy-methyltricyclo[5.2.1.0 2,6< ]decans, 2-Hydroxyethyl(meth)acrylat, 2-Hydroxypropyl-(meth)acrylat,3-Hydroxypropyl(meth)acrylat, 1,2-Dihydroxypropyl(meth)acrylat, 1,3-Dihydroxypropyl(meth)acrylat, 2,3-Dihydroxypropyl(meth)acrylat, 2,2-Bis[4-[3-(meth)acryloyloxy-2-hydroxypropoxy]phenyl]propan (Bis-GMA), Trimethylol-propantri(meth)acrylat, Trimethylolethantri(meth)acrylat, Pentaerythritoltri(meth)-acrylat, Trimethylolmethantri(meth)acrylat, Pentaerythritoltetra(meth)acrylat, Ditrimethylolpropantetra(meth)acrylat, Pentaerythritolhexa(meth)acrylat, Butylenglycoldi(meth)acrylat, Propylenglycoldi(meth)acrylat, Nonandioldi(meth)-acrylat, Decandioldi(meth)acrylat, Glycerolmono(meth)acrylat, Glycerol-di(meth)acrylat, Trimethylolpropanmono(meth)acrylat, Trimethylolpropan-di(meth)acrylat, Sorbitolmono-, di-, tri-, tetra- oder penta(meth)acrylat, Methyl(meth)acrylat, Ethyl(meth)acrylat, Propyl(meth)acrylat, Butyl(meth)acrylat, Hexyl(meth)acrylat, Tetrahydrofurfuryl(meth)acrylat, Lauryl(meth)acrylat, Cyclohexyl(meth)- acrylat, Allyl(meth)acrylat, Glycidyl(meth)acrylat,2-Ethoxyethyl(meth)acrylat, Methoxypolyethylenglycol(meth)acrylat, Isobornyl-(meth)acrylat, 2-(N, N-Dimethylamino)ethyl(meth)acrylat, N-Methylol(meth)-acrylamid, Diaceton(meth)acrylamide, 2,2-Bis[4-(meth)acryloyloxyphenyl]-propan, 2,2-Bis[4-(meth)acryloyloxyethoxyphenyl]propan, 2,2-Bis[4-(meth)-acryloyloxydiethoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxytriethoxyphenyl]-propan 2,2-Bis[4-(meth)acryloyloxytetraethoxyphenyl]propan, 2,2-Bis[4-(meth)-acryloyloxypentaethoxyphenyl]-propan, 2,2-Bis[4-(meth)acryloyloxydipropoxy-phenyl]propan, 2,2-Bis[4-(meth)acryloyloxyethoxyphenyl]-2-[4-(meth)acryloyl-oxydiethoxyphenyl]propan, 2-[4-(Meth)acryloyloxydiethoxyphenyl]-2-[4-(meth)-acryloyloxytriethoxyphenyl]propan, 2-[4-(Meth)acryloyloxdipropoxyphenyl]-2-[4-(meth)acryloyloxytriethoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxyisopropoxy phenyl]propan, Hydroxypivalinsäureneopentylglycoldi(meth)acrylat, Aceto-acetoxyethyl(meth)acrylat, Polypropylenglycoldi(meth)acrylat, Glycerolalkoxylatdimethacrylat,Neopentylglycol(meth)acrylat, N,N-(1,2-Dihydroxyethylen)bis-acrylamid, 2,2-Bis[4-(meth)acryloyloxypentaethoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxypolyethoxyphenyl]-propan, Diethylenglycoldi(meth)acrylat, Dipentaerythritoltetra(meth)acrylat, Dipentaerythritolhexa(meth)acrylat, N,N-(2,2,4-Trimethylhexamethylen)bis[2-(aminocarboxy)propan-1,3-diol]-tetra(meth)-acrylat, das Kondensationsprodukt von 3,(4)-(Meth)acryloxymethyl-8,(9)-hydroxymethyltricyclo[5.2.1.0 2,6< ]decan mit Dicarbonsäuren, 2-Ethylhexyl-(meth)acrylat, Tridecyl(meth)acrylat, Stearyl(meth)acrylat, Benzyl(meth)acrylat, Methoxydiethylenglycol(meth)acrylat, Dicyclopentenyl(meth)acrylat, Phenyl-(meth)acrylat, Pentaerythritolmono(meth)acrylat, Dipentaerythritolmono(meth)-acrylat, sowie Caprolacton modifiziertes Tetrahydrofurfuryl(meth)acrylat.,

[0309] The polymerizable monomers are monomers which - in the case of cationic polymerization - are preferably substances containing one, two or more oxirane groups, such as, for example, but not limited to, the monomer derivatives commonly used in dental chemistry with an epoxycyclohexane unit or an epoxynorbornane unit.

[0310] A variety of suitable compounds are described in the patent literature. Examples with detailed synthesis details can be found in DE 196 48 283 A1. Component (E) - monomers containing acid groups that do not contain a Si atom

[0311] Suitable monomers containing acid groups are 10-(meth)acryloyloxydecyl dihydrogen phosphate (10-MDP), 2-(meth)acryloyloxyethyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 2-(Meth)-acryloyloxynonyldihydrogen phosphate, 11-(Meth)acryloyloxyundecyldihydrogen phosphate, 20-(Meth)acryloyloxyeicosyldihydrogen phosphate, 1,3-Di(meth)acyloyl-oxypropyl-2-dihydrogen phosphate, 2-(Meth)acryloyloxyethylphenyl dihydrogen phosphate, Di(2-(meth)acyloyloxyethyl)pyrophosphate, Di(2-(meth)acyloyloxypropyl)pyrophosphate, di(2-(meth)acyloyloxybutyl)pyrophosphate, di(2-(meth)acyloyloxypentyl)pyrophosphate, di(2-(meth)acyloyloxyhexyl)pyrophosphate, di(2-(meth)acyloyloxydecyl)pyrophosphate, mono-, di- and / or triesters of phosphoric acid, which are obtained by reacting hydroxy-C2-C8-alkyl methacrylate (preferably hydroxyethyl methacrylate) or glyceryl dimethacrylate with phosphorus oxychloride,Glyceryldimethacrylatphosphat, Pentaerythritoltrimethacrylatphosphat, Dipentaerythritolpentaacrylatphosphat, Tetramethacryloxyethylpyrophosphat, Trimellitsäure-4-methacryloyloxyethylester (4-MET), Trimellitsäureanhydrid-4-methacryloyloxyethylester (4-META), Pyromellitsäuredimethacrylat, Pyromellitsäureglyce-roldimethacrylat, Methacryloyloxyethylphthalat, Methacryloyloxyethylmaleat, Methacryloyloxyethylsuccinat, 1,3-Glyceroldimethacrylatmaleat und Di-Oxyethoxymethacrylsäureethylendiamintetraessigsäureester.,

[0312] Dabei bevorzugte säuregruppenhaltige Monomere sind 10-(Meth)acryloyloxy-decyldihydrogenphosphat (10-MDP), Glyceryldimethacrylatphosphat, Pentaerythritoltrimethacrylatphosphat, Dipentaerythritolpentaacrylatphosphat, Tetramethacryloxyethylpyrophosphat, Trimellitsäure-4-methacryloyloxyethylester (4-MET), Trimellitsäureanhydrid-4-methacryloyloxyethylester (4-META), Pyromellitsäuredimethacrylat, Pyromellitsäureglyceroldimethacrylat.

[0313] Other suitable acid-containing monomers are mentioned, for example, in EP 0980682 B1 and EP 0948955 A1. Other suitable acid-containing monomers that promote adhesion are mentioned in the literature. Component (F) - other common additives

[0314] A polymerizable dental composition according to the invention may contain one, two, more than two or all other conventional additives for dental compositions from the group comprising the following additives.

[0315] These additives can have various functions. Common additives for use in dental materials are familiar to the expert, and they will select the appropriate additive(s) depending on the desired function. Typical additives and their functions are described below.

[0316] Polymerizable dental compositions preferably contain one or more inhibitors, also called stabilizers. These are typically added to prevent spontaneous polymerization. They react with prematurely formed radicals, which are then trapped, preventing premature polymerization and increasing the storage stability of the polymerizable dental composition. Common inhibitors are phenol derivatives such as hydroquinone monomethyl ether (HQME) or 2,6-di-tert-butyl-4-methylphenol (BHT). Other inhibitors such as tert-butylhydroxyanisole (BHA), 2,2-diphenyl-1-picrylhydrazyl, galvinoxyl, and triphenylmethyl radicals, 2,3,6,6-tetramethylpiperidinyl-1-oxyl radicals (TEMPO), as well as derivatives of TEMPO or phenothiazine and phenothiazine derivatives are described in EP 0 783 880 B1. Alternative inhibitors are described in DE 101 19 831 A1 or EP 1 563 821 A1.

[0317] A polymerizable dental composition preferred according to the invention thus comprises as an additive one or more polymerization inhibitor(s) to increase the storage stability of the composition, preferably selected from the group consisting of hydroquinone monomethyl ether (HQME), phenols, preferably 2,6-di-tert-butyl-4-methylphenol (BHT) and tert-butylhydroxyanisole (BHA), 2,2-diphenyl-1-picrylhydrazyl radicals, galvinoxyl radicals, triphenylmethyl radicals, 2,3,6,6,-tetramethylpiperidinyl-1-oxyl radical (TEMPO) and its derivatives and phenothiazine and its derivatives.

[0318] A polymerizable composition according to the invention may comprise, as an additive, one or more fluoride-releasing substances, preferably sodium fluoride and / or amine fluorides.

[0319] UV absorbers are also considered stabilizers or inhibitors. These are capable of absorbing UV radiation, for example, through their conjugated double bond systems and aromatic rings. They are sometimes a component of a polymerizable dental composition according to the invention. Examples of UV absorbers are 2-hydroxy-4-methoxybenzophenone, phenyl salicylate, 3-(2'-hydroxy-5'-methylphenyl)benzotriazole, and diethyl 2,5-dihydroxyterephthalate.

[0320] A polymerizable dental composition preferred according to the invention may also comprise one or more molecular weight regulators as an additive. Molecular weight regulators are known in the art and are commercially available. They are used, for example, in the solution polymerization of olefins, in the emulsion polymerization of methacrylates, or for the production of molded articles from PMMA molding compounds (PMMA = polymethyl methacrylate) by compression molding or injection molding.

[0321] Molecular weight regulators are so-called transfer reagents that undergo transfer reactions in a free radical reaction. Mechanistically, this involves hydrogen abstraction and the transfer of the radical function to the regulator. Due to its function, the regulator is then found in the form of end groups in the cross-linked polymer.

[0322] Common regulators include aldehydes and ketones such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, methyl ethyl ketone, acetone, methyl isobutyl ketone, formic acid, ammonium formate, hydroxylammonium sulfate and hydroxylammonium phosphate, compounds containing sulfur in organically bound form such as di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide and di-tert.-butyl trisulfide, compounds containing sulfur in the form of SH groups, such as n-butyl mercaptan, n-hexyl mercaptan and n-dodecyl mercaptan, octadecyl mercaptan, other sulfur compounds such as hydrogen sulfites, disulfites, compounds such as mercaptoethanol, mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerin, thioglycolic acid, diethanol sulfide, thiodiglycol, ethylthioethanol, 2,2,4,6,6-pentamethylheptane-4-thiol, 2,2,4,6,6,8,8-heptamethylnonane-4-thiol, thiourea, dimethyl sulfoxide, ethylhexyl thioglycolate, pentaerythritol tetrathioglycolate, mercaptopropyltrimethoxysilane, then allyl compounds such as allyl alcohol, allyl bromide, or Benzyl compounds such as benzyl chloride or alkyl halides such as chloroform, bromotrichloromethane or tetrachloromethane, tetrabromomethane, methylene chloride, as well as lower and higher molecular weight monohydric or polyhydric alcohols such as methanol, ethanol, n-propanol, isopropanol, tert-butanol, sec.-Butanol, n-butanol, amyl alcohol, cyclohexanol, octanol, dodecanol, 1-ethylhexanol, glycerin, stearyl alcohol, oleyl alcohol, hydroxyethyl methacrylate or amines such as triethylamine as well as toluene or ethylbenzene.

