Varnish compound comprising a monomer with a polyalicyclic structure element

0001The present invention relates to a, preferably transparent, lacquer composition which can be used as a protective and gloss lacquer for surface coating. The invention further relates to a coating composition according to the invention as a dental material and a method for producing a coating composition according to the invention. The invention also relates to new polymerizable monomers comprising at least one polyalicyclic structural element and certain ethylenic structural elements which are particularly suitable for use in a coating composition according to the invention, in particular a dental coating composition according to the invention, and the use of the new monomers in a coating composition.

0002Crown and bridge temporary restorations made of plastic are an important part of the prosthetic treatment. An essential requirement for these materials is to ensure that the temporary surface is smooth, since rough surfaces favor intraoral plaque buildup. Once a bacterial film has formed, this can quickly lead to inflammatory reactions of the periodontium and the gingiva. A smooth surface also helps to prevent aesthetically problematic discolorations, such as those caused by coffee, tea, wine or cigarettes. In addition, the use of a tooth varnish leads to a glossy surface on otherwise temporary appearances.

0003In general, provisional surfaces are smoothed either with the help of polishers and polishing pastes or using unfilled or very little filled protective lacquer systems. Many studies have shown that lacquered temporary restorations have a lower plaque settlement than polished surfaces. This is due to the fact that when using common polishing and grinding tools, there are more or less clear traces of work in all products that cannot be avoided with mechanical polishing agents. For this reason, the use of protective lacquers on these substrates is recommended.

0004When using a protective and gloss varnish to coat dentures and temporary restorations, it must be ensured that the cured system does not have a rougher surface after a certain dwell time on the prosthesis or the temporary restoration than directly after application of the varnish. Such a circumstance can occur if the paint partially detaches from the plastic and only leaves so-called "islands" with a gradual transition to the residual plastic. Germ cells of bacterial colonization can then form at these points.

0005Protective and gloss varnishes are known from the literature.

0006<patcit id="pcit0001" dnum="JP4029910A"><text>JP 4-29910 A</text></patcit> describes the composition of a dental colorless and transparent coating material which is said to have excellent abrasion resistance. The lacquer contains a polyfunctional crosslinker which can be prepared by esterifying more than three hydroxyl groups of pentaerythritol or dipentaerythritol with acrylic acid (in particular pentaerythritol hexaacrylate), a volatile methacrylate compound (in particular methyl methacrylate) and an acylphosphine oxide as a polymerization catalyst.

0007<patcit id="pcit0002" dnum="US7081485B2"><text>US 7,081,485 B2</text></patcit> discloses a light curable composition useful as a dental coating material comprising a multiacrylate compound and a photoinitiator (acylphosphine oxide), the multiacrylate compound having at least five acrylate functionalities per molecule and the composition containing no methyl methacrylate, and wherein the photoinitiator in an amount of at least 6% by weight the composition is present. The preferred photoinitiator there is 2,4,6-trimethylbenzoyldiphenylphosphine oxide. The varnish should harden free of smear layers.

0008<patcit id="pcit0003" dnum="US20050288387A1"><text>US 2005/0288387 A1</text></patcit> also relates to dental coating compositions which are intended to cure without a smear layer. These compositions are said to be odorlessly storable and comprise a multiacrylate compound, a photoinitiator (acylphosphine oxide) and an alcohol, ethanol being preferably used.

0009<patcit id="pcit0004" dnum="US20040034119A1"><text>US 2004/0034119 A1</text></patcit> also discloses a dental material that is said to harden without a smear layer. First, a varnish is applied to the tooth. In a second step, a covering layer, for example a closed, continuous layer of an essential oil, is applied to the surface of the lacquer. The paint is shielded from the surrounding atmosphere and can then be polymerized without a smear layer. The advantage of this method is that the cover layer brings a good taste and / or a good smell to the treatment, depending on the composition selected. The cover layer can optionally be removed after polymerization.

0010<patcit id="pcit0005" dnum="US20060111465A1"><text>US 2006/0111465 A1</text></patcit> claims dental polymerizable glazes that contain a polymerizable, ethylenically unsaturated resin composition, and a curing agent and a filler that is essentially a polyhedral oligomeric silsesquioxane.

0011<patcit id="pcit0006" dnum="EP1532958B1"><text>EP 1 532 958 B1</text></patcit> Aiming for a dental coating material that has nanoscale particles with average particle sizes from 1 to 100 nm that are surface-modified, at least one polyfunctional methacrylate monomer that has four or more methacryloyl groups in one molecule and contains a photopolymerizer.

0012<patcit id="pcit0007" dnum="US20070010597A1"><text>US 2007/0010597 A1</text></patcit> discloses laser curable compositions for protecting dental hard tissue. The compositions are one-component and contain curable monomers with at least two polymerizable double bonds in the molecule and benzoyl peroxide as an initiator.

0013<patcit id="pcit0008" dnum="DE102007048925A1"><text>DE 10 2007 048 925 A1</text></patcit> describes coating and varnish compositions that can be used for prostheses, relining materials or implants. The compositions described there are based on polysiloxanes.

0014Another dental lacquer is in <patcit id="pcit0009" dnum="DE102008010464A1"><text>DE 10 2008 010 464 A1</text></patcit> disclosed. In the event that, as described above, the lacquer layers, for example in abrasively stressed areas of the tooth surface, become permeable over time and partially lacquer-free, unprotected areas of the tooth surface are exposed, an increased formation of bacterial deposits is likely there. For this reason, tooth enamels have been proposed which are intended to prevent or make it more difficult for coatings to adhere to them. This is said to<patcit id="pcit0010" dnum="DE102008010464A1"><text>DE 10 2008 010 464 A1</text></patcit> can be achieved by using a lacquer which contains perfluorinated residues built into the dental material via urethane groups. The perfluorinated alkyl groups built into the coating formulation by reacting perfluoroalcohols with isocyanate groups serve to make the surface of the cured system hydrophobic. Such hydrophobic surfaces are said to make it more difficult or to prevent deposits from being deposited.

0015<patcit id="pcit0011" dnum="DE102009011537A1"><text>DE 10 2009 011 537 A1</text></patcit> relates to dental surface coating materials that lead to less discoloration after polymerization. The paint system contains 2,4,6-trimethylbenzoyldiphenylphosphine oxide as photoinitiator and dimethacrylate compounds made up of ethylene oxide units, the number of ethylene oxide structural elements being between 9 and 50. The lacquer may also contain a polyfunctional monomer such as dipentaerythritol hexaacrylate.

0016In <patcit id="pcit0012" dnum="DE102009011536A1"><text>DE 10 2009 011 536 A1</text></patcit> it is reported that the use of a (bis) acylphosphine oxide compound such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide in combination with a diketone compound such as camphorquinone in the absence of an amine in a light-curable monomer system causes various effects, e.g. the improvement in curability in a wide wavelength range, decrease the change in a hue before and after curing and the improvement in thin film surface hardenability. Dipentaerythritol hexaacrylate and dimethacrylate compounds composed of alkylene oxide units are mentioned as preferred organic matrix monomers, the number of alkylene oxide structural elements being between 5 and 50.

0017<patcit id="pcit0013" dnum="DE102008039129A1"><text>DE 10 2008 039 129 A1</text></patcit> relates to transparent, scratch-resistant coatings that are also intended for use in the dental field. The coating material comprises a siloxane-containing matrix and functionalized single or multi-walled carbon nanotubes dispersed therein.

0018<patcit id="pcit0014" dnum="US6617413B1"><text>US 6,617,413 B1</text></patcit> describes curable coating compositions by addition to isocyanate groups as well as by radiation-induced addition to activated CC double bonds. The compounds described there can be used, inter alia, in dental materials.

0019In the <patcit id="pcit0015" dnum="EP1307173B1"><text>EP 1 307 173 B1</text></patcit> describes a fluoride varnish and fissure sealing material based on silicone.

0020The describes a temporary, transparent, dental lacquer composition for coating tooth surfaces <patcit id="pcit0016" 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 caused by a total reflection taking place inside the spheres, which always occurs 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.

0021Plastics based on di (meth) acrylate, which are either not or only slightly filled, are used as standard materials in the formulation of protective and gloss coatings. Due to the lack of fillers or their very low filler loading, tooth varnishes have even lower viscosities than flow and filling composites. They are usually thin to medium-thin flowing and are removed from a bottle with a microapplication instrument, for example with a little brush, and then applied directly. Alternatively, the paint system can also be applied from a syringe using a cannula.

0022Medium-thin or viscous materials can be better controlled during application, while thin-flowing systems allow a thinner application and also flow into very small cavities. The application in just a thin layer is therefore important so that the occlusion with the antagonistic tooth is not permanently disturbed. In addition, the thinner the application of the transparent lacquer, the more accurate the reproduction of the color of the lacquered tooth and thus of the natural tooth situation.

0023However, due to the reduced filler content or completely missing filler, the coating systems are less resistant to abrasion and bending than medium and high-filled materials.

0024If dental, free-radically curable compositions are polymerized, the upper layer of the polymer often appears sticky. The surfaces are not fully hardened. This phenomenon is triggered by the oxygen in the air, which is a triplet diradical, in that oxygen molecules disrupt and inhibit radical polymerization due to their radical character. Such a moist layer must be removed with alcohol. If it is possible to prevent the formation of an oxygen inhibition layer by selecting the monomers and selecting and adjusting the initiator system, then these coating systems show better gloss properties and greater resistance to the influences of discoloring agents.

