Composite material comprising a monomer with a polyalicyclic structure as sealing material

0001The present invention relates to certain (preferably light-curable) composite materials comprising a monomer with a polyalicyclic structural element or their use in a therapeutic dental process as sealing material for sealing fissures and / or dimples and / or carious lesions. New polymerizable monomers comprising at least one polyalicyclic structural element and certain ethylenic structural elements which are particularly suitable for use in a dental composite material according to the invention or to be used according to the invention and their use in a dental composite material according to the invention or to be used according to the invention are also described below.

Sealing fissures

0002Fissure sealing is understood to mean filling up the sometimes very deep dimples, rough furrows and gullies on the surface of teeth with a well-flowing plastic material. The often narrow indentations on the occlusal surfaces are called fissures. In children and adolescents, but also in adults, caries often develops first in the fissures of the occlusal surfaces, with the occlusal surfaces of the posterior teeth showing the greatest susceptibility to caries. A strongly developed and jagged relief is also located on the inside of the front teeth, for example, so that caries-prophylactic sealing can also be useful here. In addition, a distinct fissure relief also promotes plaque attachment. Plaque accumulation was also observed in narrow fissures and on steep cusp slopes.

0003The different types of fissures (for example, ampoule-shaped, I-shaped, U-shaped, V-shaped) can absorb food residues and thus also offer an ideal and protected habitat for bacteria causing caries, since oral hygiene measures such as brushing the teeth do not work here: the bristles The toothbrushes are generally too wide to clean the bottom of the fissure. The morphology of the fissures therefore makes mechanical cleaning of the dimples almost impossible. If enamel caries develops in the fissure, it is very likely that it will expand very quickly into the dentin, since the enamel thickness in the area of ​​the fissure, especially at the base of the fissure, is usually very thin. The great susceptibility of fissures to carious infection is mainly explained by their special morphology.

0004Furthermore, it was reported that the risk of caries in the fissures is significantly increased compared to smooth tooth surfaces, since fluoride prophylaxis cannot develop the usual effectiveness in the fissures.

0005There are different types of fissure sealing:<ul id="ul0001" list-style="dash"><li>With prophylactic fissure sealing, tight, deep fissures are sealed with a suitable, thin-flowing material.</li><li>When sealing with prior grinding of the fissure, the fissure is minimally expanded using a small drill and, if there is no caries, the material is sealed.</li><li>If caries is found when grinding the fissure, it must be removed. The defect created with the preparation is first supplied with a composite filling, which is then covered with the sealing material.</li></ul>

0006By sealing the fissures, the tooth relief becomes flatter, the tooth is easier to clean and the development of caries can be prevented. Fissure sealing is now recognized as a proven and recommended, effective prophylactic measure and is being used more and more in everyday dental practice. The rule applies that all caries-prone fissures and dimples should be sealed as a precaution. It could be demonstrated that such a procedure leads to a significant decrease in cariogenic microorganisms in the fissure below the seal.

Seal carious lesions

0007While fissure sealers are liquid plastics, which are introduced into the occlusal fissure relief after the enamel has been etched, in order to form a mechanical and chemical barrier for bacteria and their cariogenic metabolic products after hardening and thus prevent caries formation or caries progression, liquid, low-viscosity Sealants can also be used to infiltrate initial carious lesions. Initial carious lesions are enamel areas with increased pore volume. These pores represent diffusion paths for a progressive dissolution of the melt structure. For this reason, it has been proposed to infiltrate with hardenable materials both to seal the diffusion paths and to stabilize the damaged melt structure. It has been shown that low-viscosity plastic compositions penetrate into lesions and can prevent further demineralization after curing.

0008So far, plastics based on dimethacrylate have been used as standard materials for sealing fissures, dimples and caries lesions, which are either not filled or, compared to filling composites, less filled. These materials show the most favorable retention behavior. Due to their lower filler loading, the sealers flow better into the depth of the fissure or lesion compared to filling composites. However, due to the reduced filler content, they are less resistant to abrasion and bending than filling materials.

0009A distinction is made between the materials, for example, according to the way in which they are cured, which can be done either by light and / or autopolymerization. Thus, light-curable fissure sealers as one-component materials are less susceptible to processing in comparison to the two-component autopolymerizable sealing materials, since there can be no blistering during mixing. These materials are therefore preferred from a clinical point of view.

0010Another distinguishing feature concerns the appearance of the material. So there are transparent and colored products. Transparent preparations are unfilled or mixed with nanoscale filler particles, the size of which is smaller than the wavelength of visible light. These materials allow the dentist, for example after sealing a fissure, to recognize a possible progression of the caries in the depth of the fissure. On the other hand, a colored material enables defects in the seal to be recognized during follow-up checks. This would not be possible with transparent seals.

0011Many variants of the dental sealing materials are also offered as fluoride-releasing materials.

0012In the <patcit id="pcit0001" dnum="DE2301067"><text>DE 23 01 067</text></patcit> propose dental fissure sealants which are said to have greatly improved handling properties and an excellent ability to completely fill and seal developing holes and fissures in teeth, their compositions containing glycol dimethacrylates such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc. as the main curable monomer component. The inventors noticed that the use of aromatic dimethacrylates is unsuitable for sealing fissures because their viscosity is too high to flow into the holes and fissures and they cannot be used to achieve a complete seal and good adhesion. Glycol dimethacrylates have always been used as so-called "reactive dilution monomers" in dental composite compositions in order to adapt and control the high viscosity of the aromatic dimethacrylates. The disclosed compositions are designed in two components and are chemically cured.

0013It is expected that compositions such as those in the <patcit id="pcit0002" dnum="DE2301067"><text>DE 23 01 067</text></patcit> are described, will absorb a lot of water due to the relatively large amount of reactive diluent monomer. The ether groups -CH₂-CH₂-O- show free, unhindered rotation and form highly flexible molecular chains. The packing of the chains in the polymer is therefore not rigid and fixed, but movable. The polymer network is opened for water to enter. It is therefore very likely that large amounts of water will get into the polymer, expand it further and then irreversibly hydrolytically split and degrade it.

0014In the <patcit id="pcit0003" dnum="US6573312B2"><text>US 6,573,312 B2</text></patcit> a composition for sealing / filling fissures and dimples is specified which contains a chemically modified bis-GMA (2,2-bis [4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl) propane). The composition is said to achieve improved physical and mechanical properties of the polymer, and the polymerization should be implemented at higher rates in the case of photocuring.

0015The bis-GMA is modified by successive reaction of the secondary hydroxyl groups of the bis-GMA with methacrylic acid chloride in the presence of an organic amine. In the first synthesis step, the dimethacrylate is reacted to a trimethacrylate (Tri-GMA) and in a second step to a tetrafunctionalized methacrylate (Tetra-GMA).

0016The compositions consist of bis-GMA and tri-GMA as well as bis-GMA, tri-GMA and tetra-GMA, the compositions also containing fillers, photoinitiators, additives and dilution monomers. Methyl methacrylate and glycol dimethacrylates are proposed as dilution monomers.

0017The special properties of dental compositions based on Bis-GMA are based on the possibility of the molecule, in addition to the linkage via the methacrylate groups, to form additional structural units, so-called superstructures or secondary / tertiary structures via hydrogen bonds, starting from the free hydroxyl groups. The structure of these superstructures can also be promoted by carbamate, amide or similarly composed groups, but not by ester groups. Furthermore, due to the rigid conformation of the bisphenol A structural motif, the polymer exhibits narrow, densely packed molecular assemblies that interact with one another via several types of bonds. These structural requirements are the basis for the good mechanical and physical properties of Bis-GMA polymers.

0018If these additional interactions are blocked by the functionalization of the free hydroxyl groups, the formation of the superstructures should be hindered and the physical and mechanical values ​​of the cured compositions should decrease.

0019In addition, they are in <patcit id="pcit0004" dnum="US6573312B2"><text>US 6,573,312 B2</text></patcit> values ​​of the physical properties listed are only estimated. Differences between the values ​​of the comparative examples and those of the examples according to the invention<patcit id="pcit0005" dnum="US6573312B2"><text>US 6,573,312 B2</text></patcit> are not apparent.

0020The <patcit id="pcit0006" dnum="US20050288387A1"><text>US 2005/0288387 A1</text></patcit> describes dental compositions that are to be used for coating teeth or as dental sealing materials. The compositions contain a multiacrylate compound, an initiator and an alcohol. The multiacrylate compound contains at least 3 acrylate units per molecule, for example dipentaerythritol pentaacrylate, di-trimethylolpropane tetraacrylate, trimethylolpropane triacrylate, etc. The initiator is preferably a photoinitiator.

0021The <patcit id="pcit0007" dnum="US20090047633A1"><text>US 2009/0047633 A1</text></patcit> also relates to a dental sealing and / or coating system that adheres to hard tooth substance itself. The composition contains 10 to 60% by weight of a polymerizable compound, comprising bis-GMA and urethane compounds and mixtures thereof, 1 to 40% by weight of a polymerizable acidic compound, 3 to 60% by weight of a silica filler with an average particle size of 1 to 100 nm, 1 to 30% by weight of water and 10 to 60% by weight of solvent.

0022The <patcit id="pcit0008" dnum="EP0969789B1"><text>EP 0 969 789 B1</text></patcit> describes dental sealing and coating materials which contain at least 10% by weight of a polymerizable material, 0.01 to 20% by weight of a filler in the nano range, which has a primary particle size between 1 and 100 nm, the surface of the filler in the nano range is modified by a chemical surface treatment with a silanizing agent and at least 10% by weight of an organic solvent with a boiling point which is below water, include.

0023Also the <patcit id="pcit0009" dnum="US6899948B2"><text>US 6,899,948 B2</text></patcit> targets dental sealing materials containing, in addition to hardenable monomers, non-aggregated, surface-modified silica particles with average particle sizes of less than 200 nm.

0024The <patcit id="pcit0010" dnum="WO2007028159A2"><text>WO 2007/028159 A2</text></patcit> relates to clear, transparent and opaque dental sealing compositions in which colloidal silica particles with an average particle size of 10 to 100 nm are dispersed in the methacrylate (acrylate) resin. The compositions are photochemically curable and are said to give hard, smooth and shiny coatings on the tooth. The non-agglomerated silica particles should be distributed homogeneously within the resin matrix so that the dispersion has a low viscosity. The polymers should have good mechanical properties such as abrasion resistance. The compositions are preferably used to seal fissures and dimples on the surface of a tooth or a restoration.

0025Among other things, the <patcit id="pcit0011" dnum="WO0130307A1"><text>WO 01/30307 A1</text></patcit> dental compositions with a visual opacity given a value less than 0.25. Since the reciprocal property of translucency represents opacity, a composition is described here with translucency values ​​that are not less than 0.75. These compositions, which can also be used as sealing materials, should also be transparent. In addition to a hardenable resin composition, they have silica particles with an average diameter of less than 200 nm.

0026The describes a temporary, transparent, dental lacquer composition for coating tooth surfaces <patcit id="pcit0012" dnum="US20060063853A1"><text>US 2006/0063853 A1</text></patcit>. Here, the transparency is brought about by the addition of hollow glass spheres to the composition, the hollow glass spheres redirecting any incoming light back to the light source. This effect is brought about by a total reflection taking place inside the spheres, which always takes place when light enters a hollow glass sphere. This phenomenon is used particularly for road markings. In order to be able to produce this effect, the refractive index of the binder must be lower than that of the hollow glass spheres.

0027Either <patcit id="pcit0013" dnum="US20070166450A1"><text>US 2007/0166450 A1</text></patcit> as well as <patcit id="pcit0014" dnum="US20100016464A1"><text>US 2010/0016464 A1</text></patcit> describe dental coating and sealing materials that contain fluorescent agents.

0028The <patcit id="pcit0015" dnum="WO2005094757A1"><text>WO 2005/094757 A1</text></patcit> claims a dental composition suitable for use as a fissure and dimple sealer and comprising a thermosetting polymerization system which is subject to step growth polymerization. The system can, for example, an epoxy-amine, an epoxy-thiol, an epoxy-carboxylic acid, an epoxy-phenol, an isocyanate-amine, an isocyanate-alcohol, an isocyanate-thiol, an isothiocyanate-amine , an isothiocyanate-alcohol, an isothiocyanate-thiol, a blocked isocyanate, a siloxane system or a similar curable system.

0029In the <patcit id="pcit0016" dnum="EP1307173B1"><text>EP 1 307 173 B1</text></patcit> describes a fluoride varnish and fissure sealing material based on silicone.

0030The pamphlets <patcit id="pcit0017" dnum="DE202006020483U1"><text>DE 20 2006 020 483 U1</text></patcit>, <patcit id="pcit0018" dnum="DE202006020480U1"><text>DE 20 2006 020 480 U1</text></patcit>, <patcit id="pcit0019" dnum="DE202006020479U1"><text>DE 20 2006 020 479 U1</text></patcit>, <patcit id="pcit0020" dnum="DE202006020477U1"><text>DE 20 2006 020 477 U1</text></patcit>, <patcit id="pcit0021" dnum="DE202006020476U1"><text>DE 20 2006 020 476 U1</text></patcit>, <patcit id="pcit0022" dnum="EP2023884A1"><text>EP 2 023 884 A1</text></patcit>, <patcit id="pcit0023" dnum="EP1854445A1"><text>EP 1 854 445 A1</text></patcit>, <patcit id="pcit0024" dnum="EP2145613A1"><text>EP 2 145 613 A1</text></patcit> and <patcit id="pcit0025" dnum="EP2151229A2"><text>EP 2 151 229 A2</text></patcit> relate to compositions for infiltration of tooth enamel in the treatment or prevention of caries lesions.

0031(Meth) acrylic acid ester of bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decans are known as monomer units for the production of dental sealants for enamel fissures. In the<patcit id="pcit0026" dnum="DE2816823C2"><text>DE 28 16 823 C2</text></patcit> the ester is used without comonomers and without filler for such a use. Compositions of the ester for tooth filling materials were mixed with the comonomers bis-GMA and hexanediol dimethacrylate according to this publication.

0032<patcit id="pcit0027" dnum="EP0254185A1"><text>EP 0 254 185 A1</text></patcit> relates to (meth) acrylic acid esters of tricyclo [5.2.1.0^2,6] decanes and their use as dental materials.

0033<patcit id="pcit0028" dnum="DE102007034457"><text>DE 10 2007 034 457</text></patcit> (corresponding <patcit id="pcit0029" dnum="EP2016931A2"><text>EP 2 016 931 A2</text></patcit>) describes formulations with a monomer mixture comprising bis-GMA and TCD-di-HEMA (bis (methacrylolyoxymethyl) tricyclo [5.2.1.0^2,6] decane) or TCD-di-HEA (bis (acrylolyoxymethyl) tricyclo [5.2.1.0^2,6] decan) with various crosslinkers. The recipes given therein relate exclusively to dental composite materials for use as stable or packable filling materials. The same applies to<patcit id="pcit0030" dnum="DE102005021332"><text>DE 10 2005 021 332</text></patcit> and the corresponding one <patcit id="pcit0031" dnum="US7601767B2"><text>US 7,601,767 B2</text></patcit>.<patcit id="pcit0032" dnum="DE3522005A1"><text>DE 35 22 005 A1</text></patcit> discloses (meth) acrylic acid derivatives of tricyclodecanes and their use in the dental field. The same applies to<patcit id="pcit0033" dnum="DE3522006A1"><text>DE 35 22 006 A1</text></patcit>.

0034<patcit id="pcit0034" dnum="DE3522005"><text>DE 35 22 005</text></patcit> discloses (meth) acrylic acid derivatives of tricyclodecanes and their use in the dental field. The same applies to the<patcit id="pcit0035" dnum="DE3522006A1"><text>DE 35 22 006 A1</text></patcit>.

0035<patcit id="pcit0036" dnum="US6617413B1"><text>US 6 617 413 B1</text></patcit> discloses compounds comprising polymerizable double bonds and other functional groups.

0036The requirements for sealing materials for sealing fissures, dimples and caries lesions are extremely diverse. First of all, the compositions must remain on the tooth surface for a long time in order to protect the tooth enamel from contamination with metabolic products of bacteria. In the best case, the material should remain on the enamel as long as the tooth is in the patient's mouth. However, such extreme requirements can hardly be met. However, it should remain on the tooth surface until the time when the greatest caries activity is recorded. This is the time until the 17th / 18th Age.

0037To achieve the longest possible seals, the most abrasion-resistant materials that can withstand the chewing pressures are required. Products with the highest possible filler content have better abrasion resistance. However, these are no longer or only very difficult to apply in the sometimes very narrow and fine fissures. A compromise must therefore be found between a filler load that is as high as possible on the one hand and a very free-flowing material that is as low-viscosity as possible.

0038Another very important property of sealing materials for sealing fissures, dimples and caries lesions should be the lowest possible water absorption of the preparation. The radical cross-linking of methacrylate / acrylate compositions creates a three-dimensionally linked network. Due to the very small size of the water molecule, water can diffuse into the mesh of the polymer, where it accumulates at certain points in the network and forms hydrogen bonds or other weakly polar bonds there. The more polar components are present in the polymer matrix, the easier it is to take up more water. The polymer expands due to the absorption of water and the intermolecular distances are increased. This hygroscopic expansion can then lead to a structural reorganization of the polymer chains. The resulting compressive stress at the bottom of the dimples and / or fissures can cause lasting damage to the hard tooth substance. The water absorption takes place over a longer period of time after hardening, so that excessive water absorption causes expansion stress and thus "overflow" of the material. In addition, water molecules can attack sensitive structural elements of the polymer, such as ester groups, and hydrolytically cleave them. This degradation can lead to complete disintegration of the network and thus loss of the product.

0039On the other hand, however, a certain polarity of the sealing materials is also desirable since the hard tooth substance is hydrophilic and polar compositions ensure good adaptation and wettability of the material to the tooth substrate.

0040The object of the invention was to find a dental material which is suitable for sealing fissures, dimples and carious lesions, which is characterized by a very low water absorption, a very good flow behavior on the tooth structure and by excellent mechanical properties.

0041In particular, the material to be found should preferably be at the same time<ul id="ul0002" list-style="dash"><li>have a water absorption in the hardened state, which is less than 25 µg / mm³,</li><li>have a good flow behavior corresponding to a contact angle on dry enamel of less than 60 ° and</li><li>have a flexural strength in the hardened state which is greater than 105 MPa.</li></ul>

0042The specified values ​​of the properties of the material to be found should be measured under measurement conditions as specified below under the "measurement methods".

0043Further objects result from the following description and the attached patent claims.