[0323] Preferred molecular weight regulators in polymerizable dental compositions according to the invention include various terpenes, in particular terpinenes ( α -Terpinene, β -Terpinene, γ -Terpinene), Phellandrene ( α -Phellandrene, β- Phellandrene) and terpinolene (also δ -terpinene), 1,4-cyclohexadiene (optionally substituted), 1,3-cyclohexadiene (optionally substituted), 1,4-dihydronaphthalene, 1,4,5,8-tetrahydronaphthalene, 2,5-dihydrofuran or dimeric α -Styrene (2,4-diphenyl-4-methyl-1-pentene) as well as linoleic acid and α-linolenic acid. These molecular weight regulators are described in the publications EP 2 374 444 B1 and EP 2 374 445 B1.

[0324] Likewise preferred molecular weight regulators in polymerizable dental compositions according to the invention are double-bond-containing substances that react according to a radical addition-fragmentation chain transfer mechanism. These agents are called AFCT reagents, based on the term "addition-fragmentation chain transfer agents." Known AFCT reagents include special sulfur compounds such as allyl sulfides, allyl sulfones, dithioesters, dithiocarbamates, xanthates, and trithiocarbonates. Other known chain transfer agents are reversible AFCT reagents, so-called RAFT reagents. These substances are also preferably used in polymerizable dental compositions according to the invention.

[0325] Further preferred transfer agents for the polymerizable compositions according to the invention are disclosed in the documents EP 3 090 722 A1, EP 2 916 801 B1, EP 2 748 206 B1, EP 2 965 742 A1, EP 3 058 014 B1, EP 3 166 569 B1, EP 3 046 962 B1 and EP 2 931 756 B1.

[0326] In some embodiments, a polymerizable dental composition preferred according to the invention may also contain one or more plasticizers as an additive. This class of substance is comprehensively described for use in polymerizable dental compositions. The following are explicitly mentioned in the literature: Acid esters, selected from the group consisting of trimellitic acid esters, fatty acid esters, acetic acid esters, maleic acid esters, fumaric acid esters and citric acid esters, further tri-2-ethylhexyl trimellitate, dimethyl adipate, dibutyl adipate, diisobutyl adipate, diisonorbornyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate, diethylene glycol adipate, dibutyl diglycol adipate, di-2-ethylhexyl azelate, dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, methyl acetyl ricinolate, epoxidized soybean oil, glyceryl triacetate, 2-ethylhexyl acetate, dimethyl maleate, dibutyl maleate, di-2-ethylhexyl maleate, dibutyl fumarate, di-2-ethylhexyl fumarate, trimethyl citrate, triethyl citrate,Tripropyl citrate and triisobutyl citrate, as well as polyethylene glycol derivatives, polypropylene glycols, low molecular weight polyesters, dibutyl, dioctyl, dinonyl, diphenyl phthalate, di(iso-nonyl) adipate, tricresyl phosphate and silicone oils, dibenzyltoluene or polyethoxylated sorbitan esters, phthalic acid esters of longer branched alcohols such as bis(2-ethylhexyl) phthalate or phthalic acid polyesters, C 2 to C 18 dialkyl esters of C 2 to C 6 dicarboxylic acids, such as dioctyl malate, diisopropyl adipate, aromatic and aliphatic sulfonic acid esters, such as C 2 to C 20 alkylsulfonic acid esters of phenol or of C 1 to C 18 alkanols and typical aromatic plasticizers such as polyphenyls, as well as isomer mixtures of C 20 to C 30 aromatics, biphenyl, 1,2-Diphenylethane, Decanol, 2,4,6-Trimethylnaphthalene, Hexamethylbenzene, Diphenylmethane, 1,1-Diphenylethane, Pentadecane, 2,3-Dimethylbiphenyl, Cinnamyl alcohol, Dibenzyl ether, Hexaethylbenzene, Refined mineral oils, Oleic acid, Castor oil (castor oil), Corn oil, Camphor,and sugar alcohols, as well as tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate and tricresyl phosphate and plasticizers comprising a central polyalicyclic structural element. For the plasticizers mentioned, see the patent literature EP 2 623 087 B1, EP 2 623 086 B1, DE 101 47 125 A1, EP 1 194 110 B1, DE 32 46 654 A1, DE 101 26 476 A1, DE 197 11 514 B4, DE 39 02 417 A1, DE 199 61 341 C2, DE 197 54 029 A1, DE 60 2004 009 552 T2, DE 10 2008 283 306, DE 699 21 231 T2, DE 692 31 737 T2, DE 690 17 484 T2, DE 697 25 380 T2, DE 698 01 010 T2, DE 20 2010 014 676 U1, DE 199 41 738 B4, DE 10 2009 046 251 A1, DE 2420351 C3.

[0327] Since teeth must be restored as naturally as possible, it is necessary to provide dental compositions according to the invention in a wide variety of shades. Preferred curable dental materials according to the invention have characteristic colors, preferably a color that is covered by the "VITA classical A1 - D4 shade scale"; such colors are designated A1 - A4 (reddish-brown), B1 - B4 (reddish-yellow), C1 - C4 (gray tones), D2 - D4 (reddish-gray). To adjust the color, inorganic dyes and organic pigments are generally used in very small amounts; these are thus used as additives in preferred embodiments.

[0328] Other optional additives are flavorings, dental medicaments, organic polymers and oligomers, microbicides, preferably bactericides, surface-active substances, preferably surfactants and preservatives, preferably parabens, rheological aids and thickeners. Component (G) - Solvent

[0329] A polymerizable dental composition according to the invention, for example a dental adhesive, can also contain a solvent up to 70% by weight, based on the total composition. The composition can also contain water as a solvent. Also suitable are the commonly used organic solvents, such as hydrocarbons, ketones, and esters, such as toluene, xylene, isooctane, acetone, butanone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, N-methylpyrrolidone, dimethylacetamine, and dimethylformamide. Alcohols such as ethanol, propanols, butanols, pentanols, hexanols, cyclohexanol, heptanols, octanols, nonanols, decanols, etc., can also be used. Cycloaliphatic and arylaliphatic alcohols are also suitable.

[0330] In a preferred embodiment, a polymerizable dental composition according to the invention, for example a dental adhesive, contains an organic solvent, preferably selected from the group consisting of water-miscible organic solvents, preferably acetone, ethanol, n-propanol and isopropanol and mixtures thereof.

[0331] A polymerizable dental composition according to the invention, for example a dental adhesive, particularly preferably contains water and a water-miscible organic solvent / mixture. The ratio of the organic solvent / mixture to water is preferably in the range of 1:1 to 10:1, preferably in the range of 2:1 to 8:1, and more preferably in the range of 3:1 to 5:1.

[0332] A polymerizable dental composition according to the invention contains the following components: (A) in an amount of 5 to 99.99 wt.%, (B) in an amount of 0.3 to 92 wt.%, (C) in an amount of 0.01 to 5 wt.%, (D) in an amount of 0 to 94 wt.%, (E) in an amount of 0 to 20 wt.% (F) in an amount of 0 to 20 wt.% and (G) in an amount of 0 to 70 wt.%, The weight information refers to the total composition.

[0333] Preferred polymerizable dental compositions according to the invention contain the following components: (A) in an amount of 5 to 19.99 wt.%, (B) in an amount of 80 to 92 wt.%, (C) in an amount of 0.01 to 5 wt.%, (D) in an amount of 0 to 14 wt.% and (F) in an amount of 0 to 8 wt.% or (A) in an amount of 5 to 49.99 wt.%, (B) in an amount of 50 to 80 wt.%, (C) in an amount of 0.01 to 5 wt.%, (D) in an amount of 0 to 35 wt.%, (E) in an amount of 0 to 20 wt.% and (F) in an amount of 0 to 20 wt.% or (A) in an amount of 5 to 99.99 wt.%, (B) in an amount of 0.3 to 50 wt.%, (C) in an amount of 0.01 to 5 wt.%, (D) in an amount of 0 to 94 wt.%, (E) in an amount of 0 to 20 wt.% (F) in an amount of 0 to 20 wt.% and (G) in an amount of 0 to 70 wt.%, The weight information refers to the total composition.

[0334] In particularly preferred cases, a polymerizable dental composition according to the invention does not contain component (D).

[0335] As described above, the polymerizable dental composition according to the invention can be cured. The present invention thus also relates to a polymerized dental composition obtainable from a polymerizable dental composition according to the invention (as defined above, preferably a polymerizable composition as defined above as preferred) by polymerizing the polysiloxane compounds contained in the composition and, if appropriate, other polymerizable constituents contained in the dental composition. The polymerization preferably takes place either radically by means of the organically polymerizable double bonds contained in the (meth)acrylate groups or cationically via a ring-opening mechanism via an oxirane group.

[0336] What has been said regarding preferred embodiments of polymerizable dental compositions according to the invention also applies correspondingly to the polymerized dental compositions according to the invention.

[0337] An essential aspect of the present invention relates to a polymerizable dental composition according to the invention (as defined above, preferably as defined above as preferred), or a polymerized dental composition according to the invention (as defined above, preferably as defined above as preferred) for use in a therapeutic method (a method for the therapeutic treatment of the human or animal body, preferably the human body).

[0338] Particularly preferred in this respect is the specific application of the polymerizable dental compositions according to the invention, or the polymerized dental compositions according to the invention, in a therapeutic method for the temporary or permanent filling of a dental cavity or

[0339] in a therapeutic procedure as a dental filling material, dental bulk-fill material, dental base material, dental core build-up material, dental luting cement, dental crown material, dental bridge material, relining material, dental adhesive (bonding), dental varnish, dental sealant material, flowable dental composite material, dental inlay, dental onlay, dental overlay, artificial tooth, orthodontic material, dental framework, dental prosthesis, dental temporary or dental block material.

[0340] A dental, polymerizable composition according to the invention or a polymerized dental material according to the invention is particularly preferred for the specific application

[0341] in a therapeutic procedure for the temporary or permanent filling of a dental cavity or in a therapeutic procedure as a.) stable filling composite, stable bulk-fill material, inlay, onlay, overlay, dental block material, artificial tooth, dental framework, wherein (A) is present in an amount of 5 to 19.99 wt.%, (B) in an amount of 80 to 92 wt.%, (C) in an amount of 0.01 to 5 wt.%, (D) in an amount of 0 to 14 wt.% and (F) in an amount of 0 to 8 wt.%, b.) flowable filling composite, flowable bulk-fill material, core build-up material, dental luting cement, crown and bridge material, orthodontic material, dental base material or dental relining material, wherein (A) is present in an amount of 5 to 49.99 wt.%, (B) in an amount of 50 to 80 wt.%, (C) in an amount of 0.01 to 5 wt.%, (D) in an amount of 0 to 35 wt.%, (E) in an amount of 0 to 20 wt.% and (F) in an amount of 0 to 20 wt.%, c.) Dental adhesive, dental sealing material, dental varnish, dental primer or dental printing composition in generative dental manufacturing processes, also known as "rapid prototyping", preferably for stereolithography and here preferably for digital light processing (DLP), selective laser assembling (SLA), microstereolithography, 3D printing, laminated object manufacturing or film transfer imaging, wherein (A) is present in an amount of 5 to 99.99 wt.%, (B) in an amount of 0.3 to 50 wt.%, (C) in an amount of 0.01 to 5 wt.%, (D) in an amount of 0 to 94 wt.%, (E) in an amount of 0 to 20 wt.%, (F) in an amount of 0 to 20 wt.% and (G) in an amount of 0 to 70 wt.%, and wherein the weight data are each based on the total composition are. .