0025Low-filled or unfilled dental lacquer systems are suitable for use as "liquid polishing materials", "dental glaze", "coating materials", "protective lacquers", "gloss lacquers", etc. for a large number of intra- and extra-oral situations and for use in the dental laboratory. Their clinical use is particularly suitable for<ul id="ul0001" list-style="dash"><li>Coatings around the edges of old and new, direct and indirect restorations made of plastics and plastic-reinforced glass ionomer cements (GIZ),</li><li>Restorations and temporary restorations to improve aesthetics and simplify finishing and polishing,</li><li>the therapy of defects in the natural tooth structure.</li></ul>

0026The requirements for protective and glossy lacquer materials are therefore extremely diverse. First of all, transparent compositions should remain on the tooth surface for a long time in order to fulfill their intended use. They should be able to withstand the regular mechanical attacks on them, for example through oral hygiene measures such as brushing their teeth.

0027Since the lacquer materials in the oral cavity are permanently exposed to extremely intensive hydrolytic attacks, for example through saliva, the polymers should have the lowest possible water absorption. 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 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. Here, parts of the lacquer can detach from the tooth surface and form the "islands" mentioned above, which then become the starting point for new bacterial colonization.

0028In 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 complete loss of the product.

0029On the other hand, a certain polarity of the lacquer systems is quite desirable since the hard tooth substance is hydrophilic and polar compositions ensure good adaptation and wettability of the material to the tooth substrate.

0030The primary object of the invention was to provide a coating composition, preferably a transparent coating composition, which is suitable for use as a protective and gloss coating, in particular in the dental field, and has a low water absorption and very good mechanical properties. In addition, the paint composition should preferably be a very good adaptation, ie very good flow behavior on the corresponding surface, especially the tooth structure. In addition, the, preferably dental, lacquer composition should preferably harden without a smear layer.

0031The primary object is achieved according to the invention by a, preferably transparent, lacquer composition, in particular a dental lacquer composition, consisting of or comprising<ol id="ol0001"><li>(a) 35 to 99% by weight, based on the total mass of the coating composition, comprising a monomer component<ul id="ul0002" list-style="none"><li>(a1) one, two or more monomers selected from the group consisting of compounds (monomers) of the structure Q (YZ_e)_b, where:<ul id="ul0003" 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>(a2) one, two or more radically polymerizable monomers selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and pentyl methacrylate,</li><li>(a3) optionally one, two or more further radically polymerizable monomers selected from the group consisting of monomers with three or more (meth) acrylate groups, preferably with three to six (meth) acrylate groups, such as</li><li>(a4) optionally one, two or more further radically polymerizable monomers from the group consisting of acrylates and methacrylates, preferably from the group of methacrylates,</li></ul>and</li><li>(b) one or more initiators and / or catalysts, such as</li><li>(c) optionally a filler component comprising one, two or more fillers,</li><li>(d) optionally one or more other additives.</li></ol>

0032In other words, the present invention relates to a, preferably transparent, lacquer composition, in particular a dental lacquer composition, consisting of or comprising<ol id="ol0002"><li>(a) 35 to 99% by weight, based on the total mass of the coating composition, comprising a monomer component<ul id="ul0004" list-style="none"><li>(a1) 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>(a2) one, two or more radically polymerizable monomers selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and pentyl methacrylate,</li><li>(a3) optionally one, two or more further free-radically polymerizable monomers selected from the group consisting of monomers with three or more (meth) acrylate groups, preferably with three to six (meth) acrylate groups, the further free-radically polymerizable monomers of component (a3) are not monomers as defined in (a1) or (a2), such as</li><li>(a4) 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 further free-radically polymerizable monomers of component (a4) not having any monomers as defined in (a1), ( a2) or (a3),</li></ul>and</li><li>(b) one or more initiators and / or catalysts such as</li><li>(c) optionally a filler component comprising one, two or more fillers,</li><li>(d) optionally one or more other additives.</li></ol>

0033In the context of the present text, (meth) acrylic means both acrylic and methacrylic.

0034All 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.

0035A compound 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.

0036Of course, for substances whose structure simultaneously falls under the definition of different components of a coating composition according to the invention, these substances are assigned to all of these components for the purposes of quantitative considerations.

0037The "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.

0038Each 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.

0039It has been found that the coating compositions according to the invention are dental protective and gloss coatings which, compared to coatings from the prior art, have a much better flow behavior (in particular on dry tooth enamel), absorb much less water and have good mechanical values ​​(in particular Flexural strength and modulus of elasticity).

0040The coating composition according to the invention is preferably light-curable.

0041The sum of the numerical values ​​of the index b and the index e is preferably 3, 4, 5, 6, 7 or 8.

0042Surprisingly, it has been shown in our own investigations that a coating composition according to the invention, in particular a dental coating composition according to the invention, which<ul id="ul0006" list-style="dash"><li>one, two or more monomers of structure Q (YZ_e)_b (as defined above and wherein each Y is selected or omitted independently of any further structural elements Y) of component (a1), and</li><li>(a2) one, two or more further radically polymerizable monomers selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and pentyl methacrylate, preferably methyl methacrylate, and preferably additionally</li><li>(a3) one, two or more further free-radically polymerizable monomers with three or more (meth) acrylate groups, preferably with three to six (meth) acrylate groups,</li></ul>exhibit low shrinkage in the hardened state, good adhesion to various substrates, high resistance to hydrolysis, low water absorption, high mechanical strength and a high gloss. The properties mentioned are particularly important in the field of dental technology.

0043Preferred is a coating composition according to the invention in which the monomer component (a) comprises or consists of<ul id="ul0007" list-style="none"><li>(a1) one, two or more monomers of structure Q (YZ_e)_b (as defined above and where each Y is selected or omitted independently of any further structural elements Y) of component (a1), where preferably Z is a group -O- (C = O) -CH = CH₂, -O- (C = O) -C (CH₃) = CH₂, - (C = O) -CH = CH₂ or - (C = O) -C (CH₃) = CH₂ means</li><li>(a2) one, two or more radically polymerizable monomers selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and pentyl methacrylate,</li><li>(a3) one, two or more further radically polymerizable monomers with three or more (meth) acrylate groups, preferably with three to six (meth) acrylate groups, such as</li><li>(a4) optionally one, two or more further radically polymerizable monomers from the group consisting of acrylates and methacrylates, preferably from the group of methacrylates.</li></ul>

0044A coating composition in which monomer component (a) comprises or consists of is preferred according to the invention<ul id="ul0008" list-style="none"><li>(a1) one, two or more monomers of structure Q (Y_xZ._e)_b component (a1), preferably Z being a group -O- (C = O) -CH = CH₂, -O- (C = O) -C (CH₃) = CH₂, - (C = O) -CH = CH₂ or - (C = O) -C (CH₃) = CH₂ means</li><li>(a2) one, two or more radically polymerizable monomers from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and pentyl methacrylate,</li><li>(a3) one, two or more further free-radically polymerizable monomers with three or more (meth) acrylate groups, preferably with three to six (meth) acrylate groups, the further free-radically polymerizable monomers of component (a3) ​​not containing any monomers as defined in (a1 ) or (a2), such as</li><li>(a4) 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 further free-radically polymerizable monomers of component (a4) being no monomers as defined in (a1), (a2 ) or (a3).</li></ul>

0045A coating composition according to the invention is preferably comprised of or consisting of<ol id="ol0003"><li>(a) comprising 38 to 96% by weight of a monomer component<ul id="ul0009" list-style="none"><li>(a1) one, two or more monomers of structure Q (YZ_e)_b (as defined above and where each Y is selected or omitted independently of any further structural elements Y) of component (a1), where preferably Z is a group -O- (C = O) -CH = CH₂, -O- (C = O) -C (CH₃) = CH₂, - (C = O) -CH = CH₂ or - (C = O) -C (CH₃) = CH₂ means</li><li>(a2) one, two or more radically polymerizable monomers selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and pentyl methacrylate,</li><li>(a3) one, two or more further radically polymerizable monomers with three or more (meth) acrylate groups, preferably with three to six (meth) acrylate groups, such as</li><li>(a4) optionally one, two or more further radically polymerizable monomers from the group consisting of acrylates and methacrylates, preferably from the group of methacrylates,</li></ul>wherein the ratio of the mass of component (a1) to the total mass of components (a2), (a3) ​​and (a4) is preferably in the range from 4: 1 to 1: 6,</li><li>(b) one or more initiators and / or catalysts,</li><li>(c) 0 to 60% by weight of a filler component comprising one, two or more fillers selected from the group consisting of<ul id="ul0010" list-style="none"><li>(c1) 0 to 60% by weight of non-agglomerated, preferably surface-modified, nanoparticles with an average particle size of less than 200 nm (preferably less than 100 nm, particularly preferably less than 60 nm),</li><li>(c2) 0 to 10% by weight of microparticles with an average particle size of 0.4 µm to 10 µm, and</li><li>(c3) 0 to 15% by weight of further fillers, preferably 0 to 10% by weight, preferably 0 to 5% by weight, further preferably 0 to 2.5% by weight of further fillers,</li></ul>and</li><li>(d) optionally one or more additives,</li></ol>wherein the percentages by weight are each based on the total mass of the coating composition.

0046The total amount of component (a1) and component (a2) in a coating composition according to the invention is preferably at least 25% by weight, preferably 30% by weight or more, preferably 35% by weight or more, in each case based on the total mass of the coating composition .