0044The primary task is solved by a composite material consisting of or comprising:<ol id="ol0001"><li>(a) as a filler component, a total amount of fillers in the range from 0.5 to 60% by weight, based on the total mass of the composite material, the total amount of fillers comprising a mixture of fillers<ul id="ul0003" list-style="none"><li>(a1) a total amount in the range from 0.5 to 60% by weight of non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm (preferably less than 60 nm) and</li><li>(a2) a total amount in the range from 0 to 59.5% by weight of microparticles with an average particle size of 0.4 μm to 10 μm such as</li><li>(a3) optionally additional fillers, wherein the percentages by weight for components (a1) and (a2) are each based on the total mass of the composite material,</li></ul></li><li>(b) as the monomer component, a total amount of polymerizable monomers in the range from 24 (preferably 39) to 98.5% by weight, based on the total mass of the composite material, the total amount comprising polymerizable monomers<ul id="ul0004" list-style="none" compact="compact"><li>(b1) one, two or more monomers selected from the group consisting of compounds (monomers) of the structure Q (Y_xZ._e)_b, where:<ul id="ul0005" list-style="dash"><li>Q represents a saturated or olefinically unsaturated polyalicyclic structural element selected from the group consisting of bicyclic, tricyclic, tetracyclic, pentacyclic and hexacyclic hydrocarbon radicals, optionally one, two or more of those not substituted by substituents Y_xZ._e substituted hydrogen atoms of this polyalicyclic structural element Q are substituted by alkyl groups (preferably C1-C4-alkyl), alkoxy groups (preferably C1-C4-alkoxy), halogen atoms (preferably F) or trifluoromethyl groups,</li><li>b is a natural number selected from the group of natural numbers 1, 2, 3 and 4,</li><li>each Z means a structural element which is selected independently of any further structural elements Z from the group consisting of          -O- (C = O) -CH = CH₂, -O- (C = O) -C (CH₃) = CH₂,          - (C = O) -CH = CH₂, - (C = O) -C (CH₃) = CH₂         -CH = CH₂, -C (CH₃) = CH₂ and -O-CH = CH₂, </li><li>each index e is a natural number, which is selected independently of any further indices e from the group of natural numbers 1, 2, 3 and 4,</li><li>each index x is independent of any other indexes x 0 or 1,</li><li>each Y in the structure means Q (Y_xZ._e)_b at x = 1 a structural element which connects the polyalicyclic structural element Q with e structural elements Z, each Y being selected independently of any further structural elements Y,</li></ul></li><li>(b2) optionally one, two or more further free-radically polymerizable monomers from the group consisting of acrylates and methacrylates, preferably from the group of methacrylates, the one or more free-radically polymerizable monomers not having any compounds (monomers) of the structure Q (Y_xZ._e)_b are,</li></ul></li><li>(c) one or more initiators and / or catalysts, preferably in an amount of up to 1% by weight, based on the total mass of the composite material, and</li><li>(d) optionally one or more additives</li></ol>for use in a therapeutic dental process as a sealing material for sealing fissures and / or dimples and / or carious lesions.

0045In other words, the object is achieved by a composite material consisting of or comprising:<ol id="ol0002"><li>(a) as a filler component, a total amount of fillers in the range from 0.5 to 60% by weight, based on the total mass of the composite material, the total amount of fillers comprising a mixture of fillers<ul id="ul0006" list-style="none"><li>(a1) a total amount in the range from 0.5 to 60% by weight of non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm and</li><li>(a2) a total amount in the range from 0 to 59.5% by weight of microparticles with an average particle size of 0.4 μm to 10 μm such as</li><li>(a3) optionally further fillers, wherein the percentages by weight for components (a1) and (a2) are each based on the total mass of the composite material,</li></ul></li><li>(b) as the monomer component, a total amount of polymerizable monomers in the range from 24 (preferably 39) to 98.5% by weight, based on the total mass of the composite material, the total amount comprising polymerizable monomers<ul id="ul0007" list-style="none" compact="compact"><li>(b1) one, two or more monomers selected from the group consisting of compounds (monomers) of the structure Q (YZ_e)_b, where:<ul id="ul0008" list-style="dash"><li>Q denotes a saturated or olefinically unsaturated polyalicyclic structural element selected from the group consisting of bicyclic, tricyclic, tetracyclic, pentacyclic and hexacyclic hydrocarbon radicals, optionally one, two or more of those not substituted by substituents YZ_e substituted hydrogen atoms of this polyalicyclic structural element Q are substituted by alkyl groups (preferably C1-C4-alkyl), alkoxy groups (preferably C1-C4-alkoxy), halogen atoms (preferably F) or trifluoromethyl groups,</li><li>b is a natural number selected from the group of natural numbers 1, 2, 3 and 4,</li><li>each Z means a structural element which is selected independently of any further structural elements Z from the group consisting of          -O- (C = O) -CH = CH₂, -O- (C = O) -C (CH₃) = CH₂,          - (C = O) -CH = CH₂, - (C = O) -C (CH₃) = CH₂         -CH = CH₂, -C (CH₃) = CH₂ and -O-CH = CH₂, </li><li>each index e is a natural number, which is selected independently of any further indices e from the group of natural numbers 1, 2, 3 and 4,</li><li>each Y means a structural element, which in the structure Q (YZ_e)_b connects the polyalicyclic structural element Q to e structural elements Z, each Y being selected or omitted independently of any further structural elements Y,</li></ul></li><li>(b2) optionally one, two or more further free-radically polymerizable monomers from the group consisting of acrylates and methacrylates, preferably from the group of methacrylates, the one or more free-radically polymerizable monomers not having any compounds (monomers) of the structure Q (YZ_e)_b are,</li></ul></li><li>(c) one or more initiators and / or catalysts, preferably in an amount of up to 1% by weight, based on the total mass of the composite material, such as</li><li>(d) optionally one or more additives</li></ol>for use in a therapeutic dental process as a sealing material for sealing fissures and / or dimples and / or carious lesions.

0046All the following statements regarding the connections of structure Q (YZ_e)_b (where each Y is selected or omitted independently of any further structural elements Y) and the preferred or particularly preferred embodiments of the present invention given in connection with these compounds apply accordingly to the compounds of the structure Q (Y_xZ._e)_b (where each index x is independent of any other indexes x 0 or 1), and vice versa.

0047Such a connection of the structure Q (Y_xZ._e)_b comprises a polyalicyclic structural element Q which is derived from a corresponding polyalicyclic hydrocarbon. In the context of the present text, this means that b hydrogen atoms of the hydrocarbon by substituents Y_xZ._e are replaced (as described above), and optionally one, two or more of those not substituted by Y._xZ._e substituted hydrogen atoms are substituted by alkyl groups, alkoxy groups, halogen atoms or trifluoromethyl groups. The polyalicyclic structural element Q is constituted by carbon ring atoms. Carbon atoms outside the rings are part of substituents.

0048In the context of the present text, (meth) acrylic means both acrylic and methacrylic.

0049The "polyalicyclic" structural element Q is a bicyclic, tricyclic, tetracyclic, pentacyclic or hexacyclic hydrocarbon radical, as defined above. The terms "bicyclic", "tricyclic", tetracyclic "," pentacyclic "and" hexacyclic "correspond to the IUPAC nomenclature.

0050In other words, Q denotes a saturated or olefinically unsaturated polyalicyclic structural element selected from the group consisting of bicyclic, tricyclic, tetracyclic, pentacyclic and hexacyclic hydrocarbon radicals, none, one, two or more of those not substituted by Y_XZ._e Substituted hydrogen atoms of this polyalicyclic structural element Q is or are substituted by alkyl groups (preferably C1-C4-alkyl), alkoxy groups (preferably C1-C4-alkoxy), halogen atoms (preferably F) or trifluoromethyl groups.

0051Each Y preferably means a structural element which is in the structure Q (Y_xZ._e)_b with x = 1 connects the polyalicyclic structural element Q with e structural elements Z, each Y being selected independently of any further structural elements Y.

0052The composite materials to be used or used according to the invention, preferably in one of the configurations identified below as preferred or particularly preferred, are particularly suitable for sealing fissures, for sealing dimples and for sealing carious lesions.

0053In a further aspect, the invention therefore relates to a composite material, preferably in one of the configurations identified below as preferred or particularly preferred, as or for use or for use as a dental sealing material, preferably as sealing material for sealing fissures, for sealing dimples or to seal carious lesions.

0054It was found that the composite materials to be used according to the invention are very good dental sealing materials for the purposes mentioned, which, compared to a sealing material from the prior art, show a much better flow behavior on the dried tooth enamel (in particular with regard to the contact angle on the dry tooth enamel). , absorb much less water and have good mechanical properties (especially flexural strength and modulus of elasticity).

0055The composite material to be used or used according to the invention is preferably light-curable.

0056The sum of the numerical values ​​of the index b and the index e is preferably 3, 4, 5, 6, 7 or 8.

0057In the uncured state, a composite material to be used or used according to the invention is distinguished by a small contact angle on dry enamel (preferably less than 60 °, preferably less than 50 °, particularly preferably less than 40 °, particularly preferably less than 35 °, measured with a contact angle measuring device from Krüss (DSA 100)).

0058Furthermore, it has been shown that a composite material to be used or used according to the invention has a very low water absorption in the hardened state, preferably less than 15 μg / mm³, preferably less than 13 µg / mm³ and particularly preferably less than 10 µg / mm³. The water absorption was determined analogously to ISO 4049.

0059A composite material to be used or used according to the invention is preferred, the filler component comprising (a)<ul id="ul0009" list-style="none"><li>(a1) a total amount in the range from 0.5 to 59.5% by weight of non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 60 nm and or</li><li>(a2) a total amount in the range from 0.5 to 59.5% by weight of microparticles with an average particle size in the range from 0.4 μm to 10 μm such as</li><li>(a3) optionally additional fillers,</li></ul>wherein the percentages by weight for components (a1) and (a2) are each based on the total mass of the composite material.

0060A composite material to be used or used according to the invention is preferred, the filler component (a)<ul id="ul0010" list-style="none" compact="compact"><li>(a3) comprises a total amount in the range from 0 to 15% by weight, preferably 0 to 10% by weight, of additional (further) fillers, the percentage by weight for component (a3) ​​being based on the total mass of the composite material.</li></ul>

0061A composite material to be used or used according to the invention is preferred, where the monomer component (b)<ul id="ul0011" list-style="none"><li>(b1) one, two or more radically polymerizable monomers of the structure Q (Y_xZ._e)_b as defined above and</li><li>(b2) one, two or more additional free-radically polymerizable monomers from the group consisting of acrylates and methacrylates, preferably from the group of methacrylates, the one or more free-radically polymerizable monomers not having any compounds (monomers) of the structure Q (Y_xZ._e)_b are as defined above, contains,</li></ul>wherein the ratio of the total mass of component (b1) to the total mass of component (b2) is preferably in the range from 4: 1 to 1: 3, preferably in the range from 3: 1 to 1: 2.

0062Also preferred is a composite material to be used or used according to the invention, comprising or consisting of<ol id="ol0003"><li>(a) as a filler component, a total amount of fillers in the range from 0.5 to 60% by weight, based on the total mass of the composite material, the total amount of fillers comprising a mixture of fillers<ul id="ul0012" list-style="none"><li>(a1) a total amount in the range from 0.5 to 60% by weight of non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm (preferably less than 60 nm) and</li><li>(a2) a total amount in the range from 0 to 59.5% by weight of microparticles with an average particle size of 0.4 μm to 10 μm such as</li><li>(a3) optionally additional fillers, wherein the percentages by weight for components (a1) and (a2) are each based on the total mass of the composite material,</li></ul></li><li>(b) as the monomer component, a total amount of polymerizable monomers in the range from 24 (preferably 39) to 89% by weight, preferably 35 (particularly preferably 44) to 60% by weight, based on the total mass of the composite material, the total amount of comprises polymerizable monomers<ul id="ul0013" list-style="none" compact="compact"><li>(b1) one, two or more monomers selected from the group consisting of compounds (monomers) of the structure Q (Y_xZ._e)_b, where:<ul id="ul0014" list-style="dash"><li>Q represents a saturated or olefinically unsaturated polyalicyclic structural element selected from the group consisting of bicyclic, tricyclic, tetracyclic, pentacyclic and hexacyclic hydrocarbon radicals, optionally one, two or more of those not substituted by substituents Y_xZ._e substituted hydrogen atoms of this polyalicyclic structural element Q are substituted by alkyl groups (preferably C1-C4-alkyl), alkoxy groups (preferably C1-C4-alkoxy), halogen atoms (preferably F) or trifluoromethyl groups,</li><li>b is a natural number selected from the group of natural numbers 1, 2, 3 and 4,</li><li>each Z means a structural element which is selected independently of any further structural elements Z from the group consisting of          -O- (C = O) -CH = CH₂, -O- (C = O) -C (CH₃) = CH₂,          - (C = O) -CH = CH₂, - (C = O) -C (CH₃) = CH₂         -CH = CH₂, -C (CH₃) = CH₂ and -O-CH = CH₂, </li><li>each index e is a natural number, which is selected independently of any further indices e from the group of natural numbers 1, 2, 3 and 4,</li><li>each index x is independent of any other indexes x 0 or 1,</li><li>each Y in the structure means Q (Y_xZ._e)_b at x = 1 a structural element which connects the polyalicyclic structural element Q with e structural elements Z, each Y being selected independently of any further structural elements Y,</li></ul></li><li>(b2) one, two or more further free-radically polymerizable monomers from the group consisting of acrylates and methacrylates, preferably from the group of methacrylates, the one or more free-radically polymerizable monomers not having any compounds (monomers) of the structure Q (Y_xZ._e)_b are, wherein the ratio of the total mass of component (b1) to the total mass of component (b2) is in the range from 4: 1 to 1: 3, preferably in the range from 3: 1 to 1: 2,</li></ul></li><li>(c) one or more initiators and / or catalysts, preferably in an amount of up to 1% by weight, based on the total mass of the composite material, such as</li><li>(d) optionally one or more additives</li></ol>for use in a therapeutic dental process as a sealing material for sealing fissures and / or dimples and / or carious lesions.

0063Composite materials to be used or used according to the invention are preferably designed in such a way that they can be used as dental material, in particular for sealing fissures, for sealing dimples and for sealing carious lesions. Corresponding uses or uses of a composite material according to the invention or to be used according to the invention are preferred.

0064The composite material to be used or used according to the invention comprises or consists of various components, for which the following applies:

Component (a): filler component

0065A composite material to be used or used according to the invention contains a total amount of fillers, this total amount being a mixture of fillers, comprising<ul id="ul0015" list-style="none"><li>(a1) a total amount in the range from 0.5 to 60% by weight of non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm and</li><li>(a2) a total amount in the range from 0 to 59.5% by weight of microparticles with an average particle size of 0.4 μm to 10 μm such as</li><li>(a3) optionally further fillers.</li></ul>

0066In embodiments preferred according to the invention, a composite material to be used or used according to the invention contains a proportion of filler component (a) in the range from 1 to 60% by weight, preferably 25 to 60% by weight, further preferably in the range from 30 to 60% by weight. %, particularly preferably in the range from 40 to 60% by weight.

0067The average particle size d₅₀ The filler particles of the filler component (a) of a composite material according to the invention to be used or to be used according to the invention are determined by means of light scattering (laser diffraction), for example using a Beckman Coulter LS 13320 particle size measuring device.

0068The filler component (a) comprises a filler (a1) in the form of non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm.

0069The filler component (a) can additionally comprise a filler (a2) different from component (a1) in the form of microparticles with an average particle size in the range from 0.4 μm to 10 μm.

0070The filler component (a) can further comprise additional fillers as component (a3), but does not have to comprise any further filler. The proportion of component (a3) ​​is preferably at most 15% by weight, preferably at most 10% by weight, more preferably less than 5% by weight, in each case based on the total mass of the composite material.

0071In a preferred embodiment, the filler component (a) comprises a mixture of a first filler (a1) in the form of non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm and a second filler (a2) in the form of microparticles with an average particle size in the range from 0.4 µm to 10 µm.

0072The combination of (a1) nanoparticles and (a2) microparticles in a composite material preferred according to the invention achieves a complete and uniform volume filling of the composite material. This reduces both the shrinkage of the composite material when the polymer matrix cures and the sensitivity of the composite material to abrasion.

0073A preferred filler component (a) of a composite material to be used or used according to the invention consists of or comprises:<ul id="ul0016" list-style="none"><li>(a1) a total amount in the range from 10 to 60% by weight of non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm, preferably a total amount in the range from 0.5 to 59.5% by weight of non-agglomerated , organic surface-modified nanoparticles with an average particle size of less than 60 nm and / or (preferably and)</li><li>(a2) a total amount in the range from 0.5 to 59.5% by weight of microparticles with an average particle size in the range from 0.4 µm to 10 µm, preferably a total amount in the range from 20 to 59.5% by weight % of microparticles with an average particle size in the range from 0.4 µm to 10 µm as well as preferably</li><li>(a3) a total amount in the range from 0 to 15% by weight of additional fillers, the percentages by weight for components (a1), (a2) and (a3) ​​being based on the total mass of the compost material.</li></ul>

0074Further preferred filler components (a) consist of:<ul id="ul0017" list-style="none"><li>(a1) a total amount in the range from 20 to 60% by weight, preferably 30 to 55% by weight, of non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm and / or (preferably and)</li><li>(a2) a total amount in the range from 25 to 59.5% by weight, preferably 30 to 55% by weight, of microparticles with an average particle size in the range from 0.4 μm to 10 μm such as</li><li>(a3) a total amount in the range from 0 to 10% by weight, preferably 0 to 5% by weight, preferably 1 to 4% by weight, of additional fillers, the percentages by weight for components (a1), (a2) and (a3) ​​being based on the total mass of the composite material.</li></ul>

0075In a composite material to be used or used according to the invention containing microparticles of component (a2), the amount of filler can be increased even further while maintaining the excellent flow and flow properties by adding one or more nanoscale fillers (a1), which increases the mechanical properties of the one to be used according to the invention or composite material to be used further improved.

0076This applies in particular to composite materials in which component (a2) contains or consists of one or more glass ceramics.

0077<u>Component (a1): non-agglomerated, organic surface-modified nanoparticles</u>

0078Within a composite material to be used or used according to the invention, the function of the nanoparticles is, inter alia, to improve the sealing (for example of fissures and dimples) and to increase the hardness and abrasion resistance.

0079If a composite material to be used or used according to the invention additionally contains microparticles of component (a2), the nanoparticles can fill up the spaces between the microparticles in order to bring about a uniform filling of the composite material.

0080In connection with the present invention, nanoparticles are understood to mean particles with an average particle size of less than 200 nm. The average particle size is preferably less than 100 nm and particularly preferably less than 60 nm.

0081The proportion of organically surface-modified nanoparticles with an average particle size of less than 200 nm is preferably greater than 10% by weight (ie> 10% by weight), preferably greater than 20% by weight and particularly preferably greater than 25% by weight.

0082In the case of transparent composite materials to be used or used according to the invention, the proportion of component (a1) is preferably greater than 30% by weight, preferably greater than 35% by weight and particularly preferably greater than 40% by weight.

0083In our own investigations, it has been shown that in the case of a content of 10% by weight or less of non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm, the composite material is no longer sufficiently abrasion-resistant. On the other hand, it has been shown that with a content of more than 60% by weight of non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm, the processability of the composite material is no longer sufficient; Because of the high solids content, its resting viscosity then becomes too high, which means that the material becomes gel-like at rest.

0084In a preferred embodiment, a composite material to be used according to the invention has a viscosity of 100 Pas or less, preferably 50 Pas or less, particularly preferably 10 Pas or less, determined under the measurement conditions which are given further below under the "measurement methods" (in summary: 23 ° C, 10 rad / s, 25 mm plate / plate system).