[0342] The present invention also relates to a process for producing a polymerizable dental composition comprising the following steps: Providing the components (A), (B), (C), and optionally the components (D), (E), (F), (G) and mixing the components

[0343] Furthermore, a process for producing a polymerized, preferably radically polymerized, dental composition is described, comprising the following steps: Providing the components (A), (B), (C), and optionally the components (D), (E), (F), (G), mixing the components and polymerizing, preferably radical polymerizing the mixture. The polymerizable, dental compositions are preferably used as a component of a kit according to the invention. The present invention thus also relates to a kit comprising one, two or more than two polymerizable, dental compositions according to the invention in a syringe and / or compule, optionally one, two or more than two bonding agents, optionally one, two or more than two etching gels, optionally one or more than one color scale, optionally one or more than one brush.

[0344] Examples: Abbreviations: CQ:DL-camphorquinone DABE:4-(dimethylamino)benzoic acid ethyl ester BHT:2,6-di-tert-butyl-4-methylphenol BPO:dibenzoyl peroxide DEPT: N,N-Bis(2-hydroxyethyl)-p-toluidine NTPB:Sodium tetraphenylborate BisGMA:2,2-Bis[4-(2-hydroxy-3-methacryloxypropyloxy)phenyl]propane) TEGDMA:Triethylene glycol dimethacrylate MDP:10-Methacryloyloxydecyl phosphate Dental glass 1:Barium aluminum borosilicate glass (D50 0.8 µm / D25 0.5 µm / D75 1.0 µm), silanized with γ-methacryloxypropyltrimethoxysilane Dental glass 2:Barium aluminum borosilicate glass (D50 2.7 µm / D25 1.4 µm / D75 6.1 µm), silanized with γ-methacryloxypropyltrimethoxysilane Pyrogen.-SiO 2 :pyrogenic silica (D50 40 nm), silanized with γ-methacryloxypropyltrimethoxysilane Nano-SiO 2 :non-agglomerated, non-aggregated silica (D50 40 nm), silanized with γ-methacryloxypropyltrimethoxysilane Synthesis of silanes (a1): Synthesis of 2-methyl-2-propenoic acid 9,9-dimethoxy-4-oxo-5,10-dioxa-3-aza-9-silaundec-1-yl ester (Example 1a)

[0345] 18.03 g (0.1 mol) of 3-(trimethoxysilyl)-1-propanol are heated with 15.52 g (0.1 mol) of 2-isocyanatoethyl methacrylate, 0.25 wt.% dibutyltin dilaurate, and 200 ppm BHT while stirring for 6 hours at 55 °C. As a reaction control, the disappearance of the NCO band at approximately 2270 cm -1 in the IR spectrum is observed. A pale yellow liquid is obtained. Viscosity (25 °C): 20 mPa*s. n D < 20:1.448.

[0346] IR (movie): ṽ (cm -1< ) ​​3361 (w, NH), 2972 ​​(w), 1715 (vs, C=O), 1639 (w), 1525 (m), 1447 (w), 1244 (m), 1166 (m), 1073 (vs), 946 (s), 771 (s).

[0347] 1< H NMR (60 MHz, CDCl 3 ): δ (ppm) 0.7 - 1.0 (m, 2H, SiC H 2 ), 1.9 - 2.1 (m, 2H, SiCH 2 C H 2 ), 2.05 (s, 3H, CH 3 ), 3.2 - 3.5 (m, 2H, SiCH 2 CH 2 C H 2 ), 3.60 (s, 9H, OC H 3 ), 4.07 (t, 2H, NC H 2 ), 4.42 (t, 2H, OC H 2 ), 5.05 (s, 1H, NH), 5.59 (1H, C=CH), 6.17 (1H, C=C H ). Synthesis of 2-methyl-2-propenoic acid 9,9-dimethoxy-4-oxo-5-oxa-3-aza-9-siladec-1-yl ester (Example 1b)

[0348] 16.43 g (0.1 mol) of 3-(methyldimethoxysilyl)-1-propanol are heated with 15.52 g (0.1 mol) of 2-isocyanatoethyl methacrylate, 0.25 wt.% dibutyltin dilaurate, and 200 ppm BHT for 6 hours while stirring at 55 °C. As a reaction control, the disappearance of the NCO band at approximately 2270 cm -1 in the IR spectrum is observed. A pale yellow liquid is obtained. Viscosity (25 °C): 20 mPa*s. n D < 20:1.460.

[0349] IR (movie): ṽ (cm -1< ) ​​3353 (w, NH), 2946 (w), 1713 (vs, C=O), 1637 (w), 1529 (m), 1451 (w), 1247 (m), 1166 (m), 1077 (vs), 945 (s), 767 (s).

[0350] 1< H NMR (60 MHz, CDCl 3 ): δ (ppm) 0.12 (s, 3H SiC H 3 ), 0.9 - 1.2 (m, 2H, SiC H 2 ), 1.9 - 2.1 (m, 2H, SiCH 2 C H 2 ), 2.05 (s, 3H, CH 3 ), 3.2 - 3.5 (m, 2H, SiCH 2 CH 2 C H 2 ), 3.62 (s, 6H, OC H 3 ), 4.08 (t, 2H, NC H 2 ), 4.42 (t, 2H, OC H2 ), 5.05 (s, 1H, NH), 5.59 (1H, C=C H ), 6.17 (1H, C=C H ). Synthesis of 2-methyl-2-propenoic acid 7,7-diethoxy-4-oxo-5,8-dioxa-3-aza-7-siladec-1-yl ester (Example 1c)

[0351] 19.43 g (0.1 mol) of 1-(triethoxysilyl)methanol are heated with 15.52 g (0.1 mol) of 2-isocyanatoethyl methacrylate, 0.25 wt.% dibutyltin dilaurate, and 200 ppm BHT while stirring for 6 hours at 55 °C. As a reaction control, the disappearance of the NCO band at approximately 2270 cm -1 in the IR spectrum is observed. A pale yellow liquid is obtained. Viscosity (25 °C): 21 mPa*s. n D < 20:1.455.

[0352] IR (movie): ν̃ (cm -1< ) ​​3352 (w, NH), 2970 (w), 1717 (vs, C=O), 1635 (w), 1532 (m), 1451 (w), 1245 (m), 1163 (m), 1072 (vs), 945 (s), 776 (s).

[0353] 1< H NMR (60 MHz, CDCl 3 ): δ (ppm) 1.32 (t, 9H, OCH 2 C H 3 ), 2.05 (s, 3H, CH 3 ), 2.70 (m, 2H, SiC H 2 ), 3.92 (q, 6H, OC H 2 CH 3 ), 4.09 (t, 2H, NC H 2 ), 4.41 (t, 2H, OC H2 ), 5.07 (s, 1H, NH), 5.57 (1H, C=C H ), 6.19 (1H, C=C H ). Synthesis of 2-methyl-2-propenoic acid 9,9-dimethoxy-4-oxo-3,10-dioxa-5-aza-9-silaundec-1-yl ester (Example 1d)

[0354] 20.53 g (0.1 mol) of 3-(trimethoxysilyl)propyl isocyanate are heated with 13.01 g (0.1 mol) of 2-hydroxyethyl methacrylate (HEMA), 0.25 wt.% dibutyltin dilaurate, and 200 ppm BHT while stirring for 6 hours at 55 °C. As a reaction control, the disappearance of the NCO band at approximately 2270 cm -1 in the IR spectrum is observed. A pale yellow liquid is obtained. Viscosity (25 °C): 21 mPa*s. n D < 20:1.448.

[0355] IR (movie): ν̃ (cm -1< ) ​​3356 (w, NH), 2974 (w), 1716 (vs, C=O), 1638 (w), 1527 (m), 1448 (w), 1242 (m), 1164 (m), 1072 (vs), 947 (s), 773 (s).

[0356] 1< H NMR (60 MHz, CDCl 3 ): δ (ppm) 0.6 - 0.9 (m, 2H, SiC H 2 ), 1.6 - 1.8 (m, 2H, SiCH 2 C H 2 ), 2.05 (s, 3H, CH 3 ), 3.1 - 3.4 (m, 2H, SiCH 2 CH 2 C H 2 ), 3.61 (s, 9H, OC H 3 ), 4.21 (t, 2H, OCH 2 ), 4.41 (t, 2H, OC H 2 ), 5.17 (s, 1H, NH), 5.68 (1H, C=C H ), 6.24 (1H, C=C H ). Synthesis of 2-methyl-2-propenoic acid 2-methyl-9,9-dimethoxy-4-oxo-3,10-dioxa-5-aza-9-silaundec-1-yl ester (Example 1e)

[0357] 20.53 g (0.1 mol) of 3-(trimethoxysilyl)propyl isocyanate are heated with 14.42 g (0.1 mol) of 2-hydroxypropyl methacrylate (HPMA), 0.25 wt.% dibutyltin dilaurate, and 200 ppm BHT while stirring for 6 hours at 55 °C. As a reaction control, the disappearance of the NCO band at approximately 2270 cm -1 in the IR spectrum is observed. A pale yellow liquid is obtained. Viscosity (25 °C): 27 mPa*s. n D < 20:1.448.

[0358] IR (movie): ν̃ (cm -1< ) ​​3360 (w, NH), 2975 (w), 1713 (vs, C=O), 1638 (w), 1526 (m), 1449 (w), 1242 (m), 1164 (m), 1072 (vs), 947 (s), 773 (s).

[0359] 1< H NMR (60 MHz, CDCl 3 ): δ (ppm) 0.4 - 0.7 (m, 2H, SiC H 2 ), 1.15 (d, 3H, CH 3 ), 0.4 - 1.7 (m, 2H, SiCH 2 C H 2 ), 1.94 (s, 3H, CH 3 ), 3.0 - 3.3 (m, 2H, SiCH 2 CH 2 CH 2 ), 3.61 (s, 9H, OC H 3 ), 4.15 (d, 4H, OC H 2 ), 4.8 - 5.2 (m, 2H, NH + OC H ), 5.52 (1H, C=C H ), 6.12 (1H, C=C H ). Synthesis of 2-methyl-2-propenoic acid 2-[[[[3-(trimethoxysilyl)propyl] amino]carbonyl]oxy]-1,3-propanediyl ester (Example 1f)

[0360] 20.53 g (0.1 mol) of 3-(trimethoxysilyl)propyl isocyanate are heated with 22.82 g (0.1 mol) of glycerol-1,3-dimethacrylate, 0.25 wt.% dibutyltin dilaurate, and 200 ppm BHT while stirring for 6 hours at 55 °C. As a reaction control, the disappearance of the NCO band at approximately 2270 cm -1 in the IR spectrum is observed. A pale yellow liquid is obtained. Viscosity (25 °C): 100 mPa*s. n D < 20:1.460.

[0361] IR (movie): ν̃ (cm -1< ) ​​3366 (w, NH), 2974 (w), 1718 (vs, C=O), 1638 (w), 1525 (m), 1450 (w), 1294 (w), 1241 (m), 1157 (m), 1072 (vs), 946 (s), 776 (s).