0047The total amount of components (a1), (a2) and (a3) ​​in a coating composition according to the invention is preferably at least 38% by weight, preferably 40% by weight or more.

0048In preferred embodiments, the total amount of components (a1), (a2) and (a3) ​​in a coating composition according to the invention is in the range from 40 to 96% by weight, more preferably in the range from 50 to 95% by weight, more preferably in Range of 60-95% by weight, more preferably in the range of 70-95% by weight, based in each case on the total mass of the coating composition.

0049In the uncured state, a lacquer composition according to the invention, in particular a dental lacquer composition according to the invention, is distinguished by a low contact angle on dry tooth enamel (preferably less than 50 °, preferably less than 40 °, particularly preferably less than 30 °, measured with a contact angle measuring device from the company Krüss (DSA 100)). Before carrying out the contact angle measurement, a human tooth was dried with a cellulose cloth ("dry tooth enamel").

0050It has also been shown that a lacquer composition according to the invention, in particular a dental lacquer composition according to the invention, has a very low water absorption in the hardened state, and preferably less than 50 µg / mm³ is preferably less than 45 µg / mm³ and preferably less than 40 µg / mm³, particularly preferably less than 35 µg / mm³. The water absorption was determined analogously to ISO 4049.

0051The coating compositions according to the invention can be used in a variety of ways on various substrates and are preferably used as cavity and surface coating in the dental field. The coating compositions according to the invention are preferably used on glass ionomer fillings, provisional crowns and bridges made of composite, and on composite restorations. The adhesive "interfaces" between the composite and the hard tooth substance can be protected by lacquer compositions according to the invention.

0052As cavity lacquers, the lacquer compositions according to the invention can serve as an underfill for tooth filling materials and thereby shield the pulp from damaging monomers. As a surface lacquer, the lacquer compositions according to the invention can protect the tooth enamel against external impairments and against the substances present in the oral cavity and on the tooth surface and prevent the occurrence of caries.

0053When used on composite surfaces in the case of final composite restorations, a lacquer composition according to the invention serves to prevent premature wear of the restoration. It therefore improves the wear resistance of the restorative material underneath. A coating composition according to the invention brings about a lasting consolidation of restored surfaces and protects against abrasion and discoloration. Because of their extremely low viscosities, lacquer compositions according to the invention are able to flow into marginal gaps, fill them up and thus close them. They show the same behavior with microcracks on restorative surfaces.

0054In addition, the coating compositions according to the invention meet demanding aesthetic requirements. By applying a very thin layer of a lacquer composition according to the invention, a long-lasting, high-gloss, extremely smooth surface is formed. A varnish composition according to the invention thus gives the tooth or the restoration a natural shine through the formation of aesthetic surfaces. The fine surface smoothness reduces the risk of dye deposits.

0055The coating compositions according to the invention can also be used for the surface treatment of temporary crowns and bridges.

0056Dental lacquer compositions according to the invention are preferably designed such that they can be used as cavity and / or surface lacquer, as an underfill for tooth filling materials, to protect the tooth enamel, to prevent tooth decay, to protect a restoration (in particular against premature wear), to improve the Wear resistance of a dental filling material, for strengthening restored surfaces, to protect against abrasion and / or discoloration of a tooth or restoration, to close marginal gaps and / or micro-cracks, to smooth restorative surfaces, to give natural shine to a tooth or restoration and to reduce dye deposits on a tooth or a restoration. Corresponding uses of a coating composition according to the invention are preferred.

Component (a): monomer component

0057Within a coating composition according to the invention, the function of the monomer component (a) is to form a matrix. This matrix is ​​formed by polymerization, in particular radical polymerization, of one, two or more monomers of the structure Q (YZ_e)_b (as defined above and wherein each Y is selected or omitted independently of any further structural elements Y) of component (a1) together with one or more further monomers of components (a2), (a3) ​​and (a4). The monomer component (a) is a monomer mixture which comprises component (a1) and component (a2) and optionally component (a3) ​​and optionally component (a4) or consists thereof.

0058The ratio of the mass of component (a1) to the total mass of components (a2), (a3) ​​and (a4) is in the range from 4: 1 to 1: 6, preferably in the range from 3: 1 to 1: 3.

0059The total amount of component (a1) is preferably at least 10% by weight, preferably at least 15% by weight, in each case based on the total mass of the coating composition according to the invention.

0060The total amount of component (a1) is preferably in the range from 10 to 80% by weight, preferably in the range from 15 to 75% by weight, in each case based on the total mass of the coating composition according to the invention.

0061The polyalicyclic structural element Q of component (a1) ensures a sterically rigid and hydrophobic backbone, the methacrylate monomers of component (a2) ensure rapid polymerization kinetics and the optional monomers of components (a3) ​​and / or (a4) sufficient networking. The latter also applies in particular to surface-modified fillers, if available.

0062Particularly preferred coating compositions according to the invention contain both component (a2) and component (a3).

0063A combination of component (a2) and component (a3) ​​allows fine adjustment of the mechanical and rheological properties of a coating composition according to the invention. In particular, the combination of highly functionalized acrylate compounds of component (a3) ​​with the extremely mobile monofunctionalized monomers of low molecular weight of component (a2) generates rapid polymerization kinetics by means of diffusion processes, thus creating a quick-curing lacquer composition.

Component (a1): one, two or more monomers of structure Q (YZ

<u>e</u>

)

<u>b</u>

with at least one polyalicyclic structural element

0064Component (a1) form one, two or more monomers of the structure Q (YZ_e)_b, (as defined above and where each Y is selected or omitted independently of any further structural elements Y) where Z preferably denotes 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 structure Q (YZ_e)_b (as defined above and where each Y is selected or omitted independently of any further structural elements Y), 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 (YZ_e)_b, (as defined above and where each Y is selected or omitted independently of any further structural elements Y) which have one, two or more acrylate and / or methacrylate groups, preferably two or more acrylate and / or methacrylate groups.

0065The polymers and products obtainable with the monomers of component (a1) according to the invention or to be used according to the invention have a pronounced hydrophobicity, which is evident, inter alia, in a very low water absorption of the polymers and products. In addition, the polymers obtainable using the monomers of component (a1) according to the invention or to be used according to the invention are notable for high mechanical stability, which can be seen inter alia shows in a high flexural strength of the polymers. The monomers of component (a1) according to the invention or to be used according to the invention, in particular according to the particularly preferred embodiments and embodiments, can be processed to give polymers which, in the cured state, have both low water absorption and high flexural strength.

0066It has also been found that the monomers of component (a1) according to the invention or to be used according to the invention have comparatively low viscosities that can be used. These monomers of component (a1) can be copolymerized with the further monomers of component (a2) and optionally component (a3) ​​and optionally component (a4), the cured polymers or Molded materials have low shrinkage, good adhesion to various substrates, high resistance to hydrolysis, low water absorption, high mechanical strength and high gloss. The properties mentioned are particularly important in the field of dental technology.

0067In particular, the preferred and particularly preferred compounds of component (a1) according to the invention or 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.

0068Preferred compounds according to the invention or 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 and tricyclic hydrocarbon radicals, preferably none of the substituents YZ_e (as defined above and where each Y is selected or omitted independently of any further structural elements Y) substituted hydrogen atoms of this polyalicyclic structural element Q is substituted.

0069If a compound according to the invention comprises two or more polyalicyclic structural elements, these can be identical or different.

0070Monomers Q (YZ.) According to the invention or to be used according to the invention are particularly preferred_e)_b (as defined above and where each Y is selected or omitted independently of any further structural elements Y) 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.

0071In the case of the particularly preferred compounds according to the invention or to be used 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 YZ_e (as defined above and where each Y is selected or omitted independently of any further structural elements Y) substituted hydrogen atoms of this polyalicyclic structural element Q is substituted.

0072Particularly preferred compounds according to the invention or 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 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.

0073Methacrylic 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="ul0011" 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) oxymethyltricyclo [5.2.1.0^2,6] dec-3-en</li><li>9-hydroxymethyl-8- (2-vinyloxyethyl) oxymethyltricyclo [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:</li><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><li>Methacrylic acid or acrylic acid esters of compounds from the group consisting of:</li><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><li>Methacrylic or acrylic acid esters containing urethane or urea groups of compounds selected from the group consisting of:</li><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>

0074Here, 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.

0075Many of the radically polymerizable methacrylic acid or acrylic acid esters with a TCD structural element listed above are known from the prior art.

0076Our own investigations have shown that in particular with the monomers Q (YZ_e)_b (as defined above and where each Y is selected or omitted independently of any further structural elements Y) of component (a1) with a tricyclo [5.2.1.0^2,6] -Decane structural element of component (a1) lacquer compositions with a low contact angle on dry enamel (preferably less than 40 °, preferably less than 30 °) and low water absorption (preferably less than 40 µg / mm³, preferably less than 35 µg / mm³) are available.

0077Y 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="EP2436364A2_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.

0078The 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.

0079The 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.

0080The 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.

0081Y 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="EP2436364A2_D0002.tif" /></chemistry><chemistry id="chem0003" num="0003"><img file="EP2436364A2_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP2436364A2_D0004.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP2436364A2_D0005.tif" /></chemistry><chemistry id="chem0006" num="0006"><img file="EP2436364A2_D0006.tif" /></chemistry><chemistry id="chem0007" num="0007"><img file="EP2436364A2_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.

0082The 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.

0083The 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.

0084The 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.