0085In a preferred embodiment, a composite material to be used or used according to the invention comprises a high proportion of nanoparticles of component (a1), preferably in an amount of greater than 25% by weight, preferably in the range of 30-60% by weight, particularly preferably in the range from 35 to 55% by weight, in each case based on the total mass of the composite material. Such a preferred to be used or Composite material to be used, in particular a preferred dental composite material to be used or used according to the invention, is characterized by low abrasion (preferably less than 100 μm, preferably less than 80 μm, more preferably less than 70 μm, determined by the ACTA method).

0086The 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 their mixtures. As stated, the preferred oxidic nanoparticles are not agglomerated.

0087In a preferred embodiment, the nanoscale particles are in non-agglomerated form, for example dispersed in a medium, preferably in monodisperse form.

0088In order to enable good integration of the nanoparticles into the polymer matrix of a composite material to be used or used according to the invention, the surfaces of the nanoparticles (preferably the preferred oxidic nanoparticles) are organically modified, ie their surfaces have organic structural elements. The surface treatment of the fillers with a silane may be mentioned as an example. Methacryloxypropyltrimethoxysilane is particularly suitable as an adhesion promoter.

0089If only a nanoscale filler (a1) is used as filler component (a), transparent sealing materials can be obtained (see <patcit id="pcit0037" dnum="WO0130307A1"><text>WO 01/30307 A1</text></patcit> and <patcit id="pcit0038" dnum="WO2007028159A2"><text>WO 2007/028159 A2</text></patcit>). Very good abrasion values ​​are then achieved according to the invention. The transparent dental composite materials to be used or used according to the invention are distinguished from the products from the prior art by a greatly improved flow behavior on the tooth enamel, in particular the dry tooth enamel, and by a much lower water absorption.

0090In a preferred embodiment, therefore, the filler mixture (a) of a composite material to be used or used according to the invention exclusively comprises (a1) non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm.

Component (a2): microparticles with an average particle size in the range from 0.4 µm to 10 µm

0091Within a composite material to be used or used according to the invention, microparticles of component (a2) can largely fill the volume, the remaining voids between the microparticles preferably being at least partially filled by the above-described nanoparticles (component (a1)).

0092In 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. Our own investigations have shown that the volume filling of the composite material that can already be achieved with the microparticles is the more complete and uniform the smaller the microparticles are.

0093The microparticles of component (a2) 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 a more complete volume filling can be achieved with them than with general use of microparticles with a monomodal particle size distribution. If there is a bimodal or multimodal particle size distribution, the particles of the fractions with the larger particle size cause a rough filling of the volume, while the particles of the fraction with the smaller particle size will fill the voids between the particles of the fractions with the larger particle size as far as possible.

0094A component (a2) which contains two or more fractions of microparticles is thus preferably used in a composite material to be used or used according to the invention, the mean particle sizes of the fractions differing.

0095Component (a2) preferably contains at least two microparticle fractions, their mean particle sizes differing by at least 0.5 μm, preferably by at least 0.7 μm, more preferably by at least 1 μm.

0096The microparticles of different fractions can consist of the same or different materials; there may also be several fractions of microparticles whose average particle size is approximately the same or is in a certain range, the materials of the particles differing between the fractions.

0097A composite material to be used or used according to the invention preferably comprises a component (a2) which has 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 ones Microparticle fractions, each of which has 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.

0098The ratio of the total mass of the first microparticle fractions to the total mass of the second microparticle fractions is preferably in the range from 1: 3 to 1:15, preferably in the range from 1: 8 to 1:13.

0099The ratio of the mean grain size of the or a first microparticle fraction to the mean grain size of the or a second microparticle fraction of component (a2) is preferably in the range from 1.5: 1 to 12: 1, preferably in the range from 2: 1 to 7: 1.

0100In a particularly preferred to be used or Composite material to be used comprises component (a2) 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; the ratio of the total mass of the first microparticle fractions to the total mass of the second microparticle fractions in the range from 1: 3 to 1:15, preferably in the range from 1: 8 to 1:13 and / or the ratio of the average grain size of the or a first microparticle fraction to the average The grain size of the or a second microparticle fraction of component (a2) is in the range from 1.5: 1 to 12: 1, preferably 2: 1 to 7: 1.

0101The base materials for the microparticles to be used in surface-modified form according to the invention are preferably selected from the group consisting of quartz glass ceramic or glass powder (in particular dental glass powder), barium or strontium glasses, fluoride ion-releasing glasses, oxides of aluminum or silicon, zeolites, apatite, zirconium silicates, poorly soluble Metal salts such as barium sulfate or calcium fluoride as well as radiopaque fillers such as ytterbium fluoride.

0102For better integration into the polymer matrix of a composite material to be used or used according to the invention, the microparticles are preferably organically surface-modified. An example is the surface treatment of the fillers with a silane, which leads to silanized microparticles. Methacryloxypropyltrimethoxysilane is particularly suitable for surface treatment (as an adhesion promoter).

0103In a particularly preferred composite material to be used according to the invention, at least some of the microparticles of component (a2) are formed by organically surface-modified particles, preferably silanized particles, and / or at least some of the microparticles of component (a2) are formed by dental glass particles; preferably at least some of the microparticles of component (a2) are organically surface-modified dental glass particles, preferably silanized dental glass particles.

0104In these cases, component (a2) is preferably distinguished by a bimodal or multimodal particle size distribution, in particular a bimodal or multimodal particle size distribution with the preferred features described above.

Component (a3) ​​- Additional (further) fillers

0105The filler component (a) can further comprise an additional filler (a3). This filler (a3) ​​does not comprise any non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm (which are to be counted as component (a1)) and also does not include microparticles with an average particle size of 0.4 µm to 10 µm ( which are to be counted as component (a2). Preferably, the filler component (a) comprises, in addition to the components (a1) and / or (a2), further fillers as component (a3).

0106For example, reinforcing filler materials, such as glass fibers, polyamide or carbon fibers, can be used. A composite material to be used or used according to the invention can also contain finely divided fragments or bead polymers, where the bead polymers can be homo- or copolymers of organic curable monomers.

Component (b): monomer component

0107Within a composite material to be used or used according to the invention, the function of the monomer component (b) is to form a matrix in which the fillers (a) mentioned above are incorporated. This matrix is ​​formed by polymerization, in particular radical polymerization, of (b1) one, two or more monomers of the structure Q (Y_xZ._e)_b, optionally together with component (b2) one, two or more further free-radically polymerizable monomers from the group consisting of acrylates and methacrylates, the one or more free-radically polymerizable monomers not having any compounds (monomers) of the structure Q (Y_xZ._e)_b are as defined above.

0108The monomer component (b) is preferably a monomer mixture which comprises both component (b1) and component (b2) or consists thereof.

0109Preferred composite materials to be used or used according to the invention comprise monomer component (b) in an amount in the range from 24 (preferably 39) to 89% by weight, preferably 30 (preferably 42) to 65% by weight, preferably in the range from 35 (preferably) 44) up to 60% by weight, based on the total mass of the composite material.

0110Particularly good results in the sense of the present invention are achieved if the weight ratio of the total amount of monomer component (b1) to the total amount of monomer component (b2) is in the range 4: 1 to 1: 3, preferably in the range 3: 1 to 1: 2 , preferably in the range 2: 1 to 2: 3, particularly preferably in the range 3: 2 to 2: 3 and very particularly preferably in the range 4: 3 to 3: 4.

0111This preferably applies to monomers of component (b1) in which the polyalicyclic structural element Q is a tricyclo [5.2.1.0^2,6] decane residue means, especially for monomers of component (b1), the reaction products of bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decans are.

0112The polyalicyclic structural element Q of component (b1) ensures a sterically rigid and hydrophobic backbone, and the other monomers of component (b2) ensure adequate crosslinking, in particular to the surface-modified fillers. Our own studies have shown that pastes with a lower proportion of component (b2) or without component (b2) have increased abrasion, whereas pastes with a lower proportion of component (b1) or without component (b1) show increased water absorption and less favorable mechanical properties (especially a reduced modulus of elasticity).

Component (b1): one, two or more monomers of the structure

Q (Y

x

Z.

e

)

b

with at least one polyalicyclic structural element

0113Component (b1) form one, two or more monomers of the structure Q (Y_xZ._e)_b, where Z is preferably a structural element which is selected independently of any further structural elements Z from the group consisting of - O- (C = O) -CH = CH₂, -O- (C = O) -C (CH₃) = CH₂, - (C = O) -CH = CH₂ or - (C = O) -C (CH₃) = CH₂. Compounds of the structure Q (Y_xZ._e)_b, where Z is selected from the group consisting of -O- (C = O) -CH = CH₂, -O- (C = O) -C (CH₃) = CH₂, ie compounds of the structure Q (Y_xZ._e)_bwhich have one, two or more acrylate and / or methacrylate groups, preferably two or more acrylate and / or methacrylate groups.

0114The polymers and composite materials obtainable with the monomers of component (b1) to be used according to the invention have a pronounced hydrophobicity, which is evident, inter alia, in the very low water absorption of the polymers and composite materials. In addition, the polymers obtainable using the monomers of component (b1) to be used according to the invention are notable for high mechanical stability, which is evident, inter alia, in the high flexural strength of the polymers. The monomers of component (b1) to be used according to the invention, in particular in accordance with the particularly preferred refinements and embodiments, can be processed to give polymers which have both low water absorption and high flexural strength.

0115The monomers of component (b1) can be copolymerized with the further monomers of component (b2), the cured polymers or molding materials having low shrinkage, good adhesion to various substrates, high resistance to hydrolysis, low water absorption and high mechanical strength . The properties mentioned are particularly important in the field of dental technology.

0116In particular, the preferred and particularly preferred compounds of component (b1) to be used according to the invention enable a high degree of crosslinking and are furthermore preferably radically crosslinkable. Because of their highly functionalized structure, they have a high probability of crosslinking and polymerization.

0117Preferred compounds of component (b1) to be used according to the invention are those in which Q is a polyalicyclic structural element, preferably a saturated polyalicyclic structural element which is selected from the group consisting of bicyclic or tricyclic hydrocarbon radicals, preferably none of the substituents Y not being substituted by substituents_xZ._e substituted hydrogen atoms of this polyalicyclic structural element Q is substituted.

0118Monomers Q (Y_xZ._e)_b, whose polyalicyclic structural element Q is derived from one of the following tricyclic hydrocarbons: tricyclo [5.2.1.0^2,6] decane (TCD), tricyclo [5.2.1.0^2,6] dec-3-en or tricyclo [3.3.1.1^3,7] decane (adamantane), ie preferred are compounds according to the invention which have a TCD skeleton, a tricyclo [5.2.1.0^2,6] dec-3-en - have a scaffold or an adamantane scaffold.

0119In the case of the particularly preferred compounds mentioned according to the invention in which the structural element Q is a tricyclo [5.2.1.0^2,6] decane residue, a tricyclo [5.2.1.0^2,6] dec-3-ene residue, a tricyclo [3.3.1.1^3,7] decane residue or a bicyclo [2.2.1] heptane residue, it is preferably those with a tricyclo [5.2.1.0^2,6] decane framework, a tricyclo [5.2.1.0^2,6] dec-3-ene skeleton, a tricyclo [3.3.1.1^3,7] decane skeleton or a bicyclo [2.2.1] heptane skeleton, in each of which none of the substituents Y_xZ._e substituted hydrogen atoms of this polyalicyclic structural element Q is substituted.

0120Particularly preferred compounds Q (Y_xZ._e)_b of component (b1) are those in which the structural element Q is a tricyclo [5.2.1.0^2,6] decane residue, a tricyclo [5.2.1.0^2,6] dec-3-ene residue, a tricyclo [3.3.1.1^3,7] decane residue or a bicyclo [2.2.1] heptane residue means, very particularly preferably the structural element Q means a tricyclo [5.2.1.0^2,6] decane residue, a tricyclo [5.2.1.0^2,6] dec-3-en residue.

0121Particularly preferred compounds Q (Y_xZ._e)_b of component (b1) are those in which the structural element Q is a tricyclo [5.2.1.0^2,6] -decane or tricyclo [5.2.1.0^2,6] -decene structural element and Z is preferably selected from the group consisting of -O- (C = O) -CH = CH₂ and -O- (C = O) -C (CH₃) = CH₂, where again the group Z particularly preferably -O- (C = O) -C (CH₃) = CH₂ is.

0122Particularly preferred composite materials according to the invention or to be used or used according to the invention contain as component (b1) one, two or more compounds of the structure Q (Y_xZ._e)_b, each a tricyclo [5.2.1.0^2,6] -decane or tricyclo [5.2.1.0^2,6] -decene structural element and Z is preferably selected from the group consisting of -O- (C = O) -CH = CH₂ and -O- (C = O) -C (CH₃) = CH₂, where again the group Z particularly preferably -O- (C = O) -C (CH₃) = CH₂ is.

0123Methacrylic acid or acrylic acid esters with a tricyclo [5.2.1.0^2,6] -decane or tricyclo [5.2.1.0^2,6] -decene structural element selected from the group consisting of<ul id="ul0018" list-style="dash"><li>8,9-bis (acryloxymethyl) tricyclo [5.2.1.0^2,6] decan</li><li>8,9-bis (methacryloyloxymethyl) tricyclo [5.2.1.0^2,6] decan</li><li>8.9- [bis (2-vinyloxyethyl) oxymethyl] tricyclo [5.2.1.0^2,6] dec-3-en</li><li>8.9- [bis (2-vinyloxyethyl) oxymethyl] tricyclo [5.2.1.0^2,6] decan</li><li>8-hydroxymethyl-9- (2-vinyloxyethyl) oxymethyl] tricyclo [5.2.1.0^2,6] dec-3-en</li><li>9-hydroxymethyl-8- (2-vinyloxyethyl) oxymethyl] tricyclo [5.2.1.0^2,6] dec-3-en</li><li>8,9-bis (acryloyloxymethyl) tricyclo [5.2.1.0^2,6] dec-3-en</li><li>8,9-bis (methacryloyloxymethyl) tricyclo [5.2.1.0^2,6] dec-3-en</li><li>Diacrylic acid or dimethacrylic acid esters of compounds selected from the group consisting of:<ul id="ul0019" list-style="dash"><li>3,8-dihydroxymethyltricyclo [5.2.1.0^2,6] decan</li><li>3,9-dihydroxymethyltricyclo- [5.2.1.0^2,6] decan</li><li>4,8-dihydroxymethyltricyclo [5.2.1.0^2,6] decan</li><li>3,8-dihydroxytricyclo [5.2.1.0^2,6] decan</li><li>3,9-dihydroxytricyclo- [5.2.1.0^2,6] decan</li><li>4,8-dihydroxytricyclo [5.2.1.0^2,6] decan</li></ul></li><li>Methacrylic acid or acrylic acid esters of compounds from the group consisting of:<ul id="ul0020" list-style="dash"><li>Poly (hydroxymethyl-tricyclo [5.2.1.0^2,6] decanyl siloxanes</li><li>oxyalkylated bishydroxymethyltricyclo [5.2.1.0^2,6] decan</li><li>oxyalkylated bishydroxytricyclo [5.2.1.0^2,6] decan</li></ul></li><li>Methacrylic or acrylic acid esters containing urethane or urea groups of compounds selected from the group consisting of:<ul id="ul0021" list-style="dash"><li>3,8-dihydroxymethyltricyclo [5.2.1.0^2,6] decan</li><li>4,8-dihydroxymethyltricyclo [5.2.1.0^2,6] decan</li><li>3,9-dihydroxymethyltricyclo [5.2.1.0^2,6] decan</li><li>4,9-dihydroxymethyltricyclo [5.2.1.0^2,6] decan</li></ul></li></ul>

0124Here, hydrogen can be tricyclo [5.2.1.0^2,6] -decane or tricyclo [5.2.1.0^2,6] -decene radical can be substituted by alkyl groups (preferably C1-C4-alkyl), alkoxy groups (preferably C1-C4-alkoxy), halogen atoms (preferably F) or trifluoromethyl groups.

0125Many of the radically polymerizable methacrylic acid or acrylic acid esters with a TCD structural element listed above are known from the prior art.

0126Our own investigations have shown that the above-mentioned monomers Q (Y_xZ._e)_b component (b1) with a tricyclo [5.2.1.0^2,6] -decane structural element of component (b1) composite materials with a small contact angle on dry enamel (preferably less than 40 °, preferably less than 30 °) or low abrasion (preferably less than 100 μm, preferably less than 80 μm, more preferably less than 70 µm, determined according to the ACTA method) are available.

0127Our own investigations have also shown that the above-mentioned monomers Q (Y_xZ._e)_b component (b1) with a tricyclo [5.2.1.0^2,6] -decane structural element - in the hardened state - composite materials with low water absorption (preferably less than 13 µg / mm³, preferably less than 10 µg / mm³) are available.

0128Y is preferably a structural element which in the structure Q (Y_xZ._e)_b the polyalicyclic structural element Q is linked to e structural elements Z and contains or consists of a structural element which is selected from the group consisting of<chemistry id="chem0001" num="0001"><img file="EP2436366A2_D0001.tif" /></chemistry>where R^y means another remainder of the connection and the binding arranged on the left in the formula picture is closer to the structural element Q and the binding arranged on the right is closer to the structural element Z.

0129The rest of R^y a compound of the structure Q (Y_xZ._e)_b is preferably selected from the group consisting of hydrogen, linear, branched or ring-comprising structural elements with 1 to 50 C atoms and 0 to 12 heteroatoms, the heteroatoms optionally present preferably being selected from the group consisting of N and O.

0130The rest of R^y is preferably selected from the group consisting of hydrogen, linear, branched or ring-comprising structural elements with 1 to 40 C atoms and 0 to 10 heteroatoms, the heteroatoms which may be present preferably being selected from the group consisting of N and O.

0131The rest of R^y is particularly preferably selected from the group consisting of hydrogen, linear, branched or rings comprising structural elements with 1 to 35 C atoms and 1 to 10 heteroatoms, the heteroatoms which may be present preferably being selected from the group consisting of N and O.

0132Y is preferably a structural element which contains or consists of a structural element, selected from the group consisting of<chemistry id="chem0002" num="0002"><img file="EP2436366A2_D0002.tif" /></chemistry><chemistry id="chem0003" num="0003"><img file="EP2436366A2_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP2436366A2_D0004.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP2436366A2_D0005.tif" /></chemistry><chemistry id="chem0006" num="0006"><img file="EP2436366A2_D0006.tif" /></chemistry><chemistry id="chem0007" num="0007"><img file="EP2436366A2_D0007.tif" /></chemistry>where R¹, R², R³, R⁴ and R⁵ mean other residues of the compound, the bond arranged on the left in the formula being closer to the structural element Q and the bond arranged on the right closer to the structural element Z.

0133The above-mentioned other residues R¹, R², R³, R⁴ or R⁵ a compound of the structure Q (Y_xZ._e)_b are, in each case independently of one another, preferably selected from the group consisting of hydrogen, linear, branched or ring-comprising structural elements with 1 to 30 C atoms and 0 to 10 heteroatoms, the heteroatoms optionally present preferably being selected from the group consisting of N and O.