[0362] 1< H NMR (60 MHz, CDCl 3 ): δ (ppm) 0.5 - 0.8 (m, 2H, SiC H2 ), 1.5 - 1.7 (m, 2H, SiCH 2 CH 2 ), 1.97 (s, 3H, CH 3 ), 3.0 - 3.3 (m, 2H, SiCH 2 CH 2 C H 2 ), 3.61 (s, 9H, OC H 3 ), 4.3 (d, 4H, OC H 2 ), 5.00 (s, 1H, NH), 5.25 1 (m, 1H, OC H ), 5.62 (1H, C=C H ), 6.15 (1H, C=C H ). Synthesis of N -(2-Methacryloyloxyethyl)- N -[[(2-Methacryloyloxyethyl)amino]-carbonylcarbamic acid 3-(trimethoxysilyl)propyl ester (Example 1g)

[0363] 12.02 g (0.067 mol) of 3-(trimethoxysilyl)-1-propanol are heated with 20.69 g (0.133 mol, 2 eq.) of 2-isocyanatoethyl methacrylate, 0.25 wt.% dibutyltin dilaurate, and 200 ppm BHT while stirring for 6 hours at 55 °C. As a reaction control, the disappearance of the NCO band at approximately 2270 cm -1 in the IR spectrum is observed. A pale yellow liquid is obtained. Viscosity (25 °C): 34 mPa*s. n D < 20:1.454.

[0364] IR (movie): ν̃ (cm -1< ) ​​3405 (s, NH), 2972 ​​(w), 1712 (vs, C=O), 1635 (w), 1527 (m), 1446 (w), 1245 (s), 1164 (w), 1072 (vs), 945 (s), 770 (s).

[0365] 1< H NMR (60 MHz, CDCl 3 ): δ(ppm) 0.7 - 1.0 (m, 2H, SiC H 2 ), 1.9 - 2.1 (m, 2H, SiCH 2 C H 2 ), 2.05 (s, 3H, CH 3 ), 2.10 (s, 3H, CH 3 ), 3.2 - 3.5 (m, 2H, SiCH 2 CH 2 C H 2 ), 3.60 (s, 9H, OC H 3 ), 4.0 - 4.2 (4H, NC H 2 ), 4.4 - 4.6 (4H, OC H 2 ), 7.5 (1H, NH), 5.5 - 5.7 (2H, C=C H ), 6.1 - 6.3 (2H, C=C H ). Synthesis of 2-methyl-2-propenoic acid 9,9-diethoxy-4-oxo-5-oxa-3-aza-9-silaundec-1-yl ester (Example 1h)

[0366] 5.81 g (0.1 mol) of 2-propen-1-ol are heated with 15.52 g (0.1 mol) of 2-isocyanatoethyl methacrylate, 0.25 wt.% dibutyltin dilaurate, and 200 ppm BHT while stirring for 6 hours at 55 °C. As a reaction control, the disappearance of the NCO band at approximately 2270 cm -1 in the IR spectrum is observed. A pale yellow liquid is obtained, which is immediately subjected to further reaction. 16.43 g (0.1 mol) of triethoxysilane and 0.2% Karstedt catalyst solution (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in vinyl-terminated poly(dimethylsiloxane, 1% Pt)) are added and heated to 80 °C for 2 hours with stirring. A pale yellow liquid is obtained. Viscosity (25 °C): 20 mPa*s. n D < 20 :1.450.

[0367] IR (movie): ṽ (cm -1< ) ​​3357 (w, NH), 2975 (w), 1716 (vs, C=O), 1637 (w), 1525 (m), 1447 (w), 1241 (m), 1164 (m), 1072 (vs), 947 (s), 773 (s).

[0368] 1< H NMR (60 MHz, CDCl 3 ): δ (ppm) 0.7 - 1.0 (m, 2H, SiC H2 ), 1.32 (t, 9H, OCH 2 C H 3 ), 1.8 - 2.0 (m, 2H, SiCH 2 C H 2 ), 2.05 (s, 3H, CH 3 ), 3.4 - 3.6 (m, 2H, SiCH 2 CH 2 CH 2 ), 3.85 (q, 6H, OCH 2 C H 3 ), 4.07 (t, 2H, NC H 2 ), 4.42 (t, 2H, OC H 2 ), 5.08 (s, 1H, NH), 5.57 (1H, C=C H ), 6.14 (1H, C=C H ). Synthesis of 2-methyl-2-propenoic acid 9,9-diethoxy-4-oxo-3-oxa-5-aza-9-silaundec-1-yl ester (Example 1i)

[0369] 8.31 g (0.1 mol) of 3-isocyanato-1-propene are heated with 13.01 g (0.1 mol) of 2-hydroxyethyl methacrylate (HEMA), 0.25 wt.% dibutyltin dilaurate, and 200 ppm BHT while stirring for 6 hours at 55 °C. As a reaction control, the disappearance of the NCO band at approximately 2270 cm -1 in the IR spectrum is observed. A pale yellow liquid is obtained, which is immediately subjected to further reaction.

[0370] 16.43 g (0.1 mol) of triethoxysilane and 0.2% Karstedt catalyst solution (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in vinyl-terminated polydimethylsiloxane, 1% Pt) are added and heated to 80 °C for 2 hours with stirring. A pale yellow liquid is obtained. Viscosity (25 °C): 21 mPa*s. n D < 20:1.450.

[0371] IR (film): ṽ (cm -1< ) ​​3356 (w, NH), 2974 (w), 1716 (vs, C=O), 1638 (w), 1527 (m), 1448 (w), 1242 (m), 1164 (m), 1072 (vs), 947 (s), 773 (s).

[0372] 1< H NMR (60 MHz, CDCl 3 ): δ (ppm) 0.6 - 0.9 (m, 2H, SiC H 2 ), 1.32 (t, 9H, OCH 2 C H 3 ), 1.6 - 1.8 (m, 2H, SiCH 2 C H 2 ), 2.05 (s, 3H, CH 3 ), 3.1 - 3.4 (m, 2H, SiCH 2 CH 2 C H 2 ), 3.92 (q, 6H, OCH 2 C H 3 ), 4.41 (s, 4H, OC H 2 C H 2 O), 5.17 (s, 1H, NH), 5.68 (1H, C=C H ), 6.24 (1H, C=C H ).

[0373] Synthesis of silanes (a2): Synthesis of (3-methacryloyloxypropyl)methyldimethoxysilane (Example 2a)

[0374] 12.62 g (0.1 mol) of allyl methacrylate, 10.62 g (0.1 mol) of methyldimethoxysilane, and 0.2% Karstedt catalyst solution (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in vinyl-terminated polydimethylsiloxane, 1% Pt) are heated to 80 °C for 2 hours with stirring. A pale yellow liquid is obtained. Viscosity (25 °C): 5 mPa*s. n D < 20 :1.436.

[0375] IR (movie): ṽ (cm -1< ) ​​2947 (w), 1718 (vs, C=O), 1638 (w), 1525 (m), 1454 (w), 1296 (m), 1162 (s), 1080 (vs), 814 (s), 765 (s).

[0376] 1< H NMR (60 MHz, CDCl 3 ): δ (ppm) 0.12 (s, 3H SiC H 3 ), 0.6 - 0.9 (m, 2H, SiC H 2 ), 1.7 - 1.9 (m, 2H, SiCH 2 C H 2 ), 2.00 (s, 3H, CH 3 ), 3.56 (s, 3H OCH 3 ), 4.16 (t, 2H, SiCH 2 CH 2 C H 2 ), 5.58 (1H, C=C H ), 6.14 (1H, C=C H ). Synthesis of N-[3-(Dimethoxymethylsilyl)propyl]-2-methyl-2-propenamide (Example 2b)

[0377] 12.52 g (0.1 mol) NAllyl methacrylamide, 10.62 g (0.1 mol) of methyldimethoxysilane, and 0.2% Karstedt catalyst solution (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in vinyl-terminated polydimethylsiloxane, 1% Pt) were heated to 80 °C for 2 hours with stirring. A pale yellow liquid was obtained. Viscosity (25 °C): 9 mPa*s. n D < 20 :1.439.

[0378] IR (movie): ṽ (cm -1< ) ​​3351 (w, NH), 2948 (w), 1716 (vs, C=O), 1636 (w), 1524 (m), 1452 (w), 1295 (m), 1162 (s), 1079 (vs), 812 (s), 766 (s).

[0379] 1< H NMR (60 MHz, CDCl 3 ): δ (ppm) 0.12 (s, 3H SiC H 3 ), 0.4 - 0.7 (m, 2H, SiC H 2 ), 1.5 - 1.7 (m, 2H, SiCH 2 C H 2 ), 2.05 (s, 3H, CH 3 ), 3.0 - 3.3 (m, 2H, SiCH 2 CH 2 C H 2 ), 3.50 (s, 3H OCH 3 ), 5.36 (1H, C=C H ), 5.85 (1H, C=C H ), 6.94 (1H, NH). Synthesis of silanes (a3): Synthesis of dimethoxyphenylmethylsilane (Example 3a)

[0380] According to Example 1 of WO 2012 / 091154 A1, 0.47 g (1.5 mmol) bismuth(III) chloride, 8.82 g (0.1 mol) tert butyl methyl ether and 19.11 g (0.1 mol) of dichlorophenylmethylsilane. A pale yellow solid was obtained. M.P.: 73 °C. n D < 20: 1.469. Synthesis of 9,9-dimethoxy-9 H -9-silafluorene (Example 3b)

[0381] According to Example 1 of WO 2012 / 091154 A1, 0.47 g (1.5 mmol) of bismuth(III) chloride, 8.82 g (0.1 mol) of tert-butyl methyl ether and 25.12 g (0.1 mol) of 9,9-dichloro-9 H -9-silafluorene. A slowly crystallizing yellow oil is obtained. n D < 20 : 1.545. Synthesis of polysiloxanes: General condensation rule:

[0382] Dissolve 0.1 mol of silane compound(s) and 0.5 mmol of BHT in 100 ml of ethyl acetate. Then, add 2.5 ml of 1N HCl solution, and heat the mixture to 30 °C for 72 h. The mixture is extracted with 2N NaOH solution, and the organic phase is washed with water. The mixture is then dried over magnesium sulfate, and the solvent is removed in vacuo.

[0383] Example 4a: Following the general condensation procedure, 0.2 mol of 2-methyl-2-propenoic acid 9,9-dimethoxy-4-oxo-5,10-dioxa-3-aza-9-silaundec-1-yl ester (silane a1), 0.2 mol of γ-(methacyloxypropyl)trimethoxysilane (silane a2), and 0.2 mol of dimethoxydiphenylsilane (silane a3) are condensed in 60 ml of ethyl acetate in the presence of 0.3 mmol of BHT. A pale yellow liquid is obtained. Viscosity (25°C): 24 Pa*s. n D < 20 : 1.515.

[0384] Example 4b: Following the general condensation procedure, 0.4 mol of 2-methyl-2-propenoic acid 9,9-dimethoxy-4-oxo-5,10-dioxa-3-aza-9-silaundec-1-yl ester (silane a1), 0.2 mol of γ-(methacyloxypropyl)trimethoxysilane (silane a2), and 0.2 mol of dimethoxydiphenylsilane (silane a3) are condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained. Viscosity (25°C): 29 Pa*s. n D < 20 : 1.509.

[0385] Example 4c: Following the general condensation procedure, 0.4 mol of 2-methyl-2-propenoic acid 7,7-diethoxy-4-oxo-5,8-dioxa-3-aza-7-siladec-1-yl ester (silane a1), 0.2 mol of γ-(methacyloxypropyl)trimethoxysilane (silane a2), and 0.2 mol of dimethoxydiphenylsilane (silane a3) are condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained. Viscosity (25°C): 28 Pa*s. n D < 20:1.510.