0085In 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="EP2436364A2_D0008.tif" /></chemistry><chemistry id="chem0009" num="0009"><img file="EP2436364A2_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.

0086The compounds of the structure Q (Y_xZ._e)_b can be obtained according to production processes known to the person skilled in the art.

0087Compounds 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.

0088Compounds 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.

0089Compounds 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.

0090Compounds 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.

0091Compounds 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.

0092Compounds of the structure Q (Y_xZ._e)_b with an N-acylurea structural element can be obtained, for example, by reacting (i) an educt compound with an amide group and (ii) an educt compound with an isocyanate group.

0093In a preferred embodiment of a coating composition according to the invention, component (a1) is selected such that it comprises or consists of bis (methacryloyloxymethyl) tricyclo [5.2.1.0^2,6] decane and / or bis (acryloyloxymethyl) tricyclo [5.2.1.0^2,6] decan.

0094In lacquer compositions according to the invention, the methacrylic acid esters are preferred because of their higher biological compatibility than the corresponding acrylic acid esters, ie that Z in compounds of the structure Q (YZ_e)_b (as defined above and where each Y is selected or omitted independently of any further structural elements Y) preferably -O- (C = O) -C (CH₃) = CH₂ means.

0095Furthermore preferred compounds (monomers) of structure Q (YZ_e)_b (as defined above and where each Y is selected or omitted independently of any further structural elements Y) of component (a1) are those having 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 linked to an N atom, an O atom or a carbonyl group.

0096<patcit id="pcit0017" 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.

0097<patcit id="pcit0018" dnum="EP0209700A2"><text>EP 0 209 700 A2</text></patcit>, <patcit id="pcit0019" dnum="DE3522006"><text>DE 35 22 006</text></patcit> and <patcit id="pcit0020" 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.

0098<patcit id="pcit0021" dnum="EP0000194A1"><text>EP 0 000 194 A1</text></patcit> (corresponding <patcit id="pcit0022" 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 varnishes .

0099<patcit id="pcit0023" 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="pcit0024" 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.

0100<patcit id="pcit0025" 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.

0101<patcit id="pcit0026" 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="pcit0027" dnum="EP0712840B1"><text>EP 0 712 840 B1</text></patcit> can be used as a binder or binder component in coating compositions.

0102<patcit id="pcit0028" 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="pcit0029" 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.

0103<patcit id="pcit0030" dnum="DE102007040240A1"><text>DE 10 2007 040 240 A1</text></patcit> and <patcit id="pcit0031" 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="pcit0032" 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.

0104<patcit id="pcit0033" 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="pcit0034" 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.

0105<patcit id="pcit0035" 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="pcit0036" dnum="DE102004060285A1"><text>DE 10 2004 060 285 A1</text></patcit> mentioned.

0106<patcit id="pcit0037" dnum="WO03035013A1"><text>WO 03/035013 A1</text></patcit> and <patcit id="pcit0038" dnum="DE60216951T2"><text>DE 602 16 951 T2</text></patcit> relate to dental adhesive compositions for binding dental restoratives to dentin and / or tooth enamel. In these documents, inter alia, the preparation of 3, (4), 8, (9) bis (2-propenamidomethyl) tricyclo [5.2.1.0]^2,6-decan described.

0107<patcit id="pcit0039" dnum="US6670499B1"><text>US 6,670,499 B1</text></patcit> describes diurethanes derived from adamantane. In the<patcit id="pcit0040" 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).

0108There is a constant need in the field of dental technology for further low-shrinkage free-radically polymerizable monomers. It was therefore a further object of the present invention to provide new radically polymerizable monomers which can be used as a component of component (a1) in a coating composition according to the invention, in particular in a dental coating composition according to the invention.

0109This further problem is solved by connecting the structure Q (YZ_e)_b (as defined above and 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 N-acylurea, allophanate, biuret and amide, the amide function not being immediate is linked to an N atom, an O atom or a carbonyl group, where:<ul id="ul0012" list-style="dash" compact="compact"><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 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></ul><ul id="ul0013" list-style="dash"><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 and - (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), - 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="ul0014" 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, or the compound is a second reaction product from a reaction of the above first reaction product with</li></ul></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>

0110It follows from the above that compounds according to the invention which contain an amide group (as defined), this amide group is not part of a urethane group.

0111Compounds according to the invention having the structure Q (YZ_e) b (as defined above and wherein each Y is selected independently of any further structural elements Y) of component (a1) with one, two, three, four or more functional groups selected from the group consisting of N-acylurea, allophanate, biuret and amide , wherein the amide function is not directly linked to an N atom, an O atom or a carbonyl group, the amide again preferably meaning (meth) acrylamide.

0112In preferred compounds of the structure Q (YZ_e)_b (as defined above and each Y being selected independently of any further structural elements Y), the link between Q and at least one structural element Z is made 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="EP2436364A2_D0010.tif" /></chemistry><chemistry id="chem0011" num="0011"><img file="EP2436364A2_D0011.tif" /></chemistry><chemistry id="chem0012" num="0012"><img file="EP2436364A2_D0012.tif" /></chemistry><chemistry id="chem0013" num="0013"><img file="EP2436364A2_D0013.tif" /></chemistry><chemistry id="chem0014" num="0014"><img file="EP2436364A2_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.

0113The 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 N-acylurea, allophanate and biuret, where:<ul id="ul0015" 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="EP2436364A2_D0015.tif" /></chemistry><chemistry id="chem0016" num="0016"><img file="EP2436364A2_D0016.tif" /></chemistry><chemistry id="chem0017" num="0017"><img file="EP2436364A2_D0017.tif" /></chemistry><chemistry id="chem0018" num="0018"><img file="EP2436364A2_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.

0114These compounds according to the invention are particularly suitable as monomers for use in coating compositions according to the invention.

0115Such a connection according to the invention preferably has 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.

0116In 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.

0117The above-mentioned other residues R¹, R² or R³ of a new compound according to the invention, in each case independently of one another, are preferably selected from the group consisting of hydrogen, linear, branched or ring-comprising structural elements having 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.

0118The other residues R¹, R² or R³ of a new compound according to the invention, in each case independently of one another, are preferably selected from the group consisting of hydrogen, linear, branched or ring-comprising structural elements having 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.

0119The other residues R¹, R² or R³ of a new compound according to the invention, in each case independently of one another, are preferably selected from the group consisting of hydrogen, linear, branched or ring-comprising structural elements having 1 to 20 C atoms and 0 to 5 heteroatoms, the heteroatoms which may be present being selected from the group consisting from N and O.

0120A new compound Q (Y_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="ul0016" 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>

0121A compound according to the invention in a preferred embodiment is a second reaction product from a reaction of the above first reaction product with<ul id="ul0017" 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>

0122In a preferred embodiment, m = 0. This applies to all aspects of the present invention.

0123In preferred connections according to the invention, the link between Q and at least one structural element Z takes place 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="EP2436364A2_D0019.tif" /></chemistry><chemistry id="chem0020" num="0020"><img file="EP2436364A2_D0020.tif" /></chemistry><chemistry id="chem0021" num="0021"><img file="EP2436364A2_D0021.tif" /></chemistry><chemistry id="chem0022" num="0022"><img file="EP2436364A2_D0022.tif" /></chemistry><chemistry id="chem0023" num="0023"><img file="EP2436364A2_D0023.tif" /></chemistry><chemistry id="chem0024" num="0024"><img file="EP2436364A2_D0024.tif" /></chemistry>where R¹, R², R³ R⁴, R⁵ mean other radicals of the compound and Q and n have the meaning given above.

0124The binding arranged on the right in the formula picture is closer to the structural element Z.

0125In 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="EP2436364A2_D0025.tif" /></chemistry><chemistry id="chem0026" num="0026"><img file="EP2436364A2_D0026.tif" /></chemistry><chemistry id="chem0027" num="0027"><img file="EP2436364A2_D0027.tif" /></chemistry><chemistry id="chem0028" num="0028"><img file="EP2436364A2_D0028.tif" /></chemistry><chemistry id="chem0029" num="0029"><img file="EP2436364A2_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.

0126As already mentioned above, preferred new compounds 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 (where each Y is selected independently of any further structural elements Y) substituted hydrogen atoms of this polyalicyclic structural element Q is substituted.

0127Particularly preferred compounds 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.

0128New compounds according to the invention are preferred 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>

0129New compounds 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.

0130New compounds according to the invention are preferred in which all existing light-curable groups correspond to the structural element Z.

0131New compounds according to the invention are preferred in which all existing terminal polymerizable groups correspond to the structural element Z.

0132In addition to light-curable groups of structural element Z, a new compound according to the invention can 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.

0133Further preferred novel compounds 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="EP2436364A2_D0030.tif" /></chemistry><chemistry id="chem0031" num="0031"><img file="EP2436364A2_D0031.tif" /></chemistry><chemistry id="chem0032" num="0032"><img file="EP2436364A2_D0032.tif" /></chemistry><chemistry id="chem0033" num="0033"><img file="EP2436364A2_D0033.tif" /></chemistry><chemistry id="chem0034" num="0034"><img file="EP2436364A2_D0034.tif" /></chemistry>where Z, R, m and n have the meaning given above and in which the following also applies:<ul id="ul0018" 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>

0134In a preferred embodiment, m = 0.