0134The other residues R¹, R², R³, R⁴ or R⁵ are, in each case independently of one another, preferably selected from the group consisting of hydrogen, linear, branched or ring-comprising structural elements with 1 to 25 C atoms and 0 to 8 heteroatoms, the heteroatoms optionally present preferably being selected from the group consisting of N. and O.

0135The other residues R¹, R², R³, R⁴ or R⁵ are, in each case independently of one another, particularly preferably selected from the group consisting of hydrogen, linear, branched or ring-comprising structural elements with 1 to 20 C atoms and 0 to 5 heteroatoms, the heteroatoms optionally present being selected from the group consisting of N. and O.

0136In compounds of the structure Q (Y_xZ._e)_b Y is a structural element which contains or consists of a structural element which is selected from the group consisting of<chemistry id="chem0008" num="0008"><img file="EP2436366A2_D0008.tif" /></chemistry><chemistry id="chem0009" num="0009"><img file="EP2436366A2_D0009.tif" /></chemistry>the binding arranged on the left in the formula picture is closer to the structural element Q and the binding arranged on the right is closer to the structural element Z.

0137The compounds of the structure Q (Y_xZ._e)_b can be obtained according to production processes known to the person skilled in the art.

0138Compounds of the structure Q (Y_xZ._e)_b with an amide structural element can be obtained, for example, by reacting (i) an educt compound with an isocyanate group and (ii) an educt compound with a carboxylic acid group.

0139Compounds of the structure Q (Y_xZ._e)_b with a urethane structural element can be obtained, for example, by reacting (i) an educt compound with an isocyanate group and an educt compound with an alcohol group.

0140Compounds of the structure Q (Y_xZ._e)_b with a urea structural element can be obtained, for example, by reacting (i) a starting material compound with an isocyanate group and (ii) a starting material compound with an amino group.

0141Compounds of the structure Q (Y_xZ._e)_b with an allophanate structural element can be obtained, for example, by reacting (i) a starting material compound with a urethane group and (ii) a starting material compound with an isocyanate group.

0142Compounds of the structure Q (Y_xZ._e)_b with a biuret structural element can be obtained, for example, by reacting (i) a starting material compound with a urea group and (ii) a starting material compound with an isocyanate group.

0143Compounds of the structure Q (Y_xZ._e)_b with a <i>N</i>Acylurea structural elements can be obtained, for example, by reacting (i) a starting material compound with an amide group and (ii) a starting material compound with an isocyanate group.

0144In a preferred embodiment of a composite material to be used according to the invention, component (b1) is selected such that it comprises or consists of bis (methacrylolyoxymethyl) tricyclo [5.2.1.0^2,6] decane and / or bis (acrylolyoxymethyl) tricyclo [5.2.1.0^2,6] decan.

0145In the composite material to be used according to the invention, the methacrylic acid esters are preferred over the corresponding acrylic acid esters because of their higher biocompatibility, ie that Z in compounds of the structure Q (Y_xZ._e)_b preferably -O- (C = O) -C (CH₃) = CH₂ means.

0146Preferred compounds (monomers) of structure Q (YZ_e)_bComponent (b1) are those with one, two, three, four or more functional groups selected from the group consisting of urethane, urea, N-acylurea, allophanate, biuret and amide, the amide function not being directly related to an N atom , an O atom or a carbonyl group.

0147In the field of dental technology there is a constant need for further, preferably free-radically, polymerizable monomers with which dental materials with certain properties can be produced.

0148In the context of the present text, (meth) acrylic means both acrylic and methacrylic.

0149<patcit id="pcit0039" dnum="EP1238993A"><text>EP 1 238 993</text></patcit> describes a process for the preparation of polyisocyanates containing acylurea groups and mixtures thereof and their use as starting components in the production of polyurethane plastics.

0150<patcit id="pcit0040" dnum="EP0209700A2"><text>EP 0 209 700 A2</text></patcit> and <patcit id="pcit0041" dnum="DE3522005"><text>DE 35 22 005</text></patcit> describe (meth) acrylic acid derivatives of certain tricyclodecanes with double-bonded bridge members from the group of urethanes or ureas, which can be used in the dental field.

0151<patcit id="pcit0042" dnum="EP0000194A1"><text>EP 0 000 194 A1</text></patcit> (corresponding <patcit id="pcit0043" dnum="US4160080A"><text>US 4,160,080</text></patcit>) describes polyisocyanates that contain allophanate groups. These allophanate polyisocyanates can be used for the production of polyurethane foams, elastomers, thermosets, coatings, bonds and paints.

0152<patcit id="pcit0044" dnum="EP0682012B1"><text>EP 0 682 012 B1</text></patcit> relates to a process for the preparation of light-colored lightfast allophanate groups (cyclo) aliphatic polyisocyanates, by reacting organic compounds containing urethane groups with organic polyisocyanates with (cyclo) aliphatic isocyanate groups in the presence of tin (II) salts. In the<patcit id="pcit0045" dnum="EP0682012B1"><text>EP 0 682 012 B1</text></patcit> The polyisocyanates described can be used as a structural component in the production of polyurethane plastics.

0153<patcit id="pcit0046" dnum="EP1727846B1"><text>EP 1 727 846 B1</text></patcit> discloses a process for the preparation of binders containing allophanate groups which, under the action of actinic radiation, have groups reacting with ethylenically unsaturated compounds under polymerization and optionally NCO-reactive groups.

0154<patcit id="pcit0047" dnum="EP0712840B1"><text>EP 0 712 840 B1</text></patcit> relates to a process for the preparation of certain polyisocyanates containing allophanate groups by reaction with allophanate formation of compounds containing urethane groups. The connections according to<patcit id="pcit0048" dnum="EP0712840B1"><text>EP 0 712 840 B1</text></patcit> can be used as a binder or binder component in coating compositions.

0155<patcit id="pcit0049" dnum="EP0867457B1"><text>EP 0 867 457 B1</text></patcit> discloses an ethylenically unsaturated polyurethane which is substantially free of isocyanate groups, which is the reaction product of an ethylenically unsaturated polyisocyanate containing allophanate groups and β, γ-ethylenically unsaturated ether groups with a hydroxy-functional, ethylenically unsaturated compound, wherein the ethylenically unsaturated polyisocyanate is prepared by allophanating the urethane group-containing reaction product of an organic diisocyanate with a β, γ-ethylenically unsaturated ether alcohol, wherein the β, γ-ethylenically unsaturated ether alcohol comprises a compound consisting of the glyceryl diallyl ether, trimethylolpropane thio-triallyl ether and penta-triallyl ether Group is selected. In the<patcit id="pcit0050" dnum="EP0867457B1"><text>EP 0 867 457 B1</text></patcit> disclosed ethylenically unsaturated polyurethanes with allophanate groups can be used as binders in one-component coating compositions.

0156<patcit id="pcit0051" dnum="DE102007040240A1"><text>DE 10 2007 040 240 A1</text></patcit> and <patcit id="pcit0052" dnum="EP1645582A1"><text>EP 1 645 582 A1</text></patcit> describe processes for the preparation of radiation-curing allophanates by reacting compounds containing isocyanate groups and hydroxy-functional compounds, the ratio of NCO groups to OH groups being 1.45: 1.0 to 1.1: 1.0. According to<patcit id="pcit0053" dnum="DE102007040239A1"><text>DE 10 2007 040 239 A1</text></patcit> Corresponding radiation-curing allophanates are obtained using certain mixtures containing hydroxyethyl acrylate and hydroxypropyl acrylate as hydroxy-functional compounds. The radiation-curing allophanates according to these three documents can be used for the production of coatings and lacquers as well as adhesives, printing inks, casting resins, dental compounds, sizes, photoresists, stereolithography systems, resins for composite materials and sealing compounds.

0157<patcit id="pcit0054" dnum="DE102004060285A1"><text>DE 10 2004 060 285 A1</text></patcit> relates to radiation-curable compositions based on a dicidol mixture (containing two or three isomeric 3,8-, 4,8- and / or 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decane) with at least one compound which has at least one ethylenically unsaturated group with at least one group which is reactive toward dicidol, which compound can be a reaction product of hydroxyalkyl (meth) acrylate and diisocyanate. The compositions according to<patcit id="pcit0055" dnum="DE102004060285A1"><text>DE 10 2004 060 285 A1</text></patcit> can be used as radiation-induced curing coating materials, adhesives, laminations, printing inks and inks, polishes, glazes, pigment pastes, fillers, cosmetic articles, packaging materials and / or sealants and / or insulating materials.

0158<patcit id="pcit0056" dnum="WO2006063891A1"><text>WO 2006/063891 A1</text></patcit> discloses free-radically polymerizable compounds, essentially containing the reaction product of a dicidol mixture and at least one compound which has at least one ethylenically unsaturated group with at least one group which is reactive toward dicidol. The areas of application correspond to those in<patcit id="pcit0057" dnum="DE102004060285A1"><text>DE 10 2004 060 285 A1</text></patcit> mentioned.

0159<patcit id="pcit0058" dnum="US6670499B1"><text>US 6,670,499 B1</text></patcit> describes diurethanes derived from adamantane. In the<patcit id="pcit0059" dnum="US6670499B"><text>US 6,670,499</text></patcit> Compounds described are suitable as intermediates for use in the dental field or for the production of optical materials (such as lenses).

0160It was therefore a further object of the present invention to provide new, preferably free-radically polymerizable, monomers which can be used in or as part of component (b1) in a dental composite material according to the invention or to be used or to be used according to the invention.

0161The polymers obtainable using the monomers should preferably have a pronounced hydrophobicity, which is evident, inter alia, in a very low water absorption. The polymers obtainable using the monomers should also preferably be distinguished by high mechanical stability, which is evident, inter alia, in a high flexural strength. It should be particularly preferred to use the monomers to produce polymers which have both low water absorption and high flexural strength as well as excellent flow behavior.

0162This further problem is solved by connecting the structure Q (YZ_e)_b (where each Y is selected independently of any further structural elements Y) with one, two, three, four or more functional groups selected from the group consisting of <i>N</i>Acylurea, allophanate, biuret and amide, where the amide function is not directly linked to an N atom, an O atom or a carbonyl group, where:<ul id="ul0022" list-style="dash"><li>Q denotes a saturated or olefinically unsaturated polyalicyclic structural element selected from the group consisting of bicyclic, tricyclic, tetracyclic, pentacyclic and hexacyclic hydrocarbon radicals, optionally one, two or more of those not substituted by substituents YZ_e substituted hydrogen atoms of this polyalicyclic structural element Q are substituted by alkyl groups (preferably C1-C4-alkyl), alkoxy groups (preferably C1-C4-alkoxy), halogen atoms (preferably F) or trifluoromethyl groups,</li><li>b is a natural number selected from the group of natural numbers 2, 3, 4,</li><li>each Z means a structural element which is selected independently of any further structural elements Z from the group consisting of          -O- (C = O) -CH = CH₂, -O- (C = O) -C (CH₃) = CH₂,          - (C = O) -CH = CH₂, - (C = O) -C (CH₃) = CH₂,          -CH = CH₂, -C (CH₃) = CH₂ and -O-CH = CH₂, </li><li>each index e is a natural number, which is selected independently of any further indices e from the group of natural numbers 1, 2, 3 and 4,</li><li>each Y means a structural element, which in the structure Q (YZ_e)_b connects the polyalicyclic structural element Q with e structural elements Z,</li></ul>wherein the compound is a first reaction product from a first reaction of<ol id="ol0004"><li>A) a connection of the structure QG_b, wherein each G represents a reactive group which is selected independently of further groups G from the group consisting of (-CH₂)_n-NH₂, (-CH₂)_n- (OCH₂-CHR)_m-OH, (-CH₂)_n-NCO and (-CH₂)_n-COOH with</li><li>B) two or more identical or different connections MZ_e, where M is a structural element which in each case has one or more group (s) reactive towards the reactive groups G selected from the group consisting of -NH, -NH₂, -OH, -NCO and -COOH, where:<ul id="ul0023" list-style="dash"><li>R each represents, independently of any further R, a hydrogen atom or an alkyl radical; R is preferably a hydrogen atom or a linear or branched alkyl radical having 1 to 6 carbon atoms; more preferably R represents a hydrogen atom or a methyl radical,</li><li>m is a natural number selected from the group of natural numbers from 0 to 10,</li><li>each index n is a natural number, which is selected independently of any further indices n from the group consisting of 0 and 1,</li></ul>or the compound is a second reaction product from a reaction of the above first reaction product with</li><li>C) a further compound according to A) or B), each further compound according to A) or B) having the above meaning, regardless of the meaning of A) or B) in the first reaction, or the compound a third reaction product is from a reaction of the above second reaction product with</li><li>D) a further compound according to A) or B), each further compound according to A) or B) having the above meaning, regardless of the meaning of A) or B) in the first or second reaction.</li></ol>

0163It follows from the above that in compounds to be used according to the invention which contain an amide group (as defined), this amide group is not part of a urethane group.

0164Compounds of the structure Q (YZ.) To be used according to the invention are further preferred_e)_b (wherein each Y is selected independently of any further structural elements Y) of component (b1) with one, two, three, four or more functional groups selected from the group consisting of <i>N</i>Acylurea, allophanate, biuret and amide, the amide function not being directly linked to an N atom, an O atom or a carbonyl group, the amide again preferably meaning (meth) acrylamide.

0165In preferred compounds of the structure Q (YZ_e)_b (where each Y is selected independently of any other structural elements Y), the link between Q and at least one structural element Z takes place via a bridge which contains or consists of a double-link bridge member, selected from the group consisting of<chemistry id="chem0010" num="0010"><img file="EP2436366A2_D0010.tif" /></chemistry><chemistry id="chem0011" num="0011"><img file="EP2436366A2_D0011.tif" /></chemistry><chemistry id="chem0012" num="0012"><img file="EP2436366A2_D0012.tif" /></chemistry><chemistry id="chem0013" num="0013"><img file="EP2436366A2_D0013.tif" /></chemistry><chemistry id="chem0014" num="0014"><img file="EP2436366A2_D0014.tif" /></chemistry>where R¹, R², R³ R⁴, R⁵ mean other residues of the compound, the bond arranged on the left in the formula being closer to the structural element Q and the bond arranged on the right closer to the structural element Z.

0166The further task is also solved by new connections of the structure Q (Y_xZ._e)_b with x = 1 with one, two, three, four or more functional groups which are selected from the group consisting of <i>N</i>-Acylurea, allophanate and biuret, where:<ul id="ul0024" list-style="dash"><li>Q represents a saturated or olefinically unsaturated polyalicyclic structural element selected from the group consisting of bicyclic, tricyclic, tetracyclic, pentacyclic and hexacyclic hydrocarbon radicals, none, one, two or more of the substituents not having YZ_e substituted hydrogen atoms of this polyalicyclic structural element Q is or are substituted by alkyl groups, alkoxy groups, halogen atoms or trifluoromethyl groups;</li><li>b is a natural number selected from the group of natural numbers 2, 3, 4;</li><li>each Z means a structural element which is selected independently of any further structural elements Z from the group consisting of          -O- (C = O) -CH = CH₂, -O- (C = O) -C (CH₃) = CH₂,          - (C = O) -CH = CH₂, - (C = O) -C (CH₃) = CH₂,          -CH = CH₂, -C (CH₃) = CH₂ and -O-CH = CH₂, </li><li>each index e is a natural number, which is selected independently of any further indices e from the group of natural numbers 1, 2, 3 and 4;</li><li>each Y means a structural element, which in the structure Q (Y_xZ._e)_b with x = 1 the polyalicyclic structural element Q is linked to e structural elements Z and contains or consists of a structural element, selected from the group consisting of<chemistry id="chem0015" num="0015"><img file="EP2436366A2_D0015.tif" /></chemistry><chemistry id="chem0016" num="0016"><img file="EP2436366A2_D0016.tif" /></chemistry><chemistry id="chem0017" num="0017"><img file="EP2436366A2_D0017.tif" /></chemistry><chemistry id="chem0018" num="0018"><img file="EP2436366A2_D0018.tif" /></chemistry></li></ul>where R¹, R² and R³ mean other residues of the compound, the bond arranged on the left in the formula being closer to the structural element Q and the bond arranged on the right closer to the structural element Z. These compounds are particularly suitable as monomers for use in composite materials according to the invention.

0167Such a connection of the structure Q (Y_xZ._e)_b with x = 1 two, three, four or more functional groups selected from the group consisting of N-acylurea, allophanate and biuret.

0168In a preferred embodiment, each index e means a natural number, which is selected independently of any further indices e from the group of natural numbers 2, 3 and 4.

0169The above-mentioned other residues R¹, R² or R³ of a new compound to be used according to the invention, in each case independently of one another, are preferably selected from the group consisting of hydrogen, linear, branched or rings comprising structural elements with 1 to 30 C atoms and 0 to 10 heteroatoms, the heteroatoms optionally present preferably being selected from the Group consisting of N and O.

0170The other residues R¹, R² or R³ of a new compound to be used according to the invention are, in each case independently of one another, preferably selected from the group consisting of hydrogen, linear, branched or rings comprising structural elements with 1 to 25 carbon atoms and 0 to 8 heteroatoms, the heteroatoms optionally present preferably being selected from the Group consisting of N and O.

0171The other residues R¹, R² or R³ of a new compound to be used according to the invention are, in each case independently of one another, preferably selected from the group consisting of hydrogen, linear, branched or rings comprising structural elements with 1 to 20 C atoms and 0 to 5 heteroatoms, the heteroatoms which may be present being selected from the group consisting of N and O.

0172A new compound Q (Y. To be used in a composite material according to the invention or to be used according to the invention_xZ._e)_b with x = 1, preferably a compound Q (Y_xZ._e)_b with x = 1 as referred to above or below as preferred, can preferably be produced by reacting a first reaction product, which is the reaction product from a first reaction of<ol id="ol0005"><li>A) a connection of the structure QG_b, wherein each G represents a reactive group which is selected independently of further groups G from the group consisting of (-CH₂)_n-NH₂, (-CH₂)_n- (OCH₂-CHR)_m-OH, (-CH₂)_n-NCO and (-CH₂)_n-COOH with</li><li>B) two or more identical or different connections MZ_e, where M is a structural element which in each case has one or more group (s) reactive towards the reactive groups G selected from the group consisting of -NH, -NH₂, -OH, -NCO and -COOH, where:<ul id="ul0025" list-style="dash"><li>R each represents, independently of any further R, a hydrogen atom or an alkyl radical;</li><li>m is a natural number selected from the group of natural numbers from 0 to 10,</li><li>each index n is a natural number, which is selected independently of any further indices n from the group consisting of 0 and 1,</li></ul>wherein the compound is a second reaction product from a reaction of the above first reaction product with</li><li>C) a further compound according to A) or B), each further compound according to A) or B) having the above meaning, regardless of the meaning of A) or B) in the first reaction, or the compound a third reaction product is from a reaction of the above second reaction product with</li><li>D) a further compound according to A) or B), each further compound according to A) or B) having the above meaning, regardless of the meaning of A) or B) in the first or second reaction.</li></ol>

0173A preferred compound to be used according to a preferred embodiment is a second reaction product from a reaction of the above first reaction product with<ul id="ul0026" list-style="none"><li>C) a further compound according to A) or B), each further compound according to A) or B) having the same meaning as in the first reaction, and or wherein the compound is a third reaction product from a reaction of the above second reaction product with</li><li>D) a further compound according to A) or B), each further compound according to A) or B) having the same meaning as in the first and / or the second reaction, preferably as in the first and the second reaction.</li></ul>

0174In a preferred embodiment, m = 0. This applies to all aspects of the present invention.