[0386] Example 4d: According to the general condensation procedure, 0.4 molN -(2-Methacryloyloxyethyl)-N-[[(2-Methacryloyloxyethyl)amino]carbonyl]-carbamic acid 3-(trimethoxysilyl)propyl ester (silane a1), 0.2 mol of γ-(methacyloxypropyl)trimethoxysilane (silane a2), and 0.2 mol of dimethoxydiphenylsilane (silane a3) were condensed in the presence of 0.4 mmol of BHT in 80 ml of ethyl acetate. A pale yellow liquid was obtained. Viscosity (25°C): 38 Pa*s. n D < 20 :1.518.

[0387] Example 5a: Following the general condensation procedure, 0.8 mol of 2-methyl-2-propenoic acid 9,9-dimethoxy-4-oxo-5,10-dioxa-3-aza-9-silaundec-1-yl ester (silane a1) is condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained.

[0388] Example 5b: Following the general condensation procedure, 0.8 mol of 2-methyl-2-propenoic acid 9,9-dimethoxy-4-oxo-5-oxa-3-aza-9-siladec-1-yl ester (silane a1) is condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained.

[0389] Example 5c: Following the general condensation procedure, 0.8 mol of 2-methyl-2-propenoic acid 7,7-diethoxy-4-oxo-5,8-dioxa-3-aza-7-siladec-1-yl ester (silane a1) is condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained.

[0390] Example 5d: Following the general condensation procedure, 0.8 mol of 2-methyl-2-propenoic acid 2-[[[[3-(trimethoxysilyl)propyl]amino]carbonyl]oxy]-1,3-propanediyl ester (silane a1) is condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained.

[0391] Example 5e: According to the general condensation procedure, 0.6 mol N -(2-Methacryloyloxyethyl)- N -[[(2-Methacryloyloxyethyl)amino]carbonyl]-carbamic acid 3-(trimethoxysilyl)propyl ester (silane a1) was condensed in 60 ml of ethyl acetate in the presence of 0.3 mmol BHT. A pale yellow liquid was obtained.

[0392] Example 5f: Following the general condensation procedure, 0.8 mol of γ-(methacyloxypropyl)trimethoxysilane (silane a2) is condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained. Viscosity (25°C): 20 Pa*s. n D < 20 : 1.479.

[0393] Example 5g: Following the general condensation procedure, 0.8 mol of γ-(methacyloxypropyl)methyldimethoxysilane (silane a2) is condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained. Viscosity (25°C): 3 Pa*s. n D < 20 : 1.466.

[0394] Example 5h: Following the general condensation procedure, 0.8 mol of (methacryloxymethyl)trimethoxysilane (silane a2) is condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained. Viscosity (25°C): 18 Pa*s. n D < 20: 1.475.

[0395] Example 5i: Following the general condensation procedure, 0.8 mol of (methacryloxymethyl)methyldimethoxysilane (silane a2) is condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained. Viscosity (25°C): 3 Pa*s. n D < 20 : 1.462.

[0396] Example 5j: Following the general condensation procedure, 0.8 mol of 2-dimethoxydiphenylsilane (silane a3) is condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained.

[0397] Example 5k: Following the general condensation procedure, 0.8 mol of 2-dimethoxyphenylmethylsilane (silane a3) is condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained.

[0398] Example 5I: Following the general condensation procedure, 0.8 mol of 2-9,9-dimethoxy-9H-9-silafluorene (silane a3) is condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained.

[0399] Example 5m: Following the general condensation procedure, 0.8 mol of dimethoxydi-1-naphthalenylsilane (silane a3) is condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained.

[0400] Example 6a: Following the general condensation procedure, 0.4 mol of γ-(methacyloxypropyl)trimethoxysilane (silane a2) and 0.4 mol of dimethoxydiphenylsilane (silane a3) are condensed in the presence of 0.4 mmol of BHT in 80 ml of ethyl acetate. A pale yellow liquid is obtained. Viscosity (25°C): 24 Pa*s. n D < 20 :1.523.

[0401] Example 6b: Following the general condensation procedure, 0.4 mol of γ-(methacyloxypropyl)methyldimethoxysilane (silane a2) and 0.4 mol of dimethoxydiphenylsilane (silane a3) are condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained. Viscosity (25°C): 2 Pa*s. n D < 20 :1.534.

[0402] Example 6c: Following the general condensation procedure, 0.4 mol of (methacryloxymethyl)trimethoxysilane (silane a2) and 0.4 mol of dimethoxydiphenylsilane (silane a3) are condensed in the presence of 0.4 mmol of BHT in 80 ml of ethyl acetate. A pale yellow liquid is obtained. Viscosity (25°C): 3 Pa*s. n D < 20 : 1.546.

[0403] Example 6d: Following the general condensation procedure, 0.4 mol of (methacryloxymethyl)trimethoxysilane (silane a2) and 0.4 mol of dimethoxydi-1-naphthalenylsilane (silane a3) are condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained. Viscosity (25°C): 4 Pa*s. n D < 20 : 1.565.

[0404] Example 6e: Following the general condensation procedure, 0.4 mol of 2-methyl-2-propenoic acid 9,9-dimethoxy-4-oxo-5,10-dioxa-3-aza-9-silaundec-1-yl ester (silane a1) and 0.4 mol of (methacryloxymethyl)trimethoxysilane (silane a2) are condensed in 80 ml of ethyl acetate in the presence of 0.4 mmol of BHT. A pale yellow liquid is obtained.

[0405] Example 7 (packable filling composites): Example 7a 7b 7c 7d Polysiloxane (a1) Example 5a + - Example 5a 6.00 Example 6e 6.00 Polysiloxane (a2) Example 5f Example 4a 9.00 Example 6a Example 6a 6.00 18.00 Polysiloxane (a3) Example 5j - 9.00 12.00 6.00 Dental glass 1 14.00 14.00 14.00 14.00 Dental glass 2 62.00 62.00 62.00 62.00 Pyrogenic SiO 2 5.00 5.00 5.00 5.00 Nano-SiO 2 - - - - CQ 0.40 0.40 0.40 0.40 DABE 0.60 0.60 0.60 0.60 BF [MPa] 120.4 125.7 122.4 128.1 Young's modulus [GPa] 9.9 10.2 10.1 10.8 Shrinkage [%] 1.72% 1.62% 1.62% 1.55% Example 7e 7f 7g 7h Polysiloxane (a1) Example 4a 18.00 Example 5a Example 5a 6.00 6.00 Polysiloxane (a2) Example 5f Example 4b 6.00 Example 6a 18.00 Polysiloxane (a3) Example 5j 12.00 6.00 Dental glass 1 12.00 12.00 12.00 12.00 Dental glass 2 56.00 56.00 56.00 56.00 Pyrogenic SiO 2 - - - - Nano-SiO 2 13.00 13.00 13.00 13.00 CQ 0.40 0.40 0.40 0.40 DABE 0.60 0.60 0.60 0.60 BF [MPa] 142.5 130.4 138.1 135.6 Young's modulus [GPa] 11.1 10.9 10.8 10.9 Shrinkage [%] 1.23% 1.32% 1.25% 1.27% Example 7i 7j 7k 7l Polysiloxane (a1) Example 4a 12.00 Example 5a Example 5c Example 4a 12.25 + Example 5a 4.00 8.00 3.25 Polysiloxane (a2) Example 5f 4.00 Example 6d Example 6d Polysiloxane (a3) Example 5j 10.00 2.25 4.00 BisGMA 4.00 4.00 - - TEGDMA 2.00 2.00 - - Dental glass 1 14.00 14.00 12.00 11.30 Dental glass 2 62.00 62.00 56.00 56.55 Pyrogenic SiO 2 5.00 5.00 - - SiO2 40 nm - - 13.00 13.40 CQ 0.40 0.40 0.40 0.40 DABE 0.60 0.60 0.60 0.60 BF [MPa] 121.3 118.7 132.5 142.5 Young's modulus [GPa] 10.4 10.1 11.2 11.6 Shrinkage [%] 1.72% 1.83% 1.24% 1.21% Example 7m 7n 7o 7p Polysiloxane (a1) Example 5e Example 5e + Example 4d 7.60 6.00 Polysiloxane (a2) Example 5f Example 4d Example 4a 17.70 Example 6a 6.00 12.25 5.45 Polysiloxane (a3) 9.90 Example 5j 6.00 Dental glass 1 11.30 11.30 11.30 11.30 Dental glass 2 56.60 56.80 56.30 56.60 Pyrogenic SiO 2 0.50 0.50 0.50 0.50 SiO2 40 nm 13.40 13.40 13.40 13.40 CQ 0.20 0.20 0.20 0.20 DABE 0.30 0.30 0.30 0.30 BF [MPa] 146.3 145.8 141.7 147.3 Young's modulus [GPa] 12.2 12.1 11.5 12.5 Shrinkage [%] 1.13% 1.16% 1.26% 1.21%

[0406] Example 8 (flowable filling composites): Example 8a 8b 8c 8d Polysiloxane (a1) Example 5a Example 5a Example 4a Example 4b 11.00 11.00 Polysiloxane (a2) Example 5f 35.00 35.00 14.00 Example 6a Polysiloxane (a3) Example 5j 21.00 7.00 Dental glass 1 10.00 10.00 10.50 10.50 Dental glass 2 43.00 43.00 45.50 45.50 Pyrogenic SiO 2 - - - - Nano-SiO 2 11.00 11.00 11.00 11.00 CQ 0.40 0.40 0.40 0.40 DABE 0.60 0.60 0.60 0.60 BF [MPa] 118.3 116.8 121.0 123.1 Young's modulus [GPa] 7.2 6.9 7.5 7.7 Shrinkage [%] 2.49% 2.38% 2.31% 2.28%

[0407] Example 9 (dual-curing core build-up material): Example 9a 9b Polysiloxane (a1) Example 5a Example 5a Example 4a Example 4a 11.00 11.00 Polysiloxane (a2) Example 5f Example 5f 35.00 35.00 14.00 14.00 Polysiloxane (a3) Example 5j Example 5j 7.00 7.00 Dental glass 1 10.00 10.00 10.50 10.50 Dental glass 2 43.00 43.00 45.50 45.50 Pyrogenic SiO 2 3.00 3.00 3.00 3.00 Nano-SiO 2 8.00 8.00 8.00 8.00 DEPT 0.60 - 0.60 - BPO - 1.00 - 1.00 BHT - 0.05 - 0.05 CQ 0.15 - 0.15 - DABE 0.25 - 0.25 - BF [MPa] 112.3 118.6 Young's modulus [GPa] 6.5 6.9 Shrinkage [%] 2.53% 2.41%

[0408] Example 10 (dual-curing bonding material): Example 10a 10b Polysiloxane (a1) Example 5a Example 5a 11.00 8.25 Polysiloxane (a2) Example 4a Example 4a Example 5f Example 5f 35.00 27.00 14.00 10.50 Polysiloxane (a3) Example 5j Example 5j 7.00 5.25 MDP 9.00 9.00 Dental glass 1 9.60 9.50 10.10 10.00 Dental glass 2 43.00 42.50 45.50 45.00 Pyrogenic SiO 2 3.00 3.00 3.00 3.00 Nano-SiO 2 8.00 8.00 8.00 8.00 DEPT 0.60 - 0.60 - NTPB 0.40 0.40 BPO - 0.95 - 0.95 BHT - 0.05 - 0.05 CQ 0.15 - 0.15 - DABE 0.25 - 0.25 - BF [MPa] 111.5 117.7 Young's modulus [GPa] 6.3 6.8 Shrinkage [%] 2.58% 2.43%

[0409] Flexural strength (BF): Flexural strength is determined according to ISO 4049. All materials are light-cured section by section for 40 seconds using a Celalux 2 lamp (VOCO GmbH). Flexural strength is determined at a feed rate of 0.75 mm / min on a Zwick universal testing machine (Zwick GmbH & Co. KG, Ulm).