0135Likewise preferred compounds 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="EP2436364A2_D0035.tif" /></chemistry><chemistry id="chem0036" num="0036"><img file="EP2436364A2_D0036.tif" /></chemistry><chemistry id="chem0037" num="0037"><img file="EP2436364A2_D0037.tif" /></chemistry><chemistry id="chem0038" num="0038"><img file="EP2436364A2_D0038.tif" /></chemistry><chemistry id="chem0039" num="0039"><img file="EP2436364A2_D0039.tif" /></chemistry><chemistry id="chem0040" num="0040"><img file="EP2436364A2_D0040.tif" /></chemistry><chemistry id="chem0041" num="0041"><img file="EP2436364A2_D0041.tif" /></chemistry><chemistry id="chem0042" num="0042"><img file="EP2436364A2_D0042.tif" /></chemistry><chemistry id="chem0043" num="0043"><img file="EP2436364A2_D0043.tif" /></chemistry><chemistry id="chem0044" num="0044"><img file="EP2436364A2_D0044.tif" /></chemistry>where each Q has the above meaning irrespective of any other structural elements and where Z, A, k and R 'and n have the meaning given above.

0136In 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, 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="chem0045" num="0045"><img file="EP2436364A2_D0045.tif" /></chemistry><chemistry id="chem0046" num="0046"><img file="EP2436364A2_D0046.tif" /></chemistry><chemistry id="chem0047" num="0047"><img file="EP2436364A2_D0047.tif" /></chemistry><chemistry id="chem0048" num="0048"><img file="EP2436364A2_D0048.tif" /></chemistry>where Z, R, m and n have the meaning given above and in which the following also applies:<ul id="ul0019" 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>

0137In a preferred embodiment, the present invention relates to a novel 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="EP2436364A2_D0049.tif" /></chemistry><chemistry id="chem0050" num="0050"><img file="EP2436364A2_D0050.tif" /></chemistry><chemistry id="chem0051" num="0051"><img file="EP2436364A2_D0051.tif" /></chemistry><chemistry id="chem0052" num="0052"><img file="EP2436364A2_D0052.tif" /></chemistry><chemistry id="chem0053" num="0053"><img file="EP2436364A2_D0053.tif" /></chemistry><chemistry id="chem0054" num="0054"><img file="EP2436364A2_D0054.tif" /></chemistry><chemistry id="chem0055" num="0055"><img file="EP2436364A2_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="ul0020" 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>

0138Again 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 comprising 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.

0139Again preferred is a compound 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 carbon atoms and 0 to 10 heteroatoms, preferably with 1 to 5 heteroatoms, the heteroatoms which may be present preferably being selected from the group consisting of N and O.

0140Further 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.

0141In 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="ul0021" 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>

0142The present invention further relates to a method for producing a compound Q (YZ_e)_b (where each Y is selected independently of any further structural elements Y) or a mixture comprising at least such a compound Q (YZ_e)_b, with the following steps:

0143Implementing 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="ul0022" 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, 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.</li></ul></li></ol>

0144A preferred method according to the invention for the preparation of a compound Q (Y_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, or a mixture comprising at least one such compound Q (Y_xZ._e)_b, is a process with the following steps:

0145Implementing in a first reaction<ol id="ol0008"><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 to a first implementation product,</li></ol>

0146in a second reaction, reacting the first reaction product with<ul id="ul0023" list-style="none"><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, e, M, R, m and n each have the meaning given above, and 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, the second and optionally the third reaction is greater than or equal to 1, preferably in the range from 1.1: 1 to 5: 1, more preferably in the range of 1.25: 1 to 4: 1, more preferably in the range of 1.5: 1 to 3: 1, and most preferably in the range of 2: 1 to 2.5: 1.</li></ul>

0147In a process according to the invention for producing a compound Q (Y_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, or a mixture comprising at least one such compound Q (Y_xZ._e)_b, is the ratio of the total number of reacted NCO groups to the total number of reacted - NH₂, -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.

0148The 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.

0149Preferred 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.

0150The 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).

0151The 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).

0152In a further aspect, the present invention relates to a mixture comprising one, two or more different compounds according to the invention, which can be prepared by a process according to the invention.

0153In a further aspect, the present invention relates to the use of a coating composition according to the invention, preferably in one of the configurations marked as preferred or particularly preferred, for coating a surface, in particular as a protective and / or gloss coating.

0154In a further aspect, the present invention relates to the use of a compound according to the invention, preferably in one of the configurations marked as preferred or particularly preferred, for producing a lacquer composition according to the invention, preferably for producing a dental lacquer composition.

0155In a further aspect, the present invention relates to the use of a compound according to the invention, preferably in one of the configurations marked as preferred or particularly preferred, in a coating composition, preferably in one of the configurations marked as preferred or particularly preferred.

0156In a further aspect, the present invention relates to the use of a compound according to the invention, preferably in one of the configurations marked as preferred or particularly preferred, in a dental lacquer composition.

0157In a further aspect, the present invention relates to a coating composition as or for use as dental material, preferably as cavity and / or surface lacquer, as an underfill for tooth filling materials, to protect tooth enamel, to prevent tooth decay, to protect a restoration (especially against premature wear), to improve the wear resistance of a dental filling material, for consolidation restored surfaces, to protect against abrasion and / or discoloration of a tooth or a restoration, for closing marginal gaps and / or micro cracks, for smoothing restorative surfaces, for imparting natural shine on a tooth or a restoration and for reducing dye deposits on a tooth or a restoration.

0158The present invention also relates to a product obtainable by curing a coating composition according to the invention, in particular in one of the configurations marked as preferred or particularly preferred.

0159The present invention thus also relates to a coating composition, preferably in one of the above or In the following, configurations designated as preferred, for use in a therapeutic process as dental material, preferably as cavity and / or surface lacquer, as underfill for tooth filling materials, to protect the tooth enamel, to prevent tooth decay, to protect a restoration (in particular against premature wear), to improve the wear resistance of a dental filling material, to consolidate restored surfaces, to protect against abrasion and / or discoloration of a tooth or restoration, to close marginal gaps and / or micro-cracks, to smooth restorative surfaces, to give natural shine to a tooth or restoration and to reduce dye deposits on a tooth or a restoration.

0160The present invention also relates to the non-therapeutic use, preferably the cosmetic or aesthetic use, of a lacquer composition according to the invention, preferably in one of the configurations designated above or below as preferred, for smoothing restorative surfaces, for imparting natural shine to a tooth or a restoration and to reduce dye deposits on a tooth or a restoration.

0161The present invention accordingly also relates to the use of a coating composition according to the invention, preferably in one of the configurations designated above or below as preferred, in a non-therapeutic process, preferably in a cosmetic or aesthetic processes, for smoothing restorative surfaces, for imparting natural shine to a tooth or a restoration and for reducing dye deposits on a tooth or a restoration.

0162Hydroxyl compounds of (meth) acrylates can preferably be used to prepare the compounds according to the invention, it also being possible to use mixtures of acrylates and methacrylates. Preferred (for use as reactants according to component B), C) and / or D)) are:<ul id="ul0024" 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>

0163Isocyanates can also be used as component B) to prepare the compounds according to the invention. Mono- and diisocyanates are preferred.

0164Preferred diisocyanates are selected from the group consisting of cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, hexane diisocyanate, such as diisocyanate diisocyanate, butane diisocyanate, butane diisocyanate, Heptane diisocyanate, octane diisocyanate, nonane diisocyanate, such as 1,6-diisocyanato-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.

0165Preferred 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).

0166In 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.

0167For 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.

0168The 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.

0169In 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)

0170Bis (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] 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.

0171The 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="pcit0041" dnum="JP7206740A"><text>JP 7-206740</text></patcit>, <patcit id="pcit0042" dnum="EP1112995B1"><text>EP 1 112 995 B1</text></patcit> or <patcit id="pcit0043" 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="pcit0044" 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.

0172The 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="pcit0045" dnum="EP0023686B1"><text>EP 0 023 686 B1</text></patcit> contains precise manufacturing instructions.

0173The 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="pcit0046" 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="pcit0047" dnum="DE3338077A1"><text>DE 33 38 077 A1</text></patcit> can be synthesized by phosgenation of dihydrooxazines.

0174The 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="EP2436364A2_D0056.tif" /></chemistry>

0175The urethane of the formula (1) also has two reactive hydrogen atoms on nitrogen, which are then reacted further in a second reaction step with excess isocyanate to form a compound 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="EP2436364A2_D0057.tif" /></chemistry><chemistry id="chem0058" num="0058"><img file="EP2436364A2_D0058.tif" /></chemistry>

0176Alternatively, 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="pcit0048" 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="EP2436364A2_D0059.tif" /></chemistry>

0177The 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="EP2436364A2_D0060.tif" /></chemistry>

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

2,6

] decan

0178The 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="EP2436364A2_D0061.tif" /></chemistry>

0179Further 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="EP2436364A2_D0062.tif" /></chemistry>If 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="EP2436364A2_D0063.tif" /></chemistry>

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

2,6

] decan

0180The 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="pcit0049" dnum="DE3703120A1"><text>DE 37 03 120 A1</text></patcit> as well as the <patcit id="pcit0050" dnum="WO2009065873A2"><text>WO 2009/065873 A2</text></patcit>). The implementation of the second reaction stage of the isocyanate-alcohol reaction according to the invention can be initiated not only starting from the tricyclodecanediol with the isocyanatoethyl methacrylate, but also starting from the 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="EP2436364A2_D0064.tif" /></chemistry>

0181This 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="EP2436364A2_D0065.tif" /></chemistry>

0182Reaction of the allophanate diisocyanate (formula (12)) with methacrylic acid provides the compound of formula (13).<chemistry id="chem0066" num="0066"><img file="EP2436364A2_D0066.tif" /></chemistry>

0183Instead 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 those explicitly mentioned above.