0175In preferred connections to be used according to the invention, the link between Q and at least one structural element Z is established via a bridge which contains or consists of a double-bonded bridge member, selected from the group consisting of<chemistry id="chem0019" num="0019"><img file="EP2436366A2_D0019.tif" /></chemistry><chemistry id="chem0020" num="0020"><img file="EP2436366A2_D0020.tif" /></chemistry><chemistry id="chem0021" num="0021"><img file="EP2436366A2_D0021.tif" /></chemistry><chemistry id="chem0022" num="0022"><img file="EP2436366A2_D0022.tif" /></chemistry><chemistry id="chem0023" num="0023"><img file="EP2436366A2_D0023.tif" /></chemistry><chemistry id="chem0024" num="0024"><img file="EP2436366A2_D0024.tif" /></chemistry>where R¹, R², R³ R⁴, R⁵ mean other radicals of the compound and Q and the index n have the meaning given above.

0176The binding arranged on the right in the formula picture is closer to the structural element Z.

0177In a preferred embodiment, a new compound Q (Y_xZ._e)_b with x = 1, preferably a compound Q (Y_xZ._e)_b with x = 1 as it is referred to as preferred above or below, one or more structural elements selected from the group consisting of<chemistry id="chem0025" num="0025"><img file="EP2436366A2_D0025.tif" /></chemistry><chemistry id="chem0026" num="0026"><img file="EP2436366A2_D0026.tif" /></chemistry><chemistry id="chem0027" num="0027"><img file="EP2436366A2_D0027.tif" /></chemistry><chemistry id="chem0028" num="0028"><img file="EP2436366A2_D0028.tif" /></chemistry><chemistry id="chem0029" num="0029"><img file="EP2436366A2_D0029.tif" /></chemistry>where R¹, R² and R³ other radicals of the compound mean (and preferably have the preferred meaning given above) and Q has the meaning given above and the index n is selected from the group consisting of 0 and 1.

0178As already mentioned above, preferred new compounds to be used according to the invention are those in which Q is a saturated polyalicyclic structural element which is selected from the group consisting of bicyclic and tricyclic hydrocarbon radicals, preferably none of the substituents YZ_e substituted hydrogen atoms of this polyalicyclic structural element Q is substituted.

0179Particularly preferred new compounds to be used according to the invention are those in which the structural element Q is a tricyclo [5.2.1.0^2,6] decane residue, a tricyclo [5.2.1.0^2,6] dec-3-ene residue, a tricyclo [3.3.1.1^3,7] decane residue or a bicyclo [2.2.1] heptane residue.

0180Preferred new compounds of component (b1) to be used according to the invention are those in which Q is a tricyclic hydrocarbon radical, preferably none of the YZ substituents not being substituted by_e (where each Y is selected or omitted independently of any further structural elements Y) substituted hydrogen atoms of this tricyclic hydrocarbon radical is substituted.

0181Particularly preferred new compounds to be used according to the invention are those in which the structural element Q is a tricyclo [5.2.1.0^2,6] decane residue, a tricyclo [5.2.1.0^2,6] dec-3-ene residue or a tricyclo [3.3.1.1^3,7] decane radical means, more preferably a tricyclo [5.2.1.0^2,6] decane residue or a tricyclo [3.3.1.1^3,7] decan rest.

0182Preferred new compounds to be used according to the invention are those in which<ol id="ol0006"><li>(i) the structural element Z = -O- (C = O) -C (CH₃) = CH₂ means, the functional groups being allophanate, biuret or acylurea groups, since particularly good results have been achieved with these compounds, and or</li><li>(ii) the structural element Q is a tricyclo [5.2.1.0^2,6] decan residue means.</li></ol>

0183Also preferred are new compounds to be used according to the invention, in which the structural element Z = -O- (C = O) -C (CH₃) = CH₂ means, the functional groups being allophanate, biuret or acylurea groups and the structural element Q being a tricyclo [5.2.1.0^2,6] decan residue means.

0184Preferred are new compounds to be used according to the invention, in which all existing light-curable groups correspond to the structural element Z.

0185Preferred are new compounds to be used according to the invention, in which all existing terminal polymerizable groups correspond to the structural element Z.

0186A new compound to be used according to the invention can, in addition to light-curable groups of the structural element Z, also comprise further polymerizable, preferably terminally polymerizable, groups which are not light-curable, in particular not under the conditions of light curing which are customary in the dental field. However, this is usually not preferred since such groups do not contribute to the desired properties of the product present after the polymerization.

0187Further preferred compounds to be used according to the invention are those in which at least one structural element YZ_e independent of the one or more structural elements YZ_e is selected, and preferably all structural elements YZ_e are selected from the group consisting of<chemistry id="chem0030" num="0030"><img file="EP2436366A2_D0030.tif" /></chemistry><chemistry id="chem0031" num="0031"><img file="EP2436366A2_D0031.tif" /></chemistry><chemistry id="chem0032" num="0032"><img file="EP2436366A2_D0032.tif" /></chemistry><chemistry id="chem0033" num="0033"><img file="EP2436366A2_D0033.tif" /></chemistry><chemistry id="chem0034" num="0034"><img file="EP2436366A2_D0034.tif" /></chemistry>where Z, R, m and n have the meaning given above and in which the following also applies:<ul id="ul0027" list-style="dash"><li>each A means a double-bonded organic bridge link,</li><li>each index k is a natural number, which is selected independently of any further indices k from the group consisting of 0 and 1;</li><li>each R 'denotes a structural element which is selected independently of any further structural elements R' from the group consisting of H and a structural element (C = O) -NH- (A)_k-Z, where A, Z and k in turn have the above meanings.</li></ul>

0188In a preferred embodiment, m = 0.

0189Likewise preferred compounds to be used according to the invention are those in which at least one structural element YZ_e independent of the one or more structural elements YZ_e is selected, and preferably all structural elements YZ_e are selected from the group consisting of<chemistry id="chem0035" num="0035"><img file="EP2436366A2_D0035.tif" /></chemistry><chemistry id="chem0036" num="0036"><img file="EP2436366A2_D0036.tif" /></chemistry><chemistry id="chem0037" num="0037"><img file="EP2436366A2_D0037.tif" /></chemistry><chemistry id="chem0038" num="0038"><img file="EP2436366A2_D0038.tif" /></chemistry><chemistry id="chem0039" num="0039"><img file="EP2436366A2_D0039.tif" /></chemistry><chemistry id="chem0040" num="0040"><img file="EP2436366A2_D0040.tif" /></chemistry><chemistry id="chem0041" num="0041"><img file="EP2436366A2_D0041.tif" /></chemistry><chemistry id="chem0042" num="0042"><img file="EP2436366A2_D0042.tif" /></chemistry><chemistry id="chem0043" num="0043"><img file="EP2436366A2_D0043.tif" /></chemistry><chemistry id="chem0044" num="0044"><img file="EP2436366A2_D0044.tif" /></chemistry>where each Q has the above meaning independently of any other structural elements Q and where Z, A, k and R 'and n have the meaning given above.

0190In a preferred embodiment, the present invention relates to a compound Q (Y_xZ._e)_b with x = 1, preferably a compound Q (Y_xZ._e)_b with x = 1 as described above or below as preferred, at least one structural element YZ_e independent of the one or more structural elements YZ_e is selected, and preferably all structural elements YZ_e are selected from the group consisting of<chemistry id="chem0045" num="0045"><img file="EP2436366A2_D0045.tif" /></chemistry><chemistry id="chem0046" num="0046"><img file="EP2436366A2_D0046.tif" /></chemistry><chemistry id="chem0047" num="0047"><img file="EP2436366A2_D0047.tif" /></chemistry><chemistry id="chem0048" num="0048"><img file="EP2436366A2_D0048.tif" /></chemistry>where Z, R, m and n have the meaning given above and in which the following also applies:<ul id="ul0028" list-style="dash"><li>each A means an organic structural element,</li><li>each index k is a natural number, which is selected independently of any further indices k from the group consisting of 0 and 1;</li><li>each R 'denotes a structural element which is selected independently of any further structural elements R' from the group consisting of H and a structural element (C = O) -NH- (A)_k-Z, where A, Z and k in turn have the above meanings.</li></ul>

0191In a preferred embodiment, the present invention relates to a new compound Q (Y_xZ._e)_b with x = 1, preferably a compound Q (Y_xZ._e)_b with x = 1 as described above or below as preferred, wherein at least one structural element YZ_e independent of the one or more structural elements YZ_e is selected, and preferably all structural elements YZ_e are selected from the group consisting of<chemistry id="chem0049" num="0049"><img file="EP2436366A2_D0049.tif" /></chemistry><chemistry id="chem0050" num="0050"><img file="EP2436366A2_D0050.tif" /></chemistry><chemistry id="chem0051" num="0051"><img file="EP2436366A2_D0051.tif" /></chemistry><chemistry id="chem0052" num="0052"><img file="EP2436366A2_D0052.tif" /></chemistry><chemistry id="chem0053" num="0053"><img file="EP2436366A2_D0053.tif" /></chemistry><chemistry id="chem0054" num="0054"><img file="EP2436366A2_D0054.tif" /></chemistry><chemistry id="chem0055" num="0055"><img file="EP2436366A2_D0055.tif" /></chemistry>where each Q has the above meaning independently of any other structural elements Q, and where Z and n have the meaning given above and where:<ul id="ul0029" list-style="dash"><li>each A means an organic structural element,</li><li>each index k is a natural number, which is selected independently of any further indices k from the group consisting of 0 and 1;</li><li>each R 'denotes a structural element which is selected independently of any further structural elements R' from the group consisting of H and a structural element (C = O) -NH- (A)_k-Z, where A, Z and k in turn have the above meanings.</li></ul>

0192Again preferred are compounds to be used according to the invention in which each structural element A is selected independently of any further structural elements A from the group consisting of linear, branched or rings-containing double-bonded organic bridge members with 1 to 25 C atoms and optionally 1 to 10, preferably 1 up to 5 heteroatoms, the heteroatoms which may be present preferably being selected from the group consisting of N and O.

0193Here again, preference is given to a compound to be used according to the invention in which each structural element A is selected independently of any further structural elements A from the group consisting of linear, branched or ring-shaped structural elements with 1 to 25 C atoms and 0 to 10 heteroatoms, preferably with 1 up to 5 heteroatoms, the heteroatoms optionally present preferably being selected from the group consisting of N and O.

0194Further preferred are compounds in which each structural element A is selected independently of any further structural elements A from the group consisting of C.₁-C₂₀Alkylene, C₁-C₂₀Heteroalkylene, C₃-C₂₀-Cycloalkylene, C₄-C₂₀-Cycloalkylalkylene, C₂-C₂₀Alkenylene, C₃-C₂₀-Cycloalkenylene, C₄-C₂₀-Cycloalkenylalkylene, C₄-C₂₀-Cycloalkenylenealkylene, C₃-C₂₅- Arlen, C₂-C₂₅Heteroarylene, C₄-C₂₅Arylalkylene, C₄-C₂₅Arylalkylene, C₄-C₂₅Aryl heteroalkylene, C₄-C₂₅Arylene heteroalkylene.

0195In preferred configurations, structural element A comprises one or more of the following atoms or groups of atoms:          -O-, -O-Ar¹-CR⁶R⁷-Ar²-O-, -NR⁸-, -N- (C = O) -, -NH- (C = O) -O-, -NH-C (= O) -NH- where:<ul id="ul0030" list-style="none"><li>Ar¹ and Ar² independently of one another represent an optionally substituted, preferably an aromatic ring substituted one or more times with C1-C4-alkyl radicals, again preferably a phenyl ring,</li><li>R⁶, R⁷ and R⁸ independently of one another denote hydrogen or a C1-C8 radical, preferably a C1-C4 alkyl radical, again preferably methyl or ethyl.</li></ul>

0196To produce the compounds of structure Q (YZ_e)_b or Q (Y_xZ._e)_b Hydroxyl compounds of (meth) acrylates can preferably be used, and mixtures of acrylates and methacrylates can also be used. The following are preferred for use as reactants according to component B), C) or D):<ul id="ul0031" list-style="none" compact="compact"><li>Alkylene oxide mono (meth) acrylates such as ethylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, etc., polyalkylene oxide mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate (polypropylene glycol mono) ) acrylate, polybutylene glycol mono (meth) acrylate, etc., hydroxyalkyl mono (meth) acrylates such as, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxynonyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxyundecyl (meth) acrylate, hydroxydodecyl (meth) acrylate, etc., poly (ε-caprolactone) mono (meth) acrylate, poly (γ-caprolactone) mono (meth ) acrylate, etc., the mono-, di-, tetra- or penta (meth) acrylates of polyhydric alcohols, such as glycerol, such as, for example, glycerol di (meth) acrylate (2-hydroxypropyl-1,3-di (meth) acrylate, 3-hydroxypropyl-1,2-di (meth) acrylate), such as trimethylolpropane, such as trimethylolpropane di (meth) acrylate, such as pentaerythritol such as, for example, pentaerythritol tri (meth) acrylate, such as dipentaerythritol, such as, for example, dipentaerythritol penta (meth) acrylate, such as ditrimethylolpropane tri (meth) acrylate, such as neopentylglycol (meth) acrylate, the (meth) acrylates of alkoxylated or phenoxylated glycerol, preferably the (meth) acrylates of ethoxylated, propoxylated, etc. glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, ditrimethylolpropane, etc. and their technical mixtures, bisphenol-A-glycidyl (meth) acrylate (bis-GMA), bisphenol-B -Glycidyl- (meth) acrylate, bisphenol-C-glycidyl- (meth) acrylate, bisphenol-F-glycidyl- (meth) acrylate, alkoxylated bisphenol-A-glycidyl- (meth) acrylate (e.g. ethoxylated bisphenol-A-glycidyl- (Meth) acrylate), etc.</li></ul>

0197Isocyanates can also be used as component B) to prepare the compounds to be used according to the invention. Mono- and diisocyanates are preferred.

0198Preferred diisocyanates are selected from the group consisting of cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyl diethylcyclohexane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, hexane diisocyanate, such as diisocyanate diisocyanate, such as diisocyanate diisocyanate, butane diisocyanate, Heptane diisocyanate, octane diisocyanate, nonane diisocyanate, such as 1,6-DÜsocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane, nonane triisocyanate, such as 4-isocyanatomethyl-1,8-octane diisocyanate, decanedi and triisocyanate, undecanedi and triisocyanate, dodecane and triisocyanates, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isocyanatomethylmethylcyclohexyl isocyanate, 1,3-bis (isocyanatomethyl) cyclohexane or 1,4-bis (isocyanatomethyl) cyclohexane.

0199Preferred monoisocyanates are (meth) acryloyl isocyanate and (meth) acrylic-C2-C8-alkyl isocyanates (ie (meth) acrylic alkyl isocyanates with alkyl spacers which have 2 to 8, particularly preferably 2 to 6 carbon atoms), and again (meth) acrylic ethyl isocyanate is preferred (2-isocyanatoethyl (meth) acrylate).

0200In addition, monoisocyanates have proven to be advantageous as component B), the reaction products are composed of amino- or hydroxyalkyl (meth) acrylates, the alkyl spacers of which have 1 to 12, preferably 2 to 8, particularly preferably 2 to 6, carbon atoms, and diisocyanates.

0201For this purpose, an above-mentioned diisocyanate is preferably reacted in an equimolar amount with an amino or hydroxylalkyl compound (identified as preferred above) of a (meth) acrylate, the hydroxylalkyl compounds in turn preferably being selected from the group consisting of hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate , Hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate.

0202The reaction products in a molar ratio of 1: 1 of hydroxyethyl methacrylate with isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate or hexamethylene diisocyanate may be mentioned as examples.

0203The present invention further relates to the use or the use of a compound mentioned above, preferably in one of the configurations identified as preferred or particularly preferred, in a composite material according to the invention or to be used according to the invention for the stated purposes, preferably in a dental composite material.

0204The present invention also relates to the use of a compound of the structure Q (YZ_e)_b or Q (Y_xZ._e)_b, preferably in one of the configurations marked as preferred or particularly preferred, for producing a composite material, preferably a dental composite material, in particular a dental sealing material for sealing fissures, for sealing dimples and for sealing carious lesions.

0205The present invention also relates to the compounds of structure Q (YZ_e)_b or Q (Y_xZ._e)_b, preferably in one of the configurations marked as preferred or particularly preferred, as or for use or for use as a dental sealing material, preferably as sealing material for sealing fissures, for sealing dimples and for sealing carious lesions.

0206The present invention further relates to a method for producing a compound Q (YZ_e)_b or a mixture comprising at least one compound Q (YZ_e)_bwhich can advantageously be used in or as component (b1) of a composite material according to the invention or to be used according to the invention, with the following steps:<ul id="ul0032" list-style="none" compact="compact"><li>Implementing in a first reaction<ol id="ol0007"><li>A) a connection of the structure QG_b, wherein each G represents a reactive group which is selected independently of further groups G from the group consisting of (-CH₂)_n-NH₂, (-CH₂)_n- (OCH₂-CHR)_m-OH, (-CH₂)_n-NCO and (-CH₂)_n-COOH, preferably a compound of structure QG_b, wherein each G represents a reactive group which is selected independently of other groups G from the group consisting of -NH₂, -CH₂NH₂, -OH, -CH₂OH, -NCO, -CH₂NCO, and - COOH, With</li><li>B) two or more identical or different connections MZ_e, where M is a structural element which in each case has one or more group (s) reactive towards the reactive groups G selected from the group consisting of -NH, -NH₂, -OH, -NCO and -COOH to a first implementation product, optionally in a second reaction, reacting the first reaction product with</li><li>C) a further compound according to A) or B), each further compound according to A) or B) having the above meaning, regardless of the meaning of A) or B) in the first reaction, to a second implementation product and optionally in a third reaction, reacting the second reaction product with</li><li>D) a further compound according to A) or B), each further compound according to A) or B) having the above meaning, regardless of the meaning of A) or B) in the first or second reaction. where Q, b, Y, Z, and e each have the meaning given above, and where:<ul id="ul0033" list-style="dash"><li>R each represents, independently of any further R, a hydrogen atom or an alkyl radical; R is preferably a hydrogen atom or a linear or branched alkyl radical having 1 to 6 carbon atoms; more preferably R represents a hydrogen atom or a methyl radical;</li><li>m is a natural number selected from the group of natural numbers from 0 to 10,</li><li>each index n is a natural number, which is selected independently of any further indices n from the group consisting of 0 and 1,</li></ul></li></ol></li></ul>where the ratio of the total number of NCO groups to the total number of -NH₂, - OH and -COOH in the total number of compounds according to A) and B) in the first, optionally second and optionally third reaction is greater than or equal to 1, preferably in the range from 1.1: 1 to 5: 1 is preferably in the range from 1.25: 1 to 4: 1, particularly preferably in the range from 1.5: 1 to 3: 1, and most preferably in the range from 2: 1 to 2.5: 1.