[0410] Modulus of elasticity (E-modulus): The modulus of elasticity is determined from the slope in the elastic range of the force-displacement curves of the flexural strength measurements.

[0411] Shrinkage: Shrinkage was determined using the bonded disk method of Watts et al. (Watts DC, Cash AJ. Determination of polymerization kinetics in visible-light cured materials: Methods development. Dent Mater 1991; 7:281-287). However, a Celalux 2 lamp (VOCO GmbH) was used for 40 seconds per measurement.

[0412] Viscosity: Viscosity is determined using a rheometer (Physica MCR 301) from Anton Paar (Graz, Austria). The measurement is performed at 25 °C in a rotation test with a plate-on-plate arrangement (diameter 25 mm, gap spacing 1 mm) in a shear rate range from 10 -2 < to 10 s -1 <. 16 readings are recorded per measurement at intervals of 30 seconds for each shear rate. The viscosities for the shear rate 10 s -1 < are given in the tables.

[0413] Since the filler phase of a dental composite material is crucial for its mechanical properties, a meaningful and reliable comparison of mechanical properties requires only comparing products with similar filler content and composition. The product categories compared above with regard to their mechanical values ​​meet this requirement, as they distinguish, for example, between packable or highly viscous (i.e., highly filled) and flowable (i.e., medium-filled) composites (for the different filler quantities, please refer to our comments on page 62 ff.).Furthermore, terms such as "hybrid composite," "microhybrid," "nano-hybrid," "microfilled composites," or "fiber-reinforced composite" provide information about the type of filler composition and thus indirectly about the amounts of added fillers. Microfilled composites, for example, consist of (pyrogenic) silica in their filler phase. Due to their high thixotropy, this product category can only contain a medium amount of filler. Hybrid composites are composed of different glasses of different size fractions (from 10 µm to < 1 µm) in combination with silica. Hybrid composites have established themselves as universal dental composites that can be used for virtually any dental restoration, from large incisal edge buildups to load-bearing fillings in the posterior region. Another variant of a hybrid composite is the "nanohybrid type."Here, nanoscale, largely non-aggregated and non-agglomerated fillers are integrated into the filler phase. The incorporation of surface-modified nanoparticles thus allows for an increase in the filler content without a corresponding increase in the viscosity of the composite. This should further improve the mechanical properties.

[0414] Our example composites 7a to 7p correspond to a typical hybrid composite featuring a bimodal glass particle distribution as the macroscopic filler component. The filler content of the composite is approximately 81 wt.%.

[0415] In order to reliably compare the mechanical properties of the inventive polymerizable dental compositions based on condensed silanes with corresponding values ​​for composites from the literature, not only must the systems be comparable, but the measurements performed must also be identical. In particular, the DIN EN ISO 4049 standard stipulates that the cured test specimens must be stored in deionized water at 37°C for 24 hours after demolding before the mechanical properties are determined. This water storage step is not considered in many tests of the mechanical properties of dental polymerizable compositions based on condensed silanes. This systematically results in higher values.

[0416] In DE 198 60 364 C2, entitled "Polymerizable dental materials based on curable siloxane compounds, their use and preparation", in examples 3 and 5 the condensed silane 1,3,5,7-tetramethyl-1,3,5,7-tetrakis-(3-methacryloxypropyl)-cyclotetrasiloxane is cured as the main monomer component with the initiator system camphorquinone / amine and an inorganic filler content of approximately 80 wt.%. In Example 3, the classical dental monomer UDMA (7,7,9-trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane-1,16-diol dimethacrylate) and in Example 5 the classical dental monomer Bis-GMA (2,2-bis-4(3-hydroxypropoxyphenyl)-propane dimethacrylate) complete the monomer matrix.

[0417] In this respect, these composites should be comparable to the composites of the invention, although the classic, proven dental monomers are still used in addition to the polysiloxanes. In Examples 3 and 5, the proportion of polysiloxane is higher than the proportion of standard monomers.

[0418] Composite 3 has a flexural strength of 119 MPa, a Young's modulus of 8731 MPa and a volume shrinkage of 2.73%.

[0419] Composite 5 has a flexural strength of 115 MPa, a Young's modulus of 8713 MPa and a volume shrinkage of 2.67%.

[0420] DE 198 60 361 A1, entitled "Crosslinkable monomers based on cyclosiloxanes, their preparation and their use in polymerizable compositions," also discloses polymerizable dental compositions based on co- and homocondensates of silanes with a filler content of approximately 80 wt.% and with the camphorquinone / amine initiator system. Compositions in which the quantitative proportion of polysiloxane is at least on the order of magnitude of the amount of conventional dental monomers are considered.

[0421] Example 3 discloses a dental composite comprising differently condensed 1-(trimethoxysilylethyl)-3,5,7-tris(3-methacryloxypropyl)-1,3,5,7-tetramethyltetrasiloxane, the cocondensate of 1-(trimethoxysilylethyl)-3,5,7-tris(3-methacryloxypropyl)-1,3,5,7-tetramethyltetrasiloxane and tetramethoxysilane, the classic dental monomer UDMA (7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diol dimethacrylate) in a small excess over the condensed silanes, fillers in an amount of approximately 82 wt.%, and the photoinitiator system camphorquinone / amine.

[0422] Composite 3 has a flexural strength of 107 MPa, a Young's modulus of 7317 MPa and a volume shrinkage of 2.57%.

[0423] Example 5 discloses a dental composite containing the homocondensate 1-(trimethoxysilylethyl)-3,5,7-tris(3-methacryloxypropyl)-1,3,5,7-tetramethyltetrasiloxane, the cocondensate of 1-(trimethoxysilylethyl)-3,5,7-tris(3-methacryloxypropyl)-1,3,5,7-tetramethyltetrasiloxane with bis-(hydroxymethyl)-tricyclo[5.2.1.0 2,6< ]-decane methacrylate (3-trimethoxysilyl-1-carbamate), the classical dental monomers Bis-GMA (2,2-bis-4(2-hydroxypropoxyphenyl)-propane dimethacrylate) and bisacryloyloxymethyltricyclo[5.2.1.0 2,6< ]decane as monomeric matrix, a filler loading of approximately 80 wt.% and the photoinitiator system Contains camphorquinone / amine.

[0424] Composite 5 has a flexural strength of 121 MPa, a Young's modulus of 8132 MPa and a volume shrinkage of 2.29%.

[0425] Example 6 discloses a dental composite comprising the homocondensate 1-(trimethoxysilylethyl)-3,5,7-tris(3-methacryloxypropyl)-1,3,5,7-tetramethyltetrasiloxane, the cocondensate of 1-(trimethoxysilylethyl)-3,5,7-tris(3-methacryloxypropyl)-1,3,5,7-tetramethyltetrasiloxane and tetramethoxysilane, the cocondensate of 1-(trimethoxysilylethyl)-3,5,7-tris(3-methacryloxypropyl)-1,3,5,7-tetramethyltetrasiloxane with 2,2-[bis-(4-hydroxyphenyl)-propane-4-methacrylate-4'-(3-trimethoxysilyl-1-carbam), the classical dental monomers Bis-GMA (2,2-bis-4(3-hydroxypropoxyphenyl)-propane dimethacrylate), 2,2-bis-4(2-hydroxyethoxyphenyl)-propane dimethacrylate), bisacryloyloxymethyltricyclo[5.2.1.0 2,6< ]decane as monomeric matrix, 80.8 wt.% filler and the photoinitiator system camphorquinone / amine.

[0426] Composite 6 has a flexural strength of 117 MPa, a Young's modulus of 8615 MPa and a volume shrinkage of 2.51%.

[0427] Example 8 discloses a dental material containing the homocondensate 1-(trimethoxysilylethyl)-3,5,7-tris(3-methacryloxypropyl)-1,3,5,7-tetramethyltetrasiloxane, the cocondensate of 1-(trimethoxysilylethyl)-3,5,7-tris(3-methacryloxypropyl)-1,3,5,7-tetramethyltetrasiloxane with 2,2-[bis-(4-hydroxyphenyl)-propane-4-methacrylate-4'-(3-trimethoxysilyl-1-carbame]], as well as the classic dental monomer UDMA (7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diol dimethacrylate) as monomeric matrix, approximately 80 wt.% filler and the photoinitiator system camphorquinone / amine.

[0428] Composite 8 has a flexural strength of 116 MPa, a Young's modulus of 7513 MPa and a volume shrinkage of 2.19%.

[0429] Example 9 discloses a dental material containing differently condensed 1-(trimethoxysilylethyl)-3,5,7-tris(3-methacryloxypropyl)-1,3,5,7-tetramethyltetrasiloxane, the cocondensate of 1-(trimethoxysilylethyl)-3,5,7-tris(3-methacryloxypropyl)-1,3,5,7-tetramethyltetrasiloxane and tetramethoxysilane, the cocondensate of 1-(trimethoxysilylethyl)-3,5,7-tris(3-methacryloxypropyl)-1,3,5,7-tetramethyltetrasiloxane with 2,2-[bis-(4-hydroxyphenyl)-propane-4-methacrylate-4'-(3-trimethoxysilyl-1-carbam]], as well as the classic dental monomers Bis-GMA (2,2-bis-4(2-hydroxypropoxyphenyl)-propane dimethacrylate) UDMA (7,7,9-trimethyl-4,13-dioxo-3, 14-dioxa-5,12-diazahexadecane-1, 16-diol dimethacrylate) and bisacryloyloxymethyltricyclo[5.2.1.0 2,6< ]decane as monomeric matrix, 80 wt.% filler and the photoinitiator system camphorquinone / amine.

[0430] Composite 9 has a flexural strength of 117 MPa, a Young's modulus of 7916 MPa and a volume shrinkage of 2.24%.

[0431] DE 41 33 494 A1, entitled "Dental Resin Materials," discloses chemically, thermally, or photochemically curing dental resin materials based on polymerizable polysiloxanes, processes for their preparation, and their use in the production of pasty, curable dental materials obtainable by hydrolytic condensation of one or more hydrolytically condensable silanes. In this publication, the systems are polymerized both radically and cationically.

[0432] Composite system L1 (Example 16, page 27) consists of a resin system obtained by reacting trimethylolpropane triacrylate (TMPTA) with (mercaptomethyl)methyldiethoxysilane in a molar ratio of 1.2 to 1 to form the corresponding Michael adduct. The ethoxy groups of the adduct are hydrolyzed under standard acidic conditions to form a transparent resin, then condensed, and finally silanized with trimethylchlorosilane to convert free Si-OH groups and thus reduce the viscosity of the resin phase, allowing a higher filler content in the composite to be achieved. A dental hybrid composite with 75 wt.% filler is obtained from the resin, which is then mixed with a photoinitiator and cured using a single-component radical process.

[0433] Composite L1 has a flexural strength (here referred to as ultimate strength, where the test specimens were not stored in water before testing) of 120 MPa, an elastic modulus of 8000 MPa and a volume shrinkage of 2.9% (see table, page 28).