0184These 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="EP2436364A2_D0067.tif" /></chemistry>

0185Reaction of the amide of formula (16) with 2-isocyanatoethyl methacrylate gives the acylurea of ​​formula (17).<chemistry id="chem0068" num="0068"><img file="EP2436364A2_D0068.tif" /></chemistry>

0186The 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="EP2436364A2_D0069.tif" /></chemistry>

0187If 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="EP2436364A2_D0070.tif" /></chemistry><chemistry id="chem0071" num="0071"><img file="EP2436364A2_D0071.tif" /></chemistry>

0188Further 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

0189The 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="pcit0051" dnum="EP0209700A2"><text>EP 0 209 700 A2</text></patcit> known urea compound of formula (26).<chemistry id="chem0072" num="0072"><img file="EP2436364A2_D0072.tif" /></chemistry>

0190Here, 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="EP2436364A2_D0073.tif" /></chemistry>

0191The 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="EP2436364A2_D0074.tif" /></chemistry>

0192Analog 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="EP2436364A2_D0075.tif" /></chemistry>

0193The reaction of the compound of formula (11) with diisocyanatoadamantane [(bis (isocyanatomethyl) tricyclo [3.3.1.1^3.7] decan] provides a monomer 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="EP2436364A2_D0076.tif" /></chemistry>

Component (a2): Monofunctionalized C1-C5 alkyl methacrylates

0194Component (a2) consists of one, two or more free-radically polymerizable monofunctionalized monomers from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and pentyl methacrylate.

0195Paint compositions according to the invention are particularly preferred which comprise a component (a2) which comprises methyl methacrylate or consists of methyl methacrylate, since particularly good results in the sense of the present invention were then achieved.

0196The total amount of component (a2) is preferably at least 5% by weight, preferably at least 8% by weight, in each case based on the total mass of the coating composition according to the invention.

0197The total amount of component (a2), in particular methyl methacrylate, is preferably in the range from 5 to 45% by weight, preferably in the range from 8 to 40% by weight, in each case based on the total mass of the coating composition according to the invention.

Component (a3): Monomers with three or more (meth) acrylate groups

0198The optional component (a3) ​​consists of one, two or more free-radically polymerizable monomers from the group consisting of further free-radically polymerizable monomers with three, four, five, six or more (meth) acrylate groups, preferably with three to six acrylate groups.

0199Preferred as component (a3) ​​are acrylate monomers, since they are significantly faster in the polymerization than the corresponding methacrylates, ie they allow a rapid polymerization process and faster curing.

0200Paint compositions according to the invention are particularly preferred which comprise a component (a3) ​​which comprises dipentaerythritol pentaacrylate or consists of dipentaerythritol pentaacrylate, since particularly good results within the meaning of the present invention have been achieved thereby.

0201Lacquer compositions preferred according to the invention therefore contain both methyl methacrylate (component (a2) and dipentaerythritol pentaacrylate (component (a3).

0202Particularly good results in the sense of the present invention were achieved with such coating compositions.

0203The total amount of component (a3) ​​is preferably at least 5% by weight, preferably at least 8% by weight, in each case based on the total mass of the coating composition according to the invention.

0204The total amount of component (a3), in particular dipentaerythritol pentaacrylate, is preferably in the range from 5 to 65% by weight, preferably in the range from 8 to 60% by weight, in each case based on the total mass of the coating composition according to the invention.

Component (a4): further radically polymerizable monomers from the group consisting of acrylates and methacrylates, preferably from the group of methacrylates

0205The optional constituent of the matrix-forming monomer mixture which cannot be counted as components (a1), (a2) and (a3) ​​form free-radically polymerizable monomers selected from the group consisting of acrylates and methacrylates.

0206The free-radically polymerizable monomers of component (a4) preferably have at least two ethylenic groups.

0207A large number of diacrylate and dimethacrylate monomers are mentioned in the patent literature (for example also in US Pat <patcit id="pcit0052" 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 range from column 6, line 15 to column 8, line 10), which are suitable for use in a coating composition according to the invention.

0208Lacquer compositions according to the invention can also contain one or more dimethacrylate monomers as component (a4), preferably 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.

0209Bisphenol-A-glycidyl methacrylate (Bis-GMA) can be used, but preferably a coating composition according to the invention, in particular a dental coating composition according to the invention, does not contain the compound Bis-GMA. A coating composition according to the invention, in particular a dental coating composition according to the invention, is preferably free from all compounds having a bisphenol A structural element.

0210The free-radically polymerizable monomers of component (a4), which therefore do not belong to component (a1), 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.

0211As 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="pcit0053" dnum="DE19903177"><text>DE 199 03 177</text></patcit> or in the <patcit id="pcit0054" dnum="DE4416857"><text>DE 44 16 857</text></patcit> are described, which are part of the present application by reference.

0212A coating composition according to the invention, in particular a dental coating composition according to the invention, can furthermore contain one or more acid group-containing acrylate and / or methacrylate monomers in component (a4). 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.

0213Suitable monomers containing a phosphoric acid group are, for example, 2- (meth) acryloyloxyethyl dihydrogen phosphate, bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 10- (meth) acryloyloxyphydylphosphate (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.

0214Suitable 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.

0215Other suitable monomers bearing acid groups are, for example, in US Pat <patcit id="pcit0055" dnum="EP0980682A1"><text>EP 0 980 682 A1</text></patcit> (in particular paragraphs [0059] to [0065]) or the <patcit id="pcit0056" 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.

0216Furthermore, the phosphoric acid esters with glycerol dimethacrylate or with hydroxyethyl methacrylate or with hydroxypropyl methacrylate can also be used.

0217The monomers mentioned can be used individually or in mixtures.

Component (b): initiators and / or catalysts

0218A coating composition according to the invention is preferably light-curable and / or chemically curable. Favor t is a coating composition according to the invention wherein component (b) comprises one or more Lichthärtungsinitiatoren and / or one or more initiators for chemical curing or consists of these.

0219The total amount of component (b), in particular of phosphine oxide initiators, is preferably in the range from 1 to 6% by weight, preferably in the range from 1.5 to 5% by weight, in each case based on the total mass of the coating composition according to the invention.

0220Preferred coating compositions according to 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.

0221Examples 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="pcit0057" dnum="DE102006019092A1"><text>DE 10 2006 019 092 A1</text></patcit> or in the <patcit id="pcit0058" dnum="DE3941629C2"><text>DE 39 41 629 C2</text></patcit>which are part of the present application by reference.

0222Examples 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="pcit0059" dnum="DE102006019092"><text>DE 10 2006 019 092</text></patcit> or in the <patcit id="pcit0060" dnum="DE3941629C2"><text>DE 39 41 629 C2</text></patcit>which are part of the present application by reference.

0223Other suitable initiators and combinations of initiators are in the <patcit id="pcit0061" dnum="DE60116142"><text>DE 601 16 142</text></patcit> described, which are part of the present application by reference.

0224The 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 which can cause curing of a lacquer composition according to the invention, in particular a dental lacquer composition according to the invention.

0225The 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.

0226A coating composition 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).

0227Particularly preferred initiators as component (b) of a coating composition according to the invention are phosphine oxides, in particular acylphosphine oxides.

0228With these phosphine oxide initiators, coating compositions according to the invention can be obtained which harden without a smear layer. Further preferred phosphine oxides are phenyl-bis (2,4,6-trimethylbenzoyl) phosphine oxide and / or 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

0229Also 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.

0230With regard to the structures of suitable phosphine oxides for use in a coating composition according to the invention, reference is made to the documents <patcit id="pcit0062" dnum="DE3801511C2"><text>DE 38 01 511 C2</text></patcit>, <patcit id="pcit0063" dnum="DE102006050153A1"><text>DE 10 2006 050 153 A1</text></patcit>, <patcit id="pcit0064" dnum="EP0184095B1"><text>EP 0 184 095 B1</text></patcit>, <patcit id="pcit0065" dnum="DE4231579C2"><text>DE 42 31 579 C2</text></patcit>, <patcit id="pcit0066" dnum="EP0366977B1"><text>EP 0 366 977 B1</text></patcit>, <patcit id="pcit0067" dnum="US7081485B2"><text>US 7,081,485 B2</text></patcit>, <patcit id="pcit0068" dnum="DE3236026A1"><text>DE 32 36 026 A1</text></patcit>, <patcit id="pcit0069" dnum="US20070027229A1"><text>US 2007/0027229 A1</text></patcit>, <patcit id="pcit0070" dnum="EP0262629B1"><text>EP 0 262 629 B1</text></patcit>, <patcit id="pcit0071" dnum="EP0073413A"><text>EP 0 073 413</text></patcit>, <patcit id="pcit0072" dnum="US7148382B2"><text>US 7,148,382 B2</text></patcit>, <patcit id="pcit0073" dnum="US5761169A"><text>US 5,761,169</text></patcit>, <patcit id="pcit0074" dnum="DE19708294A1"><text>DE 197 08 294 A1</text></patcit>, <patcit id="pcit0075" dnum="EP0057474A"><text>EP 0 057 474</text></patcit>, <patcit id="pcit0076" dnum="EP0047902A"><text>EP 0 047 902 A</text></patcit>, <patcit id="pcit0077" dnum="EP0007508A"><text>EP 0 007 508</text></patcit>, <patcit id="pcit0078" dnum="DE60029481T2"><text>DE 600 29 481 T2</text></patcit>, <patcit id="pcit0079" dnum="EP0980682B1"><text>EP 0 980 682 B1</text></patcit>, <patcit id="pcit0080" dnum="EP0948955B1"><text>EP 0 948 955 B1</text></patcit>, <patcit id="pcit0081" dnum="EP1236459B1"><text>EP 1 236 459 B1</text></patcit> and <patcit id="pcit0082" dnum="EP0173567A2"><text>EP 0 173 567 A2</text></patcit> referenced, which are part of the present application by reference.