0207The ratio of the total number of converted NCO groups to the total number of -NH converted₂, -OH and -COOH in the total number of compounds according to A) and B) in the first, optionally second and optionally third reaction, preferably in the range from 1.1: 1 to 5: 1, more preferably in the range from 1.25: 1 to 4: 1, particularly preferably in the range from 1.5: 1 to 3: 1, and most preferably in the range from 2: 1 to 2.5: 1.

0208The reaction to the first reaction product, to the second reaction product and / or to the third reaction product is preferably carried out in the presence of a catalyst.

0209Preferred catalysts here are tertiary amines or Lewis acids, in turn preferably metal salts of higher fatty acids, in particular dibutyltin dilaurate or tin (II) octoate.

0210The amount of the catalyst is preferably in the range from 0.01 to 2% by weight, preferably from 0.08 to 1% by weight, based on the total amount of the reactants according to A) and B) and, if appropriate, C) and, if appropriate D).

0211The reaction to the first reaction product, to the second reaction product and / or to the third reaction product preferably takes place in a temperature range from 0 to 160 ° C., preferably in the range from 30 to 140 ° C. and particularly preferably in the range from 60 to 120 ° C. . The reaction is preferably carried out at normal pressure (1013 mbar).

0212The above or following explanations regarding the compounds to be used according to the invention as preferred and particularly preferred apply accordingly to the preferred and particularly preferred embodiments of the methods, mixtures, mixtures, products and uses according to the invention.

0213In a further aspect, the present invention relates to a mixture comprising one, two or more different compounds to be used according to the invention, which can be prepared by a process according to the invention.

0214In the following, the invention is first described for monomers comprising tricyclic structural elements Q using the example of tricyclo [5.2.1.0^2,6] decan (TCD) derivatives explained in detail.

1.) Starting from bis (hydroxymethyl) tricyclo [5.2.1.0

2,6

] decane (TCD diol)

0215Bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] Decane is commercially available, for example as a dicidol mixture of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decane and 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decane and 3,9-bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decane and 4,9-bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decan.

0216The bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decane, starting from dicyclopentadiene (tricyclo [5.2.1.0^2,6] deca-3,8-diene). Dicyclopentadiene is easily prepared in a Diels-Alder reaction by dimerization of cyclopentadiene. Hydroformylation of dicyclopentadiene then gives the bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decan. Depending on the synthetic pathway, substituted bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decane can be obtained. So in the publications<patcit id="pcit0060" dnum="JP7206740A"><text>JP 7-206740</text></patcit>, <patcit id="pcit0061" dnum="EP1112995B1"><text>EP 1 112 995 B1</text></patcit> or <patcit id="pcit0062" dnum="EP0049631B1"><text>EP 0 049 631 B1</text></patcit> Regulations specified, such as the 8,9-bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decan can be produced. The<patcit id="pcit0063" dnum="DE10352260B3"><text>DE 103 52 260 B3</text></patcit> on the other hand describes processes for the preparation of 3 (4), 8 (9) bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decan. The notation of the positions of the hydroxymethyl groups 3 (4), 8 (9) means 3 or 4, 8 or 9.

0217The commercially available bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] Decane thus contains hydroxymethyl groups both at positions 3 or 4 and in positions 8 or 9. It is now possible to add alkylene oxides, generally in amounts of 1 to 10 mol, in particular ethylene oxide, propylene oxide, butylene oxide, etc to synthesize the corresponding polyether polyols in the presence of basic catalysts by known processes. The<patcit id="pcit0064" dnum="EP0023686B1"><text>EP 0 023 686 B1</text></patcit> contains precise manufacturing instructions.

0218The implementation of the 3 (4), 8 (9) bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] Decane with isocyanates to the corresponding urethanes is also known. So describes the<patcit id="pcit0065" dnum="DE3522006A1"><text>DE 35 22 006 A1</text></patcit> the reaction of 3 (4), 8 (9) bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decans with 2-isocyanatoethyl methacrylate. 2-isocyanatoethyl methacrylate is commercially available or can be prepared from the<patcit id="pcit0066" dnum="DE3338077A1"><text>DE 33 38 077 A1</text></patcit> can be synthesized by phosgenation of dihydrooxazines.

0219The reaction product obtained (formula (1)) of 2-isocyanatoethyl methacrylate with 3 (4), 8 (9) bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decan has a low reaction shrinkage and high mechanical strength in a formulation after curing.<chemistry id="chem0056" num="0056"><img file="EP2436366A2_D0056.tif" /></chemistry>

0220The urethane of the formula (1) still has two reactive hydrogen atoms on nitrogen, which are then reacted further in a second reaction step with excess isocyanate to form a compound to be used according to the invention. The allophanate of the formula (2) initially forms as a tetrafunctionalized, free-radically crosslinkable compound. This monomer, in turn, also has convertible hydrogen atoms on nitrogen which, according to the invention, form the hexafunctionalized, free-radically curable allophanate of the formula (3) when reacted with further isocyanate.<chemistry id="chem0057" num="0057"><img file="EP2436366A2_D0057.tif" /></chemistry><chemistry id="chem0058" num="0058"><img file="EP2436366A2_D0058.tif" /></chemistry>

0221Alternatively, the 3 (4), 8 (9) bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] Decane can also be reacted with methacryloyl isocyanate. Methacryloyl isocyanate is commercially available or by reacting methacrylamide with oxalyl chloride, as in the<patcit id="pcit0067" dnum="EP0143613B1"><text>EP 0 143 613 B1</text></patcit> described. By reaction of 3 (4), 8 (9) bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decane with methacryloyl isocyanate gives a compound of formula (4):<chemistry id="chem0059" num="0059"><img file="EP2436366A2_D0059.tif" /></chemistry>

0222The remaining reactive hydrogen atoms on the nitrogen of the compound of formula (4) can then in turn be converted to allophanates in isocyanate reactions. The reaction product with 2-isocyanatoethyl methacrylate (formula (5)) is shown here by way of example.<chemistry id="chem0060" num="0060"><img file="EP2436366A2_D0060.tif" /></chemistry>

2.) Starting from 3 (4), 8 (9) bis (carboxylic acid) tricyclo [5.2.1.0

2,6

] decan

0223The 3 (4), 8 (9) bis (carboxylic acid) tricyclo [5.2.1.0^2,6] Decane is obtained by simple oxidation of the commercially available 3 (4), 8 (9) bis (formyl) tricyclo [5.2.1.0^2,6] decans can be produced. Reaction of the dicarboxylic acid with 2-isocyanatoethyl methacrylate gives the amide of the formula (8):<chemistry id="chem0061" num="0061"><img file="EP2436366A2_D0061.tif" /></chemistry>

0224Further reaction of the two reactive amide hydrogen atoms of the amide of formula (8) with 2-isocyanatoethyl methacrylate gives the acylurea of ​​formula (9).<chemistry id="chem0062" num="0062"><img file="EP2436366A2_D0062.tif" /></chemistry>

0225If 3 (4), 8 (9) bis (carboxylic acid) tricyclo [5.2.1.0^2,6] Decane reacted with methacryloyl isocyanate, the imide of formula (10) results. Here, too, the reactive hydrogen atoms on nitrogen can be further converted into isocyanate reactions.<chemistry id="chem0063" num="0063"><img file="EP2436366A2_D0063.tif" /></chemistry>

3.) Starting from 3 (4), 8 (9) bis (isocyanatomethyl) tricyclo [5.2.1.0

2,6

] decan

0226The 3 (4), 8 (9) bis (isocyanatomethyl) tricyclo [5.2.1.0^2,6] decan is known per se and is one of the conventional diisocyanate compounds used in industrial applications (see also the <patcit id="pcit0068" dnum="DE3703120A1"><text>DE 37 03 120 A1</text></patcit> as well as the <patcit id="pcit0069" dnum="WO2009065873A2"><text>WO 2009/065873 A2</text></patcit>). The inventive implementation of the second reaction stage of the isocyanate-alcohol reaction can not only start with the tricyclodecanediol

0227Isocyanatoethyl methacrylate, but also starting from tricyclodecane diisocyanate and hydroxyethyl methacrylate. The urethane of the formula (11) is obtained by stoichiometric conversion of the two reactants.<chemistry id="chem0064" num="0064"><img file="EP2436366A2_D0064.tif" /></chemistry>

0228This carbamate (formula (11)) also has two reactive hydrogen atoms on nitrogen, which with an excess of bis (isocyanatomethyl) tricyclo [5.2.1.0^2,6] decane to the diisocyanate of formula (12) can be further implemented.<chemistry id="chem0065" num="0065"><img file="EP2436366A2_D0065.tif" /></chemistry>

0229Reaction of the allophanate diisocyanate (formula (12)) with methacrylic acid provides the compound of formula (13).<chemistry id="chem0066" num="0066"><img file="EP2436366A2_D0066.tif" /></chemistry>

0230Instead of hydroxyethyl methacrylate, other hydroxyl compounds of (meth) acrylates can also be used in the reactions exemplified above, it also being possible to use mixtures of acrylates and methacrylates. Analogously to the example above, 3 (4), 8 (9) bis (isocyanatomethyl) tricyclo [5.2.1.0^2,6] decan can be implemented. Preferred hydroxyl compounds of (meth) acrylates are:<ul id="ul0034" list-style="none" compact="compact"><li>Alkylene oxide mono (meth) acrylates such as ethylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, etc., polyalkylene oxide mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate (polypropylene glycol mono) ) acrylate, polybutylene glycol mono (meth) acrylate, etc., hydroxyalkyl mono (meth) acrylates such as, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxynonyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxyundecyl (meth) acrylate, hydroxydodecyl (meth) acrylate, etc., poly (ε-caprolactone) mono (meth) acrylate, poly (γ-caprolactone) mono (meth ) acrylate, etc., the mono-, di-, tetra- or penta (meth) acrylates of polyhydric alcohols, such as glycerol, such as, for example, glycerol di (meth) acrylate (2-hydroxypropyl-1,3-di (meth) acrylate, 3-hydroxypropyl-1,2-di (meth) acrylate), such as trimethylolpropane, such as trimethylolpropane di (meth) acrylate, such as pentaerythritol such as, for example, pentaerythritol tri (meth) acrylate, such as dipentaerythritol, such as, for example, dipentaerythritol penta (meth) acrylate, such as ditrimethylolpropane tri (meth) acrylate, such as neopentylglycol (meth) acrylate, the (meth) acrylates of alkoxylated or phenoxylated glycerol, preferably the (meth) acrylates of ethoxylated, propoxylated, etc. glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, ditrimethylolpropane, etc. and their technical mixtures, bisphenol-A-glycidyl (meth) acrylate (bis-GMA), bisphenol-B -Glycidyl- (meth) acrylate, bisphenol-C-glycidyl- (meth) acrylate, bisphenol-F-glycidyl- (meth) acrylate, alkoxylated bisphenol-A-glycidyl- (meth) acrylate (e.g. ethoxylated bisphenol-A-glycidyl- (Meth) acrylate), etc.</li></ul>

0231All of these compounds have both (meth) acrylate groups and hydroxyl groups. The latter can with isocyanate groups in the above for the reaction between hydroxyethyl methacrylate and 3 (4), 8 (9) bis (isocyanatomethyl) tricyclo [5.2.1.0^2,6] react to the manner described. In this way, a high degree of functionalization can be achieved in a single reaction step. 3 (4), 8 (9) bis (isocyanatomethyl) tricyclo [5.2.1.0^2,6] Decane can be reacted with 2-carboxylic acid ethyl methacrylate to give the corresponding amide of the formula (16).<chemistry id="chem0067" num="0067"><img file="EP2436366A2_D0067.tif" /></chemistry>

0232Reaction of the amide of formula (16) with 2-isocyanatoethyl methacrylate gives the acylurea of ​​formula (17).<chemistry id="chem0068" num="0068"><img file="EP2436366A2_D0068.tif" /></chemistry>

0233The amide of the formula (16) can also be mixed with an excess of 3 (4), 8 (9) bis (isocyanatomethyl) tricyclo [5.2.1.0^2,6] Decane to be converted to the corresponding isocyanate, the isocyanate formed being further reacted with hydroxyethyl methacrylate to give the crosslinkable monomer of the formula (18).<chemistry id="chem0069" num="0069"><img file="EP2436366A2_D0069.tif" /></chemistry>

0234If 3 (4), 8 (9) bis (isocyanatomethyl) tricyclo [5.2.1.0^2,6] Decane reacted with 2-methacryloyloxyethyl hydrogen succinate, the amide of the formula (19) is obtained, which is further reacted with 2-isocyanatoethyl methacrylate to give the acylurea of ​​the formula (20).<chemistry id="chem0070" num="0070"><img file="EP2436366A2_D0070.tif" /></chemistry><chemistry id="chem0071" num="0071"><img file="EP2436366A2_D0071.tif" /></chemistry>

0235Further suitable carboxylic acid methacrylates can be obtained by reactions of di- or tetracarboxylic acid mono- or dianhydride with suitable OH-functionalized, curable compounds such as, for example, 2-hydroxyethyl methacrylate.

4.) Starting from 3 (4), 8 (9) bis (aminomethyl) tricyclo [5.2.1.0

2,6

] decan

0236The 3 (4), 8 (9) bis (aminomethyl) tricyclo [5.2.1.0^2,6] Decane is known per se or can be prepared, for example, by reacting the corresponding tosylates with ammonia. Reaction of 3 (4), 8 (9) bis (aminomethyl) tricyclo [5.2.1.0^2,6] decans with 2-isocyanatoethyl methacrylate results from the <patcit id="pcit0070" dnum="EP0209700A2"><text>EP 0 209 700 A2</text></patcit> known urea compound of formula (26).<chemistry id="chem0072" num="0072"><img file="EP2436366A2_D0072.tif" /></chemistry>

0237Here, too, there are still active, reactive hydrogen atoms on nitrogen which react with an excess of isocyanate, for example to give the biuret of the formula (27).<chemistry id="chem0073" num="0073"><img file="EP2436366A2_D0073.tif" /></chemistry>

0238The 3 (4), 8 (9) bis (aminomethyl) tricyclo [5.2.1.0^2,6] Decane can also be reacted with methacryloyl isocyanate to give the corresponding acylurea. The further reaction of the remaining reactive hydrogen atoms on nitrogen with methacryloyl isocyanate provides the biuret of the formula (28).<chemistry id="chem0074" num="0074"><img file="EP2436366A2_D0074.tif" /></chemistry>

0239Analog to the monomers described above, which one of the tricyclo [5.2.1.0^2,6] decane-derived polyalicyclic structural element Q, monomers can also be prepared which contain a tricyclo [3.3.1.1^3,7] decane (adamantane) derived polyalicyclic structural element Q include. The following reaction products are shown as examples:<chemistry id="chem0075" num="0075"><img file="EP2436366A2_D0075.tif" /></chemistry>

0240The reaction of the compound of formula (11) with diisocyanatoadamantane [(bis (isocyanatomethyl) tricyclo [3.3.1.1^3,7] decan] provides a monomer to be used according to the invention, the molecule of which comprises two different polyalicyclic structural elements Q, as the structural formula below of the compound of the formula (69) shows.<chemistry id="chem0076" num="0076"><img file="EP2436366A2_D0076.tif" /></chemistry>

Component (b2): one, two or more further radically polymerizable monomers from the group consisting of acrylates and methacrylates, preferably from the group of methacrylates

0241The optional second component of the matrix-forming monomer component that cannot be counted as monomer component (b1) is formed by free-radically polymerizable monomers selected from the group consisting of acrylates and methacrylates. Their function within the composite material according to the invention or to be used according to the invention essentially consists in adjusting the viscosity.

0242According to the invention, the methacrylic acid esters or diesters are preferred over the corresponding acrylic acid esters or diesters because of their higher biological compatibility.

0243The free-radically polymerizable monomers of component (b2) preferably have at least two ethylenic groups.

0244A large number of diacrylate and dimethacrylate monomers are mentioned in the patent literature (for example also in US Pat <patcit id="pcit0071" dnum="DE3941629A1"><text>DE 39 41 629 A1</text></patcit>, which is part of the present application by reference, in particular the disclosure in the area from column 6, line 15 to column 8, line 10), which are suitable for use in a composite material according to the invention or to be used according to the invention.

0245In a preferred or Composite material to be used according to the invention contains component (b2) one or more dimethacrylate monomers selected from the group consisting of ethylene glycol dimethacrylate (EGDMA), 1,6-hexanediol dimethacrylate (HEDMA), triethylene glycol dimethacrylate (TEDMA), 1,12-dodecanediol dimethacrylate (DODMA) , ethoxylated bisphenol A dimethacrylate, polyethylene glycol dimethacrylate (PEGDMA), 7,7,9-trimethyl-4,13-dioxo-5,12-diazahexadecane-1,16-dioxydimethacrylate (UDMA), butanediol dimethacrylate, Tetraethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 2-hydroxypropyl-1,3-dimethacrylate, 3-hydroxypropyl-1,2-dimethacrylate, pentaerythritol dimethacrylate and glycerol dimethacrylate.

0246A composite material is preferred according to the invention, the further radically polymerizable monomers (b2) being selected from the group consisting of triethylene glycol dimethacrylate (TEDMA), urethane dimethacrylate (7,7,9-trimethyl-4,13-dioxo-3,14-dioxa) -5,12-diazahexadecane-1,16-dioxydimethacrylate, UDMA) and mixtures thereof. With these radically polymerizable monomers (b2), in combination with the monomers (b1), in particular with the as preferred or particularly preferred characterized monomers (b1), achieved particularly good effects in the sense of the present invention. The presence of UDMA in a composite material according to the invention or to be used according to the invention is particularly preferred.

0247Is used as a monomer component (b2), a mixture containing or consisting of triethylene glycol dimethacrylate (TEDMA) and urethane dimethacrylate (7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-dioxydimethacrylate , UDMA), the mechanical values ​​such as the bending strength and in particular the modulus of elasticity improve, while at the same time the water absorption and flow behavior (determined by means of contact angle measurement) is still significantly below the values ​​of a comparison material from the prior art. This applies in particular if (monomer) (b1) (meth) acrylic acid ester of dihydroxymethyltricyclo [5.2.1.0^2,6] decans can be used.

0248In our own investigations, a sealing material from the prior art was used with a resin matrix composed of conventional dental monomers (UDMA 30%, TEDMA 37%, Bis-GMA 16% and ethoxylated Bis-GMA 17%, each in% by weight based on the monomer mixture) and a filler mixture made of glass ceramic in a total amount of 52% (in% by weight based on the total composition) (see comparative example in the experimental part).

0249If the polymer matrix of a composite material according to the invention or to be used according to the invention is completely, ie exclusively, composed of one or more (meth) acrylic acid esters of bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] formed decane (see Example 2 below), surprisingly, both the water absorption and the contact angle on the dried tooth enamel are considerably lower than with a composite material from the prior art, although the mechanical values ​​(bending strength and modulus of elasticity) are somewhat reduced, but still have acceptable values.