[0434] Example 18 discloses a dental composite composition of a 2-component dental paste / paste system which is chemically prepared using the redox system BPO (benzoyl peroxide) / amine ( N,N -Bis-(2-hydroxyethyl)- p-toluidine) radically cures. The resin matrix of the hybrid composite comprises – as above – the reaction product of trimethylolpropane triacrylate (TMPTA) with (mercaptomethyl)methyldiethoxysilane in a molar ratio of 1.2 to 1, although the resulting Michael adduct is not silanized in this case. The viscosity of the resulting resin is correspondingly higher. In addition to the silane condensate, the hybrid composite also contains the classic dental monomer "2,2-bis-[4'(2'-methacroylethoxy)phenyl]propane," an ethoxylated bisphenol A dimethacrylate, as well as 76 wt.% filler.

[0435] The flexural strength of the non-water-stored test specimens is 120 MPa and the volume shrinkage is 2.3%.

[0436] DE 199 03 177 A1, entitled "Dental Materials Based on Polysiloxanes," discloses dental materials comprising at least one polysiloxane based on one or more hydrolytically condensable silanes of a specific structure. The dental material may additionally contain other ionically and / or radically polymerizable monomers.

[0437] Example 7 discloses a pasty dental cement in the form of a hybrid composite comprising, in an amount of 31.6 wt.%, a polysiloxane obtained after hydrolytic condensation and subsequent silylation of bis(methacryloylethoxycarbonylethyl)-[3-(triethoxysilylpropyl)]amine (obtained from the Michael addition of 3-aminopropyltriethoxysilane and 2-acryloyloxyethyl methacrylate), UDMA (7,7,9-trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane-1,16-diol dimethacrylate) in an amount of 7.8 wt.%, silanized fumed silica in an amount of 41.4 wt.%, ytterbium fluoride in an amount of 18.7 wt.%, and the photoinitiator mixture "camphorquinone / amine" in an amount of 0.5 wt.%.

[0438] The flexural strength of the dental composite is 62 MPa, the elastic modulus is 3260 MPa and the volume shrinkage is 3.6%.

[0439] In DE 101 02 297 A1, entitled "Dental materials based on metal oxide clusters", the dental materials described above are further improved mechanically through the use of clusters.

[0440] As above, composition K-1 uses a polysiloxane obtained by hydrolytic condensation of bis(methacryloylethoxycarbonylethyl)-[3-(triethoxysilylpropyl)]amine, which has not been silylated. This photoinitiated polysiloxane is processed into a paste in a hybrid composite at a concentration of 25 wt.% with 75 wt.% filler (1 wt.% fumed silica, 15 wt.% ytterbium fluoride, 15 wt.% Sphärosil, and 44 wt.% glass) and cured according to DIN EN ISO 4049.

[0441] The flexural strength of the dental composite K-1 is 68 MPa and the elastic modulus is 5500 MPa.

[0442] Composition K-3 uses a polysiloxane which, after hydrolytic condensation of photoinitiated (3-triethoxysilylpropylaminocarbonylbutyric acid (1,3-(2)-bismethacryloyloxypropyl) ester in a hybrid composite in an amount of 25 wt.% with 75 wt.% of the filler mixture specified above, is processed into a paste and cured according to DIN EN ISO 4049. The polysiloxane was obtained from 3-aminopropyltriethoxysilane and the adduct of glycerol dimethacrylate and glutaric anhydride under amide bond.

[0443] A mixture of 0.3 wt.% camphorquinone, 0.6 wt.% ethyl 4-(N,N-dimethylamino)benzoate and 0.4 wt.% acylphosphine oxide was used as the photoinitiator of the compositions, the weights being based on the total composition.

[0444] The flexural strength of the dental composite K-3 is 89 MPa and the elastic modulus is 7160 MPa.

[0445] Due to the higher filler loading, the mechanical values ​​of the dental hybrid composites in this publication are somewhat higher than those in the above DE 199 03 177 A1.

[0446] In DE 101 02 297 A1, the mechanical strength of dental polymerizable compositions based on condensed silanes should be improved by the addition of certain clusters of the type Zr 4 O 2 (OMc) 12 and lead to an increase in the Young's modulus of the materials.

[0447] If 10 wt.% of the monomeric matrix of K-1 is substituted with the cluster type Zr 4 O 2 (OMc) 12, the flexural strength of K-2 is 100 MPa and the Young's modulus is 9300 MPa.

[0448] If 10 wt.% of the monomeric matrix of K-3 is substituted with the cluster type Zr 4 O 2 (OMc) 12, the flexural strength of K-4 is 110 MPa and the Young's modulus is 9750 MPa.

[0449] If 20 wt.% of the monomeric matrix of K-3 is substituted with the cluster type Zr 4 O 2 (OMc) 12, the flexural strength of K-5 is 113 MPa and the Young's modulus is 10900 MPa.

[0450] DE 10 2006 016 474 A1, entitled "Dental materials containing hydrophobic, nanoparticulate silicic acid cocondensates and their use," discloses dental composite materials based on polysiloxanes with additional liquid, functionalized cocondensates of tetraalkyl silicic acid esters with functionalized trialkoxysilanes. The presence of these cocondensates, whose end groups have reacted with trimethylsilyl groups, is intended to improve the mechanical properties of the composites.

[0451] In the dental hybrid composite material A, the hydrolytic condensate of the silane (1,3-dimethacryloyloxypropyl-[4-(3-triethoxysilyl)propyl-N-methylaminocarbonyl)]butyrate, which is obtained by reacting glycerol dimethacrylate with glutaric anhydride, is mixed in an amount of 29.8 wt.% with the photoinitiator system "camphorquinone / p -Dimethylaminobenzoic acid ethyl ester" in an amount of 0.2 wt.% and a filler phase of ytterbium fluoride (12.7 wt.%), fumed silica (0.9 wt.%), barium aluminum borosilicate glass filler (44.1 wt.%) and a silica-zirconium mixed oxide (12.3 wt.%) with a total filler content of 70 wt.% based on the total composition were processed into a paste and cured.

[0452] The flexural strength is 51 MPa and the elastic modulus is 5410 MPa.

[0453] If a proportion of 5.9 wt.% of the polysiloxane from composite A is substituted with the additional low-viscosity cocondensate of tetraethoxysilane with 3-methacryloxypropyltriethoxysilane and end group reaction with trimethylchlorosilane, composite B has a flexural strength of 75 MPa and a Young's modulus of 5240 MPa.

[0454] Mechanical values ​​(state of the art) patent specification Resin / Filler Flexural strength (MPA) Young's modulus (MPa) Shrinkage (%) DE 19 860 364 C2 Example 3 20 / 80 119 8731 2,7 Example 5 20 / 80 115 8713 3,3 DE 19 860 361 A1 Example 3 20 / 80 107 7317 2,6 Example 5 20 / 80 121 8132 2,3 Example 6 19 / 81 117 8615 2,5 Example 8 20 / 80 116 7513 2,2 Example 9 20 / 80 117 7916 2,2 DE 41 33 494 A1 Example 16 25 / 75 120 8000 2,9 Example 18 24 / 76 120 - 2,3 DE 19 903 177 A1 Example 7 40 / 60 62 3260 3,6 DE 10102297 A1 K1 25 / 75 68 5500 - K3 25 / 75 89 7160 - K2 25 / 75 100 9300 - K4 25 / 75 110 9750 - K5 25 / 75 113 10900 - DE 10 2006 016 474 A1 A 30 / 70 51 5410 - B 30 / 70 75 5240 -

[0455] A comparison of the clinically relevant values ​​of the compositions according to the invention with the corresponding values ​​from the prior literature demonstrates a clear superiority of the new systems based on condensed silanes according to the invention. Considering the improvement in these values ​​in the order of the literature data from 2009 and 2018 (see above), the values ​​of comparable dental compositions of the "hybrid composite" type according to the invention reach new highs, even exceeding the values ​​of fiber-reinforced composites from the current compilation by Rosentritt, Illie, and Lohbauer from 2018. In addition, the extremely low shrinkage induces only a very slight change in the density ratios during the transition from the liquid / paste-like phase to the solid phase, allowing a particularly advantageous depth of cure to be achieved.

Claims

1. Dental polymerizable composition comprising (A) polysiloxanes, wherein the polysiloxanes comprise a mixture of the condensates of the three silanes (a1), (a2) and (a3) and / or a cocondensate of a mixture of the three silanes (a1), (a2) and (a3) and / or a mixture of at least two of the cocondensates (a1) / (a2), (a1) / (a3) and (a2) / (a3) and / or a mixture of the condensate of one of the three silanes (a1), (a2) or (a3) with the cocondensate of the other two silanes, wherein the silane (a1) conforms to the formula (R1O)aR2bSi[-A(-Y{-B[-PG]f}e)d]c wherein Y = -C(=O)NH-, - NHC(=O)-, -OC(=O)NH-, -NHC(=O)O-, -SC(=O)NH-, -NHC(=O)S-, -NHC(=O)NH-, -OC(=O)N(-C(=O)NH-)-, -SC(=O)N(-C(=O)NH-)-, -NHC(=O)N(-C(=O)NH-)-, -C(=O)NHC(=O)NH-, - NHC(=O)NHC(=O)-, wherein the bond on the left in the formula image is closer to the structure element A and the bond arranged on the right is closer to the structure element B, PG = polymerizable group, wherein the polymerizable group PG is selected from the group consisting of -Z-C(=O)-CH=CH2 and -Z-C(=O)-C(CH3)=CH2 wherein Z is selected from the group consisting of O and NH, A = an organic connecting group that connects Si to Y and has 1 to 20 carbon atoms, B = an organic connecting group that connects Y to PG and has 1 to 20 carbon atoms, R1 = H or C1- to C4-alkyl, R2 = C1- to C4-alkyl, a = 2 or 3, b = 0 or 1, c = 1 or 2, d = 1 to 3, e = 1 or 2, f = 1 to 5, a + b + c = 4 , and wherein the silane (a2) conforms to the formula (R1O)aR2bSi[-A'(-PG)f]c wherein PG = polymerizable group, wherein the polymerizable group PG is selected from the group consisting of -Z-C(=O)-CH=CH2 and -Z-C(=O)-C(CH3)=CH2 wherein Z is selected from the group consisting of O and NH, A' = an organic connecting group that connects Si to PG and has 1 to 20 carbon atoms and does not contain any of the following groups: -C(=O)NH-, -NHC(=O)-, -OC(=O)NH-, -NHC(=O)O-, -SC(=O)NH-, -NHC(=O)S-, -NHC(=O)NH-, - OC(=O)N(-C(=O)NH-)-, -SC(=O)N(-C(=O)NH-)-, or - NHC(=O)N(-C(=O)NH-)-, -C(=O)NHC(=O)NH-, -NHC(=O)NHC(=O)-, R1 = H or C1- to C4-alkyl, R2 = C1- to C4-alkyl, a = 2 or 3 b = 0 or 1 c = 1 or 2 f = 1 to 5, a + b + c = 4 , and wherein the silane (a3) conforms to the formula (R1O) aR2bSiArc wherein R1 = H or C1- to C4-alkyl, R2 = C1- to C4-alkyl, Ar = aryl, wherein different Ar groups may be the same or different, a = 2 or 3, b = 0 or 1, c = 1 or 2 a + b + c = 4 , (B) fillers and (C) initiators and / or catalysts and / or activators for the polymerization; wherein the proportions of silanes (a1), (a2) and (a3) in the cocondensate or in the mixture of condensates or cocondensates are (a1) in an amount of 10% to 70% by weight, (a2) in an amount of 10% to 70% by weight, and (a3) in an amount of 5% to 60% by weight, based in each case on the total amount of silanes (a1), (a2) and (a3).

2. Dental polymerizable composition according to Claim 1, additionally comprising (D) organic polymerizable monomers that are not polysiloxanes according to the invention and / or (E) organic monomers that contain acid groups and do not include a silicon atom, and / or (F) additives and / or (G) solvents.