0231The phosphine oxides specified in these publications are particularly suitable on their own or in combination with the "alpha-diketone / amine" system as a photopolymerization initiator system in a coating composition according to the invention.

0232Alternatively, borate salts, as described, for example, in <patcit id="pcit0083" dnum="US4772530A"><text>US 4,772,530</text></patcit>, <patcit id="pcit0084" dnum="US4954414A"><text>US 4,954,414</text></patcit>, <patcit id="pcit0085" dnum="US4874450A"><text>US 4,874,450</text></patcit>, <patcit id="pcit0086" dnum="US5055372A"><text>US 5,055,372</text></patcit> and <patcit id="pcit0087" dnum="US5057393A"><text>US 5,057,393</text></patcit> are used as photoinitiators, which are part of the present application by reference.

0233Other 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.

0234Various initiators for chemical curing are known to the person skilled in the art. In this respect it is exemplary of the<patcit id="pcit0088" dnum="EP1720506A"><text>EP 1 720 506</text></patcit> referred.

0235Preferred 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.

0236The 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).

0237Dual curing systems include a combination of photoinitiators and chemical curing initiators.

0238For 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.

0239In addition to the oxidatively active organic peroxide compounds, barbituric acids or barbituric acid derivatives and malonyl sulfamides can also be used as redox systems.

0240Of 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="pcit0089" dnum="EP1839640A"><text>EP 1 839 640</text></patcit> as in <patcit id="pcit0090" dnum="DE1495520"><text>DE 1495520</text></patcit>, <patcit id="pcit0091" dnum="WO02092021A"><text>WO 02/092021</text></patcit> or in <patcit id="pcit0092" dnum="WO02092023A"><text>WO 02/092023</text></patcit>which are part of the present application by reference.

0241Suitable malonyl sulfamides are in the <patcit id="pcit0093" 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.

0242Sulfur compounds in the oxidation state +2 or +4 such as sodium benzene sulfinate or sodium paratoluenesulfinate can also be used.

0243To 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 (c): filler component

0244A coating composition according to the invention can contain a proportion of a filler component (c) from 0 to 60% by weight, based on the total mass of the coating composition according to the invention, the filler component comprising one, two or more fillers.

0245In accordance with the above and following explanations, the present invention also relates to a coating composition (as defined above)<ul id="ul0025" list-style="none" compact="compact"><li>(c) 0 to 60% by weight of a filler component comprising one, two or more fillers selected from the group consisting of<ul id="ul0026" list-style="none"><li>(c1) a total amount in the range from 0 to 60% by weight of non-agglomerated, preferably surface-modified, nanoparticles with an average particle size of less than 200 nm (preferably less than 100 nm, particularly preferably less than 60 nm),</li><li>(c2) a total amount in the range from 0 to 10% by weight of microparticles with an average particle size of 0.4 µm to 10 µm, and</li><li>(c3) a total amount in the range from 0 to 15% by weight of further fillers, preferably 0 to 10% by weight, preferably 0 to 5% by weight, further fillers,</li></ul>where the percentages by weight each relate to the total mass of the coating composition.</li></ul>

0246The average particle size d₅₀ The filler particles of filler component (c) of a coating composition according to the invention, which can optionally be used according to the invention, is determined by means of light scattering (laser diffraction), preferably using a Beckman Coulter LS 13320 particle size measuring device.

0247The filler component (c) can preferably comprise a filler (c1) in the form of non-agglomerated nanoparticles with an average particle size of less than 200 nm.

0248The filler component (c) can preferably comprise a filler (c1) in the form of non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm.

0249The filler component (c) can preferably alternatively or additionally comprise a filler (c2) in the form of microparticles with an average particle size in the range from 0.4 μm to 10 μm.

0250In a preferred embodiment, the filler component (c) comprises a mixture of a first filler (c1) in the form of non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm and a second filler (c2) in the form of microparticles with an average particle size in the range from 0.4 µm to 10 µm.

0251The combination of (c1) nanoparticles and (c2) microparticles in a coating composition preferred according to the invention achieves a complete and uniform volume filling of the coating composition. This reduces both the shrinkage of the coating composition when the polymer matrix cures and the sensitivity of the coating composition to abrasion.

0252In particular to adjust the rheology, a coating composition according to the invention preferably comprises a small amount of pyrogenic silica, preferably in an amount in the range from 0.1 to 5% by weight, more preferably in the range from 0.5 to 2.5% by weight , based on the total mass of the paint composition.

Component (c1): non-agglomerated nanoparticles

0253In 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.

0254The filler component (c) of a paint composition according to the invention can comprise a filler (c1) in an amount of 0 to 60% by weight, based on the total mass of the paint composition.

0255The proportion of non-agglomerated, optionally organically surface-modified, nanoparticles with an average particle size of less than 200 nm should not be more than 60% by weight, since the processability of the coating composition is then no longer sufficient; Because of the high solids content, their viscosity can become too high.

0256The 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.

0257In a preferred embodiment, the nanoscale particles are in non-agglomerated form, for example dispersed in a medium, preferably in monodisperse form.

0258In order to enable good integration of the nanoparticles in the polymer matrix of a coating composition 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.

0259If only a nanoscale filler (c1) is used as filler component (c), transparent sealing materials can be obtained (see <patcit id="pcit0094" dnum="WO0130307A1"><text>WO 01/30307 A1</text></patcit> and <patcit id="pcit0095" dnum="WO2007028159A2"><text>WO 2007/028159 A2</text></patcit>). Very good abrasion values ​​are then achieved according to the invention.

0260The transparent dental lacquer compositions according to the invention are also distinguished from the products from the prior art by a greatly improved flow behavior (in the uncured state) on the tooth enamel, in particular the dry tooth enamel, and by a much lower water absorption (in the cured state).

0261In a preferred embodiment, therefore, the filler component (c) of a coating composition according to the invention exclusively comprises (c1) non-agglomerated nanoparticles with an average particle size of less than 200 nm.

0262In a further preferred embodiment, the filler component (c) of a coating composition according to the invention consists exclusively of (c1) non-agglomerated, organically surface-modified nanoparticles with an average particle size of less than 200 nm.

Component (c2): microparticles with an average particle size in the range from 0.4 µm to 10 µm

0263In 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 smaller the microparticles, the more complete and uniform the volume filling of the lacquer composition that can be achieved with the microparticles.

0264The filler component (c) of a paint composition according to the invention can comprise a filler (c2) in an amount of 0 to 10% by weight, based on the total mass of the paint composition.

0265The microparticles of component (c2) 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.

0266A component (c2) which contains two or more fractions of microparticles is thus preferably used in a coating composition according to the invention, the mean particle sizes of the fractions differing.

0267Component (c2) preferably contains at least two microparticle fractions, the mean particle sizes of which differ from one another by at least 1 μm.

0268The 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.

0269A coating composition according to the invention preferably comprises a component (c2) 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 microparticle fractions, each have 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.

0270The 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: 1 to 10: 1, preferably in the range from 1.5: 1 to 5: 1.

0271The 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 (c2) is preferably in the range from 1.5: 1 to 10: 1, preferably in the range from 2: 1 to 5: 1.

0272In a particularly preferred coating composition according to the invention, component (c2) comprises one or more first microparticle fractions, each having an average particle size in the range from 1 μm to 10 μm, preferably 1 μm to 5 μm, and one or more second microparticle fractions, each have 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: 1 to 10: 1, preferably 1.5: 1 to 5: 1 and / or the ratio of the average particle size of the or a first microparticle fraction to the average particle size the or a second microparticle fraction of component (c2) is in the range from 1.5: 1 to 10: 1, preferably 2: 1 to 5: 1.

0273The base materials for the microparticles to be used in surface-modified form according to the invention are preferably selected from the group consisting of amorphous materials based on SiO₂, ZrO₂ and / or TiO₂, as well as mixed oxides, pyrogenic silica or precipitated silica, such as 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 fluoropaque fillers like ytterbium fluoride.

0274For better integration into the polymer matrix of a coating composition 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).

0275In a particularly preferred coating composition according to the invention, at least some of the microparticles of component (c2) are formed by organically surface-modified particles, preferably silanized particles, and / or at least some of the microparticles of component (c2) are formed by dental glass particles; preferably at least some of the microparticles of component (c2) are organically surface-modified dental glass particles, preferably silanized dental glass particles.

0276In these cases, component (c2) 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 (c3) - Other fillers

0277The filler component (c) of a coating composition according to the invention can also contain a filler (c3) in an amount of 0 to 15% by weight, preferably in an amount of 0 to 10% by weight, preferably in an amount of 0 to 5% by weight. -%, preferably in an amount of 0 to 2.5 wt .-%, each based on the total mass of the coating composition.

0278These quantitative ranges given above apply in particular to some fillers made of agglomerated particles, since such fillers can lead to an undesirably high viscosity of the coating composition, so that the coating composition is significantly less suitable or is no longer suitable for the purposes mentioned.