0250If the polymer matrix of a composite material according to the invention or to be used according to the invention consists of (i) one or more (meth) acrylic acid esters of bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decans and (ii) triethylene glycol dimethacrylate (TEDMA) and / or urethane dimethacrylate (7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-dioxydimethacrylate, UDMA) , the mechanical values ​​such as the flexural strength and in particular the modulus of elasticity improve, while the water absorption and the flow behavior (represented by the contact angle measurement) are acceptable and are still significantly below the values ​​of the comparative material from the prior art.

0251Very good results are achieved if a mixture of TEDMA and UDMA is used as the monomer component (b2), the weight ratio of TEDMA to UDMA being in the range from 4: 1 to 1: 4, preferably in the range from 3: 1 to 1: 3, preferably in the range 2: 1 to 1: 2, particularly preferably in the range 3: 2 to 2: 3 and very particularly preferably in the range 4: 3 to 3: 4.

0252Particularly good results are achieved if the weight ratio of the total amount of (meth) acrylic acid esters of bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decans (monomer component (b1)) to the total amount of the mixture of TEDMA and UDMA (monomer component (b2)) is in the range 4: 1 to 1: 3, preferably in the range 3: 1 to 1: 2, preferably in the range 2: 1 to 2: 3, particularly preferably in the range 3: 2 to 2: 3 and very particularly preferably in the range 4: 3 to 3: 4, the weight ratios of TEDMA to UDMA again preferably being set in the monomer component (b2) .

0253Bisphenol-A-glycidyl methacrylate (Bis-GMA) can be used, but preferably a dental composite material to be used or used according to the invention does not contain the compound Bis-GMA. A dental composite material to be used or used according to the invention is preferably free of all compounds with a bisphenol A structural element.

0254The free-radically polymerizable monomers of component (b2), which therefore do not belong to component (b1), can also be hydroxyl compounds. All hydroxyl compounds of acrylates or methacrylates commonly used in dental chemistry can be used. Hydroxyl compounds of methacrylates are preferred, again preferably 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 1,2-dihydroxypropyl methacrylate, 1,3-dihydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxypropyl-1,3-dimethacrylate, 3 Hydroxypropyl 1,2-dimethacrylate, pentaerythritol dimethacrylate, glycerol dimethacrylate, 2,2-bis [4- [3-methacryloyloxy-2-hydroxypropoxy] phenyl] propane.

0255As a further component, light-curable acrylate or methacrylate monomers based on polysiloxanes can also be used, as described, for example, in US Pat <patcit id="pcit0072" dnum="DE19903177"><text>DE 199 03 177</text></patcit> or in the <patcit id="pcit0073" dnum="DE4416857"><text>DE 44 16 857</text></patcit> are described, which are part of the present application by reference.

0256A dental composite material to be used or used according to the invention may further contain one or more acid group-containing acrylate and / or methacrylate monomers in component (b2). Such acid group-containing monomers can preferably have a carboxylic acid, a phosphoric acid, a phosphonic acid, a sulfonic acid and / or a thiophosphoric acid function. The monomer can contain one or a variety of acid functions in one molecule.

0257Suitable monomers containing a phosphoric acid group are, for example, 2- (meth) acryloyloxyethyl dihydrogen phosphate, bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 10- (meth) acryloyloxyphosphate (phosphate) 6- (meth) -acryloyloxyhexylphenyl hydrogen phosphate, 1- 0- (meth) acryloyloxydecyl dihydrogen phosphate, 1,3-di (meth) acryloyloxypropane-2-dihydrogen phosphate, 1,3-di- (meth) acryloyloxypropane-2-phenyl hydrogen phosphate and bis [5- (2- (meth) acryloyloxyethoxycarbonyl) heptyl] hydrogen phosphate.

0258Suitable monomers containing a carboxylic acid group are, for example, 4- (meth) acryloxyethyltrimellitic acid (4-MET), 4- (meth) acryloxyethyltrimellitic acid anhydride (4-META), 4- (meth) acryloxydecyltrimellitic acid, 4- (meth) acryloxydecyltrimellitic acid anhydride, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, 1,4-di (meth) acryloyloxypyromellitic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylphthalic acid and 2- (meth) acryloyloxyethylhexahydrophthalic acid.

0259Other suitable monomers bearing acid groups are, for example, in US Pat <patcit id="pcit0074" dnum="EP0980682A1"><text>EP 0 980 682 A1</text></patcit> (in particular paragraphs [0059] to [0065]) or the <patcit id="pcit0075" dnum="EP0948955A1"><text>EP 0 948 955 A1</text></patcit> (in particular paragraphs [0031] to [0034]), which are part of the present application by reference.

0260Furthermore, the phosphoric acid esters with glycerol dimethacrylate or with hydroxyethyl methacrylate or with hydroxypropyl methacrylate can also be used.

0261The monomers mentioned can be used individually or in mixtures.

Component (c): initiators and / or catalysts

0262Preferred composite materials to be used or used in accordance with the invention are light-curable (photo-curable) and include light-curing initiators. Examples of a light curing initiator include substances that only have a photosensitizing effect and combinations of a sensitizer and accelerator.

0263Examples of photosensitizers are alpha-diketones, benzoin alkyl ethers, thioxanthones, benzophenones, acylphosphine oxides, acetophenones, ketals, titanocenes, sensitizing dyes, etc. The sensitizers can be used alone or in combination. Specific substance examples of the different classes can be found, for example, in the<patcit id="pcit0076" dnum="DE102006019092A1"><text>DE 10 2006 019 092 A1</text></patcit> or in the <patcit id="pcit0077" dnum="DE3941629C2"><text>DE 39 41 629 C2</text></patcit>which are part of the present application by reference.

0264Examples of accelerators which are used together with the sensitizers are tertiary amines, secondary amines, barbituric acids, tin compounds, aldehydes and sulfur compounds. Specific substance examples of the different classes can be found in the<patcit id="pcit0078" dnum="DE102006019092"><text>DE 10 2006 019 092</text></patcit> or in the <patcit id="pcit0079" dnum="DE3941629C2"><text>DE 39 41 629 C2</text></patcit>which are part of the present application by reference.

0265Other suitable initiators and combinations of initiators are in the <patcit id="pcit0080" dnum="DE60116142"><text>DE 601 16 142</text></patcit> described, which are part of the present application by reference.

0266The photoinitiators which can be used in the context of the present invention are characterized in that they are absorbed by 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 or several coinitiators, the curing of a composite material according to the invention or to be used or used according to the invention, in particular an inventive or dental composite material to be used or used according to the invention.

0267The maximum absorption of camphorquinone (CC) is around 470 nm and thus in the range of blue light. Camphorquinone (CC) is one of the PI₂Initiators and is used regularly together with a coinitiator.

0268A composite material to be used or used according to the invention preferably contains the combination of an alpha-diketone and an aromatic tertiary amine; preference is given to the combination of camphorquinone (CC) and ethyl-pN, N-dimethylaminobenzoate (DABE).

0269Also preferred is the further combination of the "alpha-diketone / aromatic tertiary amine" system with a phosphine oxide, in particular with the phenyl-bis (2,4,6-trimethylbenzoyl) phosphine oxide and / or the 2,4,6-trimethylbenzoyldiphenylphosphine oxide. With regard to the structures of suitable phosphine oxides for use in a composite material according to the invention or to be used or used according to the invention, reference is made to the documents<patcit id="pcit0081" dnum="DE3801511C2"><text>DE 38 01 511 C2</text></patcit>, <patcit id="pcit0082" dnum="DE102006050153A1"><text>DE 10 2006 050 153 A1</text></patcit>, <patcit id="pcit0083" dnum="EP0184095B1"><text>EP 0 184 095 B1</text></patcit>, <patcit id="pcit0084" dnum="DE4231579C2"><text>DE 42 31 579 C2</text></patcit>, <patcit id="pcit0085" dnum="EP0366977B1"><text>EP 0 366 977 B1</text></patcit>, <patcit id="pcit0086" dnum="US7081485B2"><text>US 7,081,485 B2</text></patcit>, <patcit id="pcit0087" dnum="DE3236026A1"><text>DE 32 36 026 A1</text></patcit>, <patcit id="pcit0088" dnum="US20070027229A1"><text>US 2007/0027229 A1</text></patcit>, <patcit id="pcit0089" dnum="EP0262629B1"><text>EP 0 262 629 B1</text></patcit>, <patcit id="pcit0090" dnum="EP0073413A"><text>EP 0 073 413</text></patcit>, <patcit id="pcit0091" dnum="US7148382B2"><text>US 7,148,382 B2</text></patcit>, <patcit id="pcit0092" dnum="US5761169A"><text>US 5,761,169</text></patcit>, <patcit id="pcit0093" dnum="DE19708294A1"><text>DE 197 08 294 A1</text></patcit>, <patcit id="pcit0094" dnum="EP0057474A"><text>EP 0 057 474</text></patcit>, <patcit id="pcit0095" dnum="EP0047902A"><text>EP 0 047 902 A</text></patcit>, <patcit id="pcit0096" dnum="EP0007508A"><text>EP 0 007 508</text></patcit>, <patcit id="pcit0097" dnum="DE60029481T2"><text>DE 600 29 481 T2</text></patcit>, <patcit id="pcit0098" dnum="EP0980682B1"><text>EP 0 980 682 B1</text></patcit>, <patcit id="pcit0099" dnum="EP0948955B1"><text>EP 0 948 955 B1</text></patcit>, <patcit id="pcit0100" dnum="EP1236459B1"><text>EP 1 236 459 B1</text></patcit> and <patcit id="pcit0101" dnum="EP0173567A2"><text>EP 0 173 567 A2</text></patcit> referenced, which are part of the present application by reference.

0270The phosphine oxides specified in these documents are particularly suitable on their own or in combination with the "alpha-diketone / amine" system as a photopolymerization initiator system in a composite material according to the invention or to be used or used according to the invention.

0271Alternatively, borate salts, as described, for example, in <patcit id="pcit0102" dnum="US4772530A"><text>US 4,772,530</text></patcit>, <patcit id="pcit0103" dnum="US4954414A"><text>US 4,954,414</text></patcit>, <patcit id="pcit0104" dnum="US4874450A"><text>US 4,874,450</text></patcit>, <patcit id="pcit0105" dnum="US5055372A"><text>US 5,055,372</text></patcit> and <patcit id="pcit0106" dnum="US5057393A"><text>US 5,057,393</text></patcit> are used as photoinitiators, which are part of the present application by reference.

0272Other suitable photoinitiators are in <nplcit id="ncit0001" npl-type="b"><text>J.-P. Fouassier, Photoinitiation, Photopolymerization and Photocuring, Hanser Publishers, Munich, Vienna, New York 1995</text></nplcit> as in <nplcit id="ncit0002" npl-type="b"><text>JF Rabek (ed.), Radiation Curing in Polymer Science and Technology, Vol. II, Elsevier Applied Science, London, New York 1993</text></nplcit> described, which are part of the present application by reference.

0273Various initiators for chemical curing are known to the person skilled in the art. In this respect it is exemplary of the<patcit id="pcit0107" dnum="EP1720506A"><text>EP 1 720 506</text></patcit> referred.

0274Preferred initiators for chemical hardening 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.

0275The peroxides and the amines are divided into two different components of the dental material. When the amine-containing component (so-called base paste) is mixed with the peroxide-containing component (so-called initiator or catalyst paste), the radical reaction is initiated by the reaction of amine and peroxide (redox reaction).

0276Dual curing systems include a combination of photoinitiators and chemical curing initiators.

0277For example, the base paste can additionally contain a photoinitiator, so that the base paste can be used either alone as a light-curing dental material or together with the initiator paste as a light- and self-curing dental material.

0278In addition to the oxidatively active organic peroxide compounds, barbituric acids or barbituric acid derivatives and malonyl sulfamides can also be used as redox systems.

0279Of the barbituric acid systems, the so-called "Bredereck systems" are of great importance. Examples of suitable "Bredereck systems" as well as references to the corresponding patent literature can be found in the<patcit id="pcit0108" dnum="EP1839640A"><text>EP 1 839 640</text></patcit> as in <patcit id="pcit0109" dnum="DE1495520"><text>DE 1495520</text></patcit>, <patcit id="pcit0110" dnum="WO02092021A"><text>WO 02/092021</text></patcit> or in <patcit id="pcit0111" dnum="WO02092023A"><text>WO 02/092023</text></patcit>which are part of the present application by reference.

0280Suitable malonyl sulfamides are in the <patcit id="pcit0112" dnum="EP0059451A"><text>EP 0 059 451</text></patcit> described which is part of the present application by reference. Preferred compounds are 2,6-dimethyl-4-isobutylmalonylsulfamide, 2,6-diisobutyl-4-propylmalonylsulfamide, 2,6-dibutyl-4-propylmalonylsulfamide, 2,6-dimethyl-4-ethylmalonylsulfamide and 2,6-diocytyl- 4-isobutylmalonylsulfamide.

0281Sulfur compounds in the oxidation state +2 or +4 such as sodium benzene sulfinate or sodium paratoluenesulfinate can also be used.

0282To accelerate curing, the polymerization can be carried out in the presence of heavy metal compounds such as Ce, Fe, Cu, Mn, Co, Sn or Zn, 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 ethyl hexanoate, copper di (methacrylate), copper acetylacetonate and copper naphthenate.

Component (d): optional additional additives

0283In some cases, a composite material to be used or used according to the invention comprises one or more further additives.

0284These additives can have different functions. Usual additives for use in dental composite materials are known to the person skilled in the art, depending on the desired function, he will select the suitable additive (s). Typical additives and their functions are described below by way of example.

0285Light-curable dental composite materials, as are preferred according to the invention, preferably contain one or more inhibitors, also called stabilizers. These are usually added to avoid spontaneous polymerization. They react with premature radicals that are trapped, prevent premature polymerization and increase the storage stability of the light-curable 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 and tert-butylhydroxyanisole (BHA), 2,2 diphenyl-1-picrylhydrazyl, galvinoxyl, triphenylmethyl radicals, 2,3,6,6, tetramethylpiperidinyl-1-oxyl radicals (TEMPO) and derivatives of TEMPO or phenothiazine and derivatives of this compound are in the<patcit id="pcit0113" dnum="EP0783880B1"><text>EP 0 783 880 B1</text></patcit> described which are part of the present application by reference. Alternative inhibitors are in the<patcit id="pcit0114" dnum="DE10119831A1"><text>DE 101 19 831 A1</text></patcit> or in the <patcit id="pcit0115" dnum="EP1563821A1"><text>EP 1 563 821 A1</text></patcit> specified, which are part of the present application by reference.

0286A preferred dental composite material according to the invention thus comprises, as an additive, one or more polymerization inhibitors to increase the storage stability of the composite material, 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.

0287A preferred dental composite material according to the invention, which is particularly suitable for use in a therapeutic dental process as a sealing material for sealing fissures and / or dimples and / or carious lesions, comprises one or more fluoride-releasing substances as an additive, preferably sodium fluoride and / or amine fluoride.

0288UV absorbers, which, for example, are able to absorb UV radiation due to their conjugated double bond systems and aromatic rings, are in some cases part of a dental composite material to be used according to the invention. Examples of UV absorbers are 2-hydroxy-4-methoxybenzophenone, salicylic acid phenyl ester 3- (2'-hydroxy-5'-methylphenyl) benzotriazole or diethyl-2,5-dihydroxy-terephthalate.

0289Since the teeth are to be restored as true to nature as possible, it is necessary to provide dental composite materials to be used according to the invention in a wide variety of shades. In general, inorganic dyes and organic pigments are used in very small amounts for this purpose, which are therefore used as an additive in preferred configurations.

0290Flavorings are further optional additives.

0291Preferred composite materials according to the invention or to be used according to the invention are those which comprise constituents designated as preferred above. A large number of combinations are advantageous here. Particularly preferred are new composite materials which, in or as component (b1), preferred compounds of the structure Q (Y_xZ._e)_b with x = 1.

0292A composite material consisting of or comprising:<ol id="ol0008"><li>(a) as a filler component, a total amount of fillers in the range from 0.5 to 60% by weight, based on the total mass of the composite material, the total amount of fillers comprising a mixture of fillers<ul id="ul0035" list-style="none"><li>(a1) a total amount in the range from 0.5 to 60% by weight of non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm (preferably less than 60 nm) and</li><li>(a2) a total amount in the range from 0 to 59.5% by weight of microparticles an average particle size of 0.4 µm to 10 µm such as</li><li>(a3) optionally further fillers, wherein the percentages by weight for components (a1) and (a2) are each based on the total mass of the composite material,</li></ul></li><li>(b) as a monomer component, a total amount of polymerizable monomers in the range from 39 to 98.5% by weight, based on the total mass of the composite material, the total amount comprising polymerizable monomers<ul id="ul0036" list-style="none" compact="compact"><li>(b1) one, two or more monomers selected from the group consisting of compounds (monomers) of the structure Q (Y_xZ._e)_b, where:<ul id="ul0037" list-style="dash"><li>Q represents a saturated or olefinically unsaturated polyalicyclic structural element selected from the group consisting of bicyclic, tricyclic, tetracyclic, pentacyclic and hexacyclic hydrocarbon radicals, optionally one, two or more of those not substituted by substituents Y_xZ._e substituted hydrogen atoms of this polyalicyclic structural element Q are substituted by alkyl groups (preferably C1-C4-alkyl), alkoxy groups (preferably C1-C4-alkoxy), halogen atoms (preferably F) or trifluoromethyl groups,</li><li>b is a natural number selected from the group of natural numbers 1, 2, 3 and 4,</li><li>each Z means a structural element which is selected independently of any further structural elements Z from the group consisting of          -O- (C = O) -CH = CH₂, -O- (C = O) -C (CH₃) = CH₂,          - (C = O) -CH = CH₂, - (C = 0) -C (CH₃) = CH₂         -CH = CH₂, -C (CH₃) = CH₂ and -O-CH = CH₂, </li><li>each index e is a natural number, which is selected independently of any further indices e from the group of natural numbers 1, 2, 3 and 4,</li><li>each index x is independent of any other indexes x 0 or 1,</li><li>each Y in the structure means Q (Y_xZ._e)_b at x = 1 a structural element which connects the polyalicyclic structural element Q with e structural elements Z, each Y being selected independently of any further structural elements Y,</li></ul></li><li>(b2) optionally one, two or more further radically polymerizable monomers from the group consisting of acrylates and methacrylates, preferably from the group of methacrylates, where the further radically polymerizable monomer (s) do not contain any compounds (monomers) of the structure Q (Y_xZ._e)_b are,</li></ul></li><li>(c) one or more initiators and / or catalysts, preferably in an amount of up to 1% by weight, based on the total mass of the composite material, and</li><li>(d) optionally one or more additives for use in a therapeutic dental process as a sealing material for sealing fissures and / or dimples and / or carious lesions, wherein one, two or more of the monomers of component (b1) is selected or are selected from the group consisting of compounds (monomers ) of the structure Q (Y_xZ._e)_b with x = 1 with one, two, three, four or more functional groups which are selected from the group consisting of N-acylurea, allophanate and biuret, where:<ul id="ul0038" list-style="dash"><li>Q represents a saturated or olefinically unsaturated polyalicyclic structural element selected from the group consisting of bicyclic, tricyclic, tetracyclic, pentacyclic and hexacyclic hydrocarbon radicals, none, one, two or more of the substituents not having YZ_e substituted hydrogen atoms of this polyalicyclic structural element Q is or are substituted by alkyl groups, alkoxy groups, halogen atoms or trifluoromethyl groups;</li><li>b is a natural number selected from the group of natural numbers 2, 3, 4;</li><li>each Z means a structural element which is selected independently of any further structural elements Z from the group consisting of          -O- (C = O) -CH = CH₂, -O- (C = O) -C (CH₃) = CH₂,          - (C = O) -CH = CH₂, - (C = O) -C (CH₃) = CH₂,          -CH = CH₂, -C (CH₃) = CH₂ and -O-CH = CH₂, </li><li>each index e is a natural number, which is selected independently of any further indices e from the group of natural numbers 1, 2, 3 and 4;</li><li>each Y means a structural element, which in the structure Q (Y_xZ._e)_b with x = 1 the polyalicyclic structural element Q is linked to e structural elements Z and contains or consists of a structural element, selected from the group consisting of<chemistry id="chem0077" num="0077"><img file="EP2436366A2_D0077.tif" /></chemistry><chemistry id="chem0078" num="0078"><img file="EP2436366A2_D0078.tif" /></chemistry><chemistry id="chem0079" num="0079"><img file="EP2436366A2_D0079.tif" /></chemistry><chemistry id="chem0080" num="0080"><img file="EP2436366A2_D0080.tif" /></chemistry></li></ul></li></ol>where R¹, R² and R³ mean other residues of the compound, the bond arranged on the left in the formula being closer to the structural element Q and the bond arranged on the right closer to the structural element Z.