3. Dental polymerizable composition according to either of the preceding claims, wherein the composition contains constituent (A) in an amount of 5% to 99.99% by weight, (B) in an amount of 0.3% to 92% by weight, (C) in an amount of 0.01% to 5% by weight, (D) in an amount of 0% to 94% by weight, (E) in an amount of 0% to 20% by weight, (F) in an amount of 0% to 20% by weight and (G) in an amount of 0% to 70% by weight, and wherein the weight figures are each based on the overall composition.

4. Dental polymerizable composition according to any of the preceding claims, wherein the Y group from silane (a1) is selected from the group consisting of -(X)x-C (=O)NH-, -NHC (=O)-(X)x- and - (X)xC(=O)N (-C(=O)NH-) - wherein X is selected from the group consisting of O, S and NH, preferably O and S, and wherein the index x is either 0 or 1, preferably 1, and wherein the polymerizable group PG is selected from the group consisting of Z-C(=O)-CH=CH2 and -Z-C(=O)-C(CH3)=CH2, and wherein Z is selected from the group consisting of O and NH, preferably O.

5. Dental polymerizable composition according to any of the preceding claims, wherein constituent (D) comprises organic polymerizable monomers that are not polysiloxanes according to the invention, preferably for reaction with the polysiloxanes according to the invention, and wherein (D) is selected from the group consisting of monofunctional or polyfunctional (meth)acrylate monomers, preferably from esters of (meth)acrylic acid having alkyl groups of 1 to 12 carbon atoms and from esters of (meth)acrylic acid containing aromatic groups having 6 to 12 carbon atoms, wherein the alkyl groups and aromatic groups forming the esters may contain substituents such as hydroxyl groups and ether bonds, and polymerizable monomers that are hydroxyl compounds having at least one ethylenic double bond, and polyfunctional (meth)acrylate monomers, preferably from di(meth)acrylates of alkylene glycol having 2 to 20 carbon atoms, di(meth)acrylates of oligomers of alkylene glycol, polyalkylene glycol di(meth)acrylate, di(meth)acrylates of bisphenol A or of diglycidyl ether of bisphenol A, and polymerizable compounds based on a central polyalicyclic structural element, such as 3(4), 8(9)-bis((meth)acryloyloxymethyl) tricyclo [5.2.1.02,6] decane, alkoxylated 3(4), 8(9)-bis((meth)acryloyloxymethyl)tricyclo[5.2.1.02,6] decane, 2,3-bis((meth)acryloyloxymethyl)bicyclo[2.2.1]heptane, alkoxylated 2,3-bis((meth)acryloyloxymethyl)bicyclo[2.2.1]heptane, 1,3,5-tri-(meth)acryloyloxytricyclo[3.3.1.13,7]decane, alkoxylated tri(meth)acryloyloxytricyclo[3.3.1.13,7]decane and (meth) acrylic esters of tricyclo[S.2.1.02,6]decane-3(4),8(9)-dimethanol, alkoxylated tricyclo[5.2.1.02,6]decane-3(4),8(9)-dimethano1, bicyclo[2.2.1]heptane-2,3-dimethanol, alkoxylated bicyclo[2.2.1]heptane-2,3-dimethanol, adamantane-1,3,5-triol, alkoxylated adamantane-1,3,5-triol, with urethane, urea, amide, allophanate, acylurea or biuret groups between the polyalicyclic structural element and the (meth)acrylic esters, and urethane (meth)acrylates, reaction products of 2 mol of a (meth)acrylate having a hydroxyl group and one mole of a diisocyanate, and ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, hexane-1,6-diol di(meth)acrylate (HEDMA), triethylene glycol di(meth)acrylate (TEGDMA), dodecane-1,12-diol di(meth)acrylate, bisphenol A di(meth)acrylate, alkoxylated bisphenol A di(meth)acrylate, bisphenol B di(meth)acrylate, alkoxylated bisphenol B di(meth)acrylate, bisphenol C di(meth)acrylate, alkoxylated bisphenol C di(meth)acrylate, bisphenol F di(meth)acrylate, alkoxylated bisphenol F di(meth)acrylate, polyethylene glycol di(meth)acrylate, 7,7,9-trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane-1,16-dioxydi(meth)acrylate (UDMA), butanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-hydroxypropyl 1,3-di(meth)acrylate, 3-hydroxypropyl 1,2-di(meth)acrylate, pentaerythritol di(meth)acrylate, di(meth)acrylates of dihydroxymethyltricyclo[5.2.1.02,6]decane, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1,2-dihydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2,2-bis[4-[3-(meth)acryloyloxy-2-hydroxypropoxy]phenyl]propane (bis-GMA), trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, butylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, sorbitol mono-, di-, tri-, tetra- or penta(meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, allyl (meth)acrylate, glycidyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxy polyethylene glycol(meth)acrylate, isobornyl (meth)acrylate, 2-(N,N-dimethylamino)ethyl (meth)acrylate, N-methylol(meth)acrylamide, diacetone(meth)acrylamide, 2,2-bis[4-(meth)acryloyloxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxyethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxydiethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxytriethoxyphenyl]propane 2,2-bis[4-(meth)acryloyloxytetraethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxypentaethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxydipropoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxyethoxyphenyl]-2-[4-(meth)acryloyloxydiethoxyphenyl]propane, 2-[4-(meth)acryloyloxydiethoxyphenyl]-2-[4-(meth)acryloyloxytriethoxyphenyl]propane, 2-[4-(meth)acryloyloxdipropoxyphenyl]-2-[4-(meth)acryloyloxytriethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxyisopropoxy phenyl]propane, hydroxypivalic acid neopentyl glycol di(meth)acrylate, acetoacetoxyethyl (meth)acrylate, polypropylene glycol di(meth)acrylate, glycerol alkoxylate dimethacrylate, neopentyl glycol (meth)acrylate, N,N-(1,2-dihydroxyethylene)bisacrylamide, 2,2-bis[4-(meth)acryloyloxypentaethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxypolyethoxyphenyl]propane, diethylene glycol di(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa (meth) acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol] tetra (meth) acrylate, the condensation product of 3, (4)-(meth) acryloxymethyl-8, (9)-hydroxymethyltricyclo[5.2.1.02 6]decane with dicarboxylic acids, 2-ethylhexyl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, methoxy diethylene glycol(meth)acrylate, dicyclopentenyl (meth)acrylate, phenyl (meth)acrylate, pentaerythritol mono(meth)acrylate, dipentaerythritol mono(meth)acrylate, and caprolactone-modified tetrahydrofurfuryl (meth)acrylate.

6. Dental polymerizable composition according to any of the preceding claims, wherein constituent (E) is monomers that contain acid groups and do not include a silicon atom, selected from the group consisting of 10-(meth)acryloyloxydecyl dihydrogenphosphate (10-MDP), 2-(meth)acryloyloxyethyl dihydrogenphosphate, 6-(meth)acryloyloxyhexyl dihydrogenphosphate, 4-(meth)acryloyloxybutyl dihydrogenphosphate, 8-(meth)acryloyloxyoctyl dihydrogenphosphate, 2-(meth)acryloyloxynonyl dihydrogenphosphate, 11-(meth)acryloyloxyundecyl dihydrogenphosphate, 20-(meth)acryloyloxyeicosyl dihydrogenphosphate, 1,3-di(meth)acryloyloxypropyl 2-dihydrogenphosphate, 2-(meth)acryloyloxyethylphenyl dihydrogenphosphate, di(2-(meth)acryloyloxyethyl) pyrophosphate, di(2-(meth)acryloyloxypropyl) pyrophosphate, di(2-(meth)acryloyloxybutyl) pyrophosphate, di(2-(meth)acryloyloxypentyl) pyrophosphate, di(2-(meth)acryloyloxyhexyl) pyrophosphate, di(2-(meth)acryloyloxydecyl) pyrophosphate, mono-, di- and / or triesters of phosphoric acid with hydroxy-C2-C8-alkyl methacrylate, glyceryl dimethacrylate phosphate, pentaerythritol trimethacrylate phosphate, dipentaerythritol pentaacrylate phosphate, tetramethacryloyloxyethyl pyrophosphate, trimellitic acid 4-methacryloyloxyethyl ester (4-MET), trimellitic anhydride 4-methacryloyloxyethyl ester (4-META), pyromellitic acid dimethacrylate, pyromellitic acid glycerol dimethacrylate, methacryloyloxyethyl phthalate, methacryloyloxyethyl maleate, methacryloyloxyethyl succinate, 1,3-glycerol dimethacrylate maleate and dioxyethoxymethacrylic acid ethylenediaminetetraacetic ester, wherein (E) is preferably selected from the group consisting of 10-(meth)acryloyloxydecyl dihydrogenphosphate (10-MDP), glyceryl dimethacrylate phosphate, pentaerythritol trimethacrylate phosphate, dipentaerythritol pentaacrylate phosphate, tetramethacryloyloxyethyl pyrophosphate, trimellitic acid 4-methacryloyloxyethyl ester (4-MET), trimellitic anhydride 4-methacryloyloxyethyl ester (4-META), pyromellitic acid dimethacrylate and pyromellitic acid glycerol dimethacrylate.

7. Dental polymerizable composition according to any of the preceding claims, wherein constituent (F) additives is selected from the group consisting of rheological aids, colourants, preferably colour pigments, flavours, stabilizers, in particular daylight stabilizers, inhibitors, molecular weight regulators, preservatives, preferably parabens, interface-active substances, preferably surfactants, microbicides, preferably bactericides, organic polymers and oligomers and compounds having high molecular weights, thickeners, dental medicaments and plasticizers.

8. Dental polymerizable composition according to any of the preceding claims, wherein constituent (G) solvent is selected from the group consisting of water, toluene, xylene, isooctane, acetone, butanone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, N-methylpyrrolidone, dimethylacetamide and dimethylformamide, ethanol, propanols, butanols, pentanols, hexanols, cyclohexanol, heptanols, octanols, nonanols, decanols, preferably selected from the group consisting of water-miscible organic solvents, preferably acetone, ethanol, n-propanol and isopropanol and mixtures thereof, wherein the ratio of the organic solvent(s) / mixture to water is preferably in the range of 1:1 to 10:1, preferably in the range from 2:1 to 8:1 and further preferably in the range from 3:1 to 5:1.

9. Dental polymerizable composition according to any of the preceding claims, wherein the refractive index nA of the entirety of the polymerizable monomers (A) and (D) is in the range of 1.45 to 1.55, preferably in the range of 1.48 to 1.55, and / or the refractive index nB of the entirety of the fillers (B) is in the range of 1.50 to 1.55 and / or the magnitude of the difference |nA - nB| between the refractive index nA of the entirety of the polymerizable monomers (A) and (D) and the refractive index nB of the entirety of the fillers (B) is less than 0.05, preferably less than 0.03, more preferably less than 0.02 and most preferably less than 0.01, and / or the difference nP - nA between the refractive index nP of the polymerized resin matrix of (A) and (D) and the refractive index nA of the entirety of the polymerizable monomers (A) and (D) prior to polymerisation is less than 0.03 and preferably less than 0.02.

10. Method of producing a polymerizable dental composition according to Claims 1 to 9, comprising the following steps: - providing constituents (A), (B), (C) and optionally constituents (D), (E), (F), (G), and - mixing the constituents.

11. Kit comprising - one, two or more than two polymerizable dental compositions according to any of Claims 1 to 9 in a syringe and / or compule, - optionally one, two or more than two adhesives, - optionally one, two or more than two etching gels, - optionally one or more than one shade guide, - optionally one or more than one brush.