0293With regard to preferred configurations of such preferred composite materials, the above statements regarding preferred constituents apply.

0294The present invention also relates to a method for the treatment or prophylaxis of a dental disease, characterized in that a composite material to be used according to the invention, preferably in one of the configurations indicated as preferred, is used as the sealing material for sealing fissures and / or dimples and / or carious lesions .

Embodiments

0295The invention is further illustrated by the following examples. Unless otherwise stated, all information is based on weight.

0296Abbreviations and materials used<ul id="ul0039" list-style="none"><li>TEDMA = triethylene glycol dimethacrylate</li><li>UDMA = 7,7,9-trimethyl-4,13-dioxo-5,12-diazahexadecane-1,16-dioxydimethacrylate</li><li>DABE = N, N-dimethyl-p-aminobenzoic acid</li><li>CC = camphorquinone</li><li>BHT = 2,6-di-tert-butyl-4-methylphenol (stabilizer)</li></ul>

Manufacture of composite materials

0297Composite materials to be used or used according to the invention and a comparative material not according to the invention were each produced as follows:<ul id="ul0040" list-style="none" compact="compact"><li>The monomer (b1) and optionally the monomer (s) (b2), initiators (c) and additives (d) are first homogenized in a plastic container using a KPG stirrer. Then the filler (s) of component (a) are added and a homogeneous paste is produced by intimately mixing with a double planetary mixer. If necessary, the homogenization can also be carried out by subsequent rolling on a 3-roll mill.</li></ul>

Measurement methods:

Determination of abrasion (ACTA)

0298The three-media acta abrasion was in accordance <nplcit id="ncit0003" npl-type="s"><text>J. Dent. Suppl. 1, 1994, 22, 21-27</text></nplcit> determined after 200000 cycles.

Flexural strength

0299The flexural strength was determined analogously to ISO 4049. For this purpose, the respective material to be examined was filled into appropriate Teflon molds without air bubbles, covered with foil and glass plate and the excess was pressed out with a screw clamp. The test specimens were cured in a water bath at 37 ° C. for 24 hours.

0300The dimensions of the test specimen (2 mm x 2 mm) were measured in the middle with a measuring accuracy of 0.01 mm. The test specimens were then loaded in a Zwick Z005 universal testing machine (Zwick GmbH, Ulm, Germany) at a feed rate of 0.75 mm / min until they broke.

Flow behavior: contact angle on dry enamel

0301The flow behavior was determined by measuring the contact angle on dry enamel.

0302An extracted human molar was used for the contact angle measurements (KW, in degrees [°]) on dry enamel. This was dried by wiping with a cellulose cloth before the measurement. Then a drop of the material to be examined was applied to the enamel area of ​​the tooth. The contact angle was then determined over a period of 30 seconds using a contact angle measuring device (DSA 100, Krüss).

Water absorption

0303The water absorption was determined analogously to ISO 4049. For this purpose, the composite materials were filled into appropriate Teflon molds without air bubbles, covered with foils and glass plates and the excess was pressed out with a screw clamp. The test specimens with a diameter of 15.0 ± 0.1 mm and a height of 1.0 ± 0.1 mm were light-cured in segments. The test specimens were then stored in a desiccator at 37 ° C. After 22 hours, the test specimens were removed, placed in a second desiccator at 23 ° C. for 2 hours and then weighed to 0.1 mg. This cycle was repeated until a constant mass,<i>m₁</i>was reached.

0304After drying was complete, the diameter was measured twice at right angles to one another with a measuring accuracy of 0.01 mm and the mean diameter was calculated from this. The thickness of the test specimen was measured in the middle and at four equally spaced locations on the edge to 0.01 mm. The volume, V, was calculated from the mean diameter and the mean thickness.

0305The test specimens were then stored in water at 37 ° C. for 7 days. The test specimens were then removed, rinsed with water and blotted until no more moisture was visible on the surface. The test specimens were swung back and forth in the air for 15 s and weighed 1 min after removal from the water. This mass is called<i>m₂</i> specified.

0306The test specimens were then stored again in a desiccator at 37 ° C. After 22 hours, the test specimens were removed, placed in a second desiccator at 23 ° C. for 2 hours and then weighed to 0.1 mg. This cycle was repeated until a constant mass,<i>m₃</i>was reached.

0307The water intake, <i>W_sp</i>was calculated using the following equation: <maths id="math0001"><math display="block"><msub><mi>W</mi><mi>sp</mi></msub><mo>=</mo><mfrac><mrow><msub><mi>m</mi><mn>2</mn></msub><mo>-</mo><msub><mi>m</mi><mn>3</mn></msub></mrow><mi>V</mi></mfrac></math><img file="EP2436366A2_D0081.tif" /></maths>

0308It is<i>m</i>₂ the mass of the test specimen after water storage for 7 days in µg;<i>m</i>₃ the mass of the re-dried specimen in µg;<i>V</i> the volume of the test specimen in mm³

viscosity

0309The viscosity was determined using a Physica MCR 301 rheometer (Anton Paar GmbH, Graz, Austria). For this purpose, the material to be examined was applied to the measuring plate of a plate / plate system (D = 25 mm, gap = 1 mm) and the viscosity was determined at 23 ° C. and a shear rate of 10 / s.

0310The nanofiller used below (silanized) was silanized silica particles with an average particle size of 40 nm.

0311Other definitions:<ul id="ul0041" list-style="none" compact="compact"><li>The compound "TCD monomer" used below was bis (methacrylolyoxymethyl) tricyclo [5.2.1.0^2,6] decan.</li></ul>

0312The filler "pyrogenic silica (organic surface modified)" used below is a hydrophobic silica with a BET surface area (according to DIN EN ISO 9277) of 150 m²/ g, a tamped density (according to DIN EN ISO 787-11) of approx. 200 g / L and a (presumed) primary particle size of 12 nm. The surface of the silica is coated with -OSi (CH3) 3 groups.<tables id="tabl0001" num="0001"><table frame="all"><title><u>Table 1:</u></title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="83mm" /><colspec colnum="2" colname="col2" colwidth="15mm" /><colspec colnum="3" colname="col3" colwidth="13mm" /><colspec colnum="4" colname="col4" colwidth="13mm" /><colspec colnum="5" colname="col5" colwidth="13mm" /><colspec colnum="6" colname="col6" colwidth="19mm" /><thead><row><entry valign="top">example</entry><entry align="center" valign="top">1</entry><entry align="center" valign="top">2</entry><entry align="center" valign="top">3</entry><entry align="center" valign="top">4</entry><entry align="center" valign="top">comparison</entry></row></thead><tbody><row><entry /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry>TCD monomer</entry><entry align="center">0,00</entry><entry align="center">47,12</entry><entry align="center">31,56</entry><entry align="center">15,72</entry><entry align="center">0,00</entry></row><row><entry>Monomer of formula (2)</entry><entry align="center">21,38</entry><entry align="center">0,00</entry><entry align="center">0,00</entry><entry align="center">0,00</entry><entry align="center">0,00</entry></row><row><entry>UDMA</entry><entry align="center">17,35</entry><entry align="center">0,00</entry><entry align="center">0,00</entry><entry align="center">7,07</entry><entry align="center">14,14</entry></row><row><entry>TEDMA</entry><entry align="center">12,44</entry><entry align="center">0,00</entry><entry align="center">0,00</entry><entry align="center">8,71</entry><entry align="center">17,43</entry></row><row><entry /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry>Bis-GMA</entry><entry align="center">0,00</entry><entry align="center">0,00</entry><entry align="center">7,54</entry><entry align="center">7,55</entry><entry align="center">7,54</entry></row><row><entry>Ethoxylated bis-GMA</entry><entry align="center">0,00</entry><entry align="center">0,00</entry><entry align="center">8,02</entry><entry align="center">8,07</entry><entry align="center">8,01</entry></row><row><entry /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry>UV stabilizer</entry><entry align="center">0,25</entry><entry align="center">0,24</entry><entry align="center">0,24</entry><entry align="center">0,24</entry><entry align="center">0,24</entry></row><row><entry>There</entry><entry align="center">0,22</entry><entry align="center">0,21</entry><entry align="center">0,21</entry><entry align="center">0,21</entry><entry align="center">0,21</entry></row><row><entry>Catalytic converter (CC)</entry><entry align="center">0,15</entry><entry align="center">0,14</entry><entry align="center">0,14</entry><entry align="center">0,14</entry><entry align="center">0,14</entry></row><row><entry>BHT</entry><entry align="center">0,09</entry><entry align="center">0,09</entry><entry align="center">0,09</entry><entry align="center">0,09</entry><entry align="center">0,09</entry></row><row><entry>Glass ceramic 0.7 µm (silanized)</entry><entry align="center">26,85</entry><entry align="center">45,94</entry><entry align="center">45,94</entry><entry align="center">45,94</entry><entry align="center">45,94</entry></row><row><entry>Reactive aluminum silicate glass (&lt;10 µm)</entry><entry align="center">4,13</entry><entry align="center">4,07</entry><entry align="center">4,07</entry><entry align="center">4,07</entry><entry align="center">4,07</entry></row><row><entry>fumed silica (organic surface modified)</entry><entry align="center">1,65</entry><entry align="center">1,59</entry><entry align="center">1,59</entry><entry align="center">1,59</entry><entry align="center">1,59</entry></row><row><entry>Titanium dioxide (silanized)</entry><entry align="center">0,62</entry><entry align="center">0,60</entry><entry align="center">0,60</entry><entry align="center">0,60</entry><entry align="center">0,60</entry></row><row><entry>Nanofiller (silanized)</entry><entry align="center">14,87</entry><entry align="center">0,00</entry><entry align="center">0,00</entry><entry align="center">0,00</entry><entry align="center">0,00</entry></row><row><entry /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry>Flexural strength [MPa]</entry><entry align="center">138</entry><entry align="center">109</entry><entry align="center">126</entry><entry align="center">128</entry><entry align="center">104</entry></row><row><entry>Modulus of elasticity [MPa]</entry><entry align="center">6319</entry><entry align="center">3684</entry><entry align="center">4603</entry><entry align="center">4675</entry><entry align="center">4446</entry></row><row><entry>KW [°] enamel dry</entry><entry align="center">29,5</entry><entry align="center">29,0</entry><entry align="center">51,90</entry><entry align="center">45,10</entry><entry align="center">67,1</entry></row><row><entry>Water absorption [µg / mm³]</entry><entry align="center">11,91</entry><entry align="center">5,12</entry><entry align="center" /><entry align="center" /><entry align="center">25,14</entry></row><row><entry>Viscosity [Pas]</entry><entry align="center" /><entry align="center">3,00</entry><entry align="center">8,30</entry><entry align="center">4,60</entry><entry align="center">2,80</entry></row><row><entry>Acta abrasion</entry><entry align="center">75 µm</entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center">145 µm</entry></row><row><entry>Total fillers</entry><entry align="center">48,12</entry><entry align="center">52,20</entry><entry align="center">52,20</entry><entry align="center">52,20</entry><entry align="center">52,20</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><table frame="all"><title><u>Table 2:</u></title><tgroup cols="7"><colspec colnum="1" colname="col1" colwidth="83mm" /><colspec colnum="2" colname="col2" colwidth="13mm" /><colspec colnum="3" colname="col3" colwidth="13mm" /><colspec colnum="4" colname="col4" colwidth="13mm" /><colspec colnum="5" colname="col5" colwidth="13mm" /><colspec colnum="6" colname="col6" colwidth="13mm" /><colspec colnum="7" colname="col7" colwidth="15mm" /><thead><row><entry valign="top">example</entry><entry align="center" valign="top">5</entry><entry align="center" valign="top">6</entry><entry align="center" valign="top">7</entry><entry align="center" valign="top">8</entry><entry align="center" valign="top">9</entry><entry align="center" valign="top">10</entry></row></thead><tbody><row><entry /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry>TCD monomer</entry><entry align="center">23,64</entry><entry align="center">28,37</entry><entry align="center">18,91</entry><entry align="center">21,38</entry><entry align="center">17,91</entry><entry align="center">21,38</entry></row><row><entry>UDMA</entry><entry align="center">11,82</entry><entry align="center">11,82</entry><entry align="center">14,19</entry><entry align="center">17,35</entry><entry align="center">12,31</entry><entry align="center">16,91</entry></row><row><entry>TEDMA</entry><entry align="center">11,47</entry><entry align="center">6,74</entry><entry align="center">13,83</entry><entry align="center">12,44</entry><entry align="center">10,44</entry><entry align="center">13,75</entry></row><row><entry /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry>UV stabilizer</entry><entry align="center">0,24</entry><entry align="center">0,24</entry><entry align="center">0,24</entry><entry align="center">0,25</entry><entry align="center">0,25</entry><entry align="center">0,25</entry></row><row><entry>There</entry><entry align="center">0,21</entry><entry align="center">0,21</entry><entry align="center">0,21</entry><entry align="center">0,22</entry><entry align="center">0,22</entry><entry align="center">0,22</entry></row><row><entry>Catalytic converter (CC)</entry><entry align="center">0,14</entry><entry align="center">0,14</entry><entry align="center">0,14</entry><entry align="center">0,15</entry><entry align="center">0,15</entry><entry align="center">0,15</entry></row><row><entry>BHT</entry><entry align="center">0,09</entry><entry align="center">0,09</entry><entry align="center">0,09</entry><entry align="center">0,09</entry><entry align="center">0,09</entry><entry align="center">0,09</entry></row><row><entry>Glass ceramic 0.7 µm (silanized)</entry><entry align="center">46,11</entry><entry align="center">46,11</entry><entry align="center">46,11</entry><entry align="center">26,85</entry><entry align="center">27,15</entry><entry align="center">0,00</entry></row><row><entry>Reactive aluminum silicate glass (&lt;10 µm)</entry><entry align="center">4,08</entry><entry align="center">4,08</entry><entry align="center">4,08</entry><entry align="center">4,13</entry><entry align="center">4,13</entry><entry align="center">0,00</entry></row><row><entry>fumed silica (organic surface modified)</entry><entry align="center">1,60</entry><entry align="center">1,60</entry><entry align="center">1,60</entry><entry align="center">1,65</entry><entry align="center">1,65</entry><entry align="center">0,00</entry></row><row><entry>Titanium dioxide (silanized)</entry><entry align="center">0,60</entry><entry align="center">0,60</entry><entry align="center">0,60</entry><entry align="center">0,62</entry><entry align="center">0,62</entry><entry align="center">0,00</entry></row><row><entry>Nanofiller (silanized)</entry><entry align="center">0,00</entry><entry align="center">0,00</entry><entry align="center">0,00</entry><entry align="center">14,87</entry><entry align="center">25,08</entry><entry align="center">47,25</entry></row><row><entry /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry>Flexural strength [MPa]</entry><entry align="center">137</entry><entry align="center">127</entry><entry align="center">130</entry><entry align="center">135</entry><entry align="center">131</entry><entry align="center" /></row><row><entry>Modulus of elasticity [MPa]</entry><entry align="center">6106</entry><entry align="center">6070</entry><entry align="center">5334</entry><entry align="center">6214</entry><entry align="center">6279</entry><entry align="center" /></row><row><entry>KW [°] enamel dry</entry><entry align="center">29,3</entry><entry align="center">46,7</entry><entry align="center">30,4</entry><entry align="center">31,5</entry><entry align="center">36,3</entry><entry align="center">33,7</entry></row><row><entry>Water absorption [µg / mm³]</entry><entry align="center">7,61</entry><entry align="center">6,53</entry><entry align="center">11,72</entry><entry align="center">13,45</entry><entry align="center">12,61</entry><entry align="center">12,89</entry></row><row><entry>Acta abrasion</entry><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center">62 µm</entry></row><row><entry>Total fillers</entry><entry align="center">52,39</entry><entry align="center">52,39</entry><entry align="center">52,39</entry><entry align="center">48,12</entry><entry align="center">58,63</entry><entry align="center">47,25</entry></row></tbody></tgroup></table></tables>

Synthesis of the compound of formula (2)

03130.95 g (4.84 mmol) 3 (4), 8 (9) bis (hydroxymethyl) tricyclo [5.2.1.0^2,6] decane were dissolved in 10 mL toluene and 0.04 g BHT and 0.103 g of the catalyst solution were added. 3.00 g (19.34 mmol, 4 equivalents) of isocyanatoethyl methacrylate, dissolved in 10 ml of toluene, were added dropwise with stirring. After the addition had ended, the dropping funnel was replaced by a reflux condenser and the reaction mixture was heated to 120 ° C. and the progress of the reaction was monitored by means of IR spectroscopy. After 72 hours, a further 0.102 g of catalyst solution were added and the mixture was heated until no more isocyanate band was detected. The solvent was removed on a rotary evaporator. The allophanate of formula (2) was obtained in a yield of 3.83 g (4.69 mmol, 97%) as a slightly yellowish oil.

0314Examples 2 to 10 were repeated with the exchange of the TCD monomer used in each case for the compound of the formula (2); these further examples are referred to as examples S2 to S10 0. All parameters determined in Examples 2 to 10 were also determined for Examples S2 to S10. The determined parameter values ​​for examples S2 to S10 are similar to those from examples 2 to 10 and partially exceed them. In addition to Example 1 according to the invention, this shows that the compound of the formula (2), which is representative of the compounds according to the invention, is outstandingly suitable for use in composite materials according to the invention.