0279For example, reinforcing filler materials, such as glass fibers, polyamide or carbon fibers, can be used. A coating composition 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 (d): optional additional additives

0280In some cases, a coating composition according to the invention comprises one or more further additives.

0281These additives can have different functions. Usual additives for use in dental lacquer compositions 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.

0282Light-curable dental lacquer compositions, 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="pcit0096" 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="pcit0097" dnum="DE10119831A1"><text>DE 101 19 831 A1</text></patcit> or in the <patcit id="pcit0098" dnum="EP1563821A1"><text>EP 1 563 821 A1</text></patcit> specified, which are part of the present application by reference.

0283A dental lacquer composition preferred according to the invention thus comprises, as an additive, one or more polymerization inhibitors to increase the storage stability of the lacquer composition, preferably selected from the group consisting of hydroquinone monomethyl ether (HQME), phenols, preferably 2,6-di-tert.butyl-4-methylphenol ( BHT) and tert-butylhydroxyanisole (BHA), 2,2-diphenyl-1-picrylhydrazyl radicals, Galvinoxyl radicals, triphenylmethyl radicals, 2,3,6,6, -Tetramethylpiperidinyl-1-oxyl radical (TEMPO) and its derivatives and phenothiazine and its derivatives.

0284A dental lacquer composition preferred according to the invention comprises, as an additive, one or more fluoride-releasing substances, preferably sodium fluoride and / or amine fluorides.

0285Furthermore, one or more surfactants can be part of a (preferably dental) coating composition according to the invention.

0286UV 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 (preferably dental) coating composition 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.

0287Since the teeth are to be restored as true to nature as possible, it is necessary to provide dental lacquer compositions 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.

0288Flavorings are further optional additives.

0289The invention also relates to a method for producing a coating composition according to the invention, in particular a dental coating composition according to the invention, with the following step:<ul id="ul0027" list-style="dash" compact="compact"><li>Mixing components (a) and (b) and optionally (c) and optionally (d).</li></ul>

Examples

0290The invention is further illustrated by the following examples. Unless otherwise stated, all information is based on weight. The following abbreviations are used:<ul id="ul0028" list-style="none"><li>TCD monomer = bis (methacryloyloxymethyl) tricyclo [5.2.1.0^2,6] decan</li><li>BHT = 2,6-di-tert-butyl-4-methylphenol (stabilizer)</li><li>Nano-SiO₂: Nanoscale silica with an average particle size of 50 nm was used</li><li>Aerosil: Aerosil A200 (Evonik)</li><li>Surfactant: BYK307 (Byk-Chemie GmbH)</li><li>KW = contact angle on dry enamel</li><li><u>Manufacture of paint compositions</u></li></ul>

0291Paint compositions according to the invention and a paint composition not according to the invention were each produced as follows:<ul id="ul0029" list-style="none" compact="compact"><li>The monomers, as well as initiators and additives are first homogenized in a plastic container using a KPG stirrer. The fillers are then optionally added and mixed with a double planetary mixer.</li></ul>

Measurement methods:

Flexural strength

: 3-point bending strength

0292The flexural strength was determined in accordance with ISO 4049. Test pieces with the dimensions 2 x 2 x 50 mm were produced in a mold made of PTFE. These were then polymerized in a light box for 60 minutes. After removal from the mold, the test specimens were stored in distilled water at 37 ° C. for 24 hours until measurement. The flexural strength was measured with a universal testing machine at a crosshead speed of 0.75 mm / min and a clamping length of 25 mm until it broke.

E-module:

0293The modulus of elasticity was determined from the measurements of the bending strengths by calculating the gradient in the linear range.

Water absorption:

0294The water absorption was determined analogously to ISO 4049. For this purpose, the material to be examined was 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>m</i>₁was reached.

0295After 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.

0296The 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.

0297The 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.

0298The 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="EP2436364A2_D0077.tif" /></maths>

0299It is<i>m₂</i> the mass of the test specimen after water storage for 7 days in µg;<i>m₃</i> the mass of the re-dried specimen in µg;<i>V</i> the volume of the test specimen in mm³

Flow behavior: contact angle on dry enamel

0300The flow behavior was determined by measuring the contact angle on dry enamel.

0301An extracted human molar was used for the contact angle measurements 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).

0302The compositions of the mixtures (in parts by weight) and the results of the measurements are listed in the tables below.<tables id="tabl0001" num="0001"><table frame="all"><title>Table 1:</title><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="48mm" /><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="19mm" /><thead><row><entry align="center" valign="top">Example No.</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">comparison</entry></row></thead><tbody><row><entry>Phosphine oxide initiator</entry><entry align="center">3,970</entry><entry align="center">3,970</entry><entry align="center">3,970</entry><entry align="center">4,130</entry></row><row><entry>UV stabilizer</entry><entry align="center">0,029</entry><entry align="center">0,029</entry><entry align="center">0,029</entry><entry align="center">0,029</entry></row><row><entry>BHT</entry><entry align="center">0,016</entry><entry align="center">0,016</entry><entry align="center">0,016</entry><entry align="center">0,017</entry></row><row><entry>Aerosil</entry><entry align="center">0,760</entry><entry align="center">0,760</entry><entry align="center">0,760</entry><entry align="center">0,840</entry></row><row><entry>Surfactant</entry><entry align="center">0,760</entry><entry align="center">0,760</entry><entry align="center">0,760</entry><entry align="center">0,840</entry></row><row><entry>Methyl methacrylate</entry><entry align="center">20,14</entry><entry align="center">20,16</entry><entry align="center">35,13</entry><entry align="center">30,51</entry></row><row><entry>Dipentaerythritol pentaacrylate</entry><entry align="center">44,32</entry><entry align="center">59,30</entry><entry align="center">44,33</entry><entry align="center">63,63</entry></row><row><entry>TCD monomer</entry><entry align="center">30,00</entry><entry align="center">15,00</entry><entry align="center">15,00</entry><entry align="center">0,00</entry></row><row><entry>Nano-SiO₂</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" /></row><row><entry>Flexural strength [MPa]</entry><entry align="center">85</entry><entry align="center">65</entry><entry align="center">94</entry><entry align="center">54</entry></row><row><entry>Modulus of elasticity [MPa]</entry><entry align="center">2846</entry><entry align="center">2730</entry><entry align="center">2656</entry><entry align="center">2300</entry></row><row><entry>KW [°] dry enamel</entry><entry align="center">31,9</entry><entry align="center">30,2</entry><entry align="center">19,8</entry><entry align="center">30,8</entry></row><row><entry>Water absorption [µg / mm³]</entry><entry align="center">34,80</entry><entry align="center">39,64</entry><entry align="center">42,19</entry><entry align="center">49,12</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><table frame="all"><title>Table 2:</title><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="48mm" /><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" /><thead><row><entry valign="top">Example No.</entry><entry align="center" valign="top">4</entry><entry align="center" valign="top">5</entry><entry align="center" valign="top">6</entry><entry align="center" valign="top">7</entry></row></thead><tbody><row><entry>Phosphine oxide initiator</entry><entry align="right">3,970</entry><entry align="right">3,970</entry><entry align="right">1,998</entry><entry align="right">1,998</entry></row><row><entry>UV stabilizer</entry><entry align="right">0,030</entry><entry align="right">0,030</entry><entry align="right">0,029</entry><entry align="right">0,029</entry></row><row><entry>BHT</entry><entry align="right">0,017</entry><entry align="right">0,017</entry><entry align="right">0,017</entry><entry align="right">0,017</entry></row><row><entry>Aerosil</entry><entry align="right">0,764</entry><entry align="right">0,764</entry><entry align="right">0,000</entry><entry align="right">0,000</entry></row><row><entry>Surfactant</entry><entry align="right">0,764</entry><entry align="right">0,769</entry><entry align="right">0,000</entry><entry align="right">0,000</entry></row><row><entry>Methyl methacrylate</entry><entry align="right">42,30</entry><entry align="right">20,00</entry><entry align="right">9,52</entry><entry align="right">9,52</entry></row><row><entry>Dipentaerythritol pentaacrylate</entry><entry align="right">0,00</entry><entry align="right">0,00</entry><entry align="right">9,52</entry><entry align="right">9,52</entry></row><row><entry>TCD monomer</entry><entry align="right">52,15</entry><entry align="right">74,45</entry><entry align="right">19,05</entry><entry align="right">0,00</entry></row><row><entry>Monomer of formula (2)</entry><entry align="right">0,00</entry><entry align="right">0,00</entry><entry align="right">0,00</entry><entry align="right">19,05</entry></row><row><entry>Nano-SiO₂</entry><entry align="right">0,00</entry><entry align="right">0,00</entry><entry align="right">59,87</entry><entry align="right">59,87</entry></row><row><entry /><entry align="right" /><entry align="right" /><entry align="right" /><entry align="right" /></row><row><entry>Flexural strength [MPa]</entry><entry align="right">86</entry><entry align="right">70</entry><entry align="right">109</entry><entry align="right">112</entry></row><row><entry>Modulus of elasticity [MPa]</entry><entry align="right">2917</entry><entry align="right">3178</entry><entry align="right">3670</entry><entry align="right">3735</entry></row><row><entry>KW [°] dry enamel</entry><entry align="right" /><entry align="right" /><entry align="right">27,4</entry><entry align="right">25,6</entry></row><row><entry>Water absorption [µg / mm³]</entry><entry align="right" /><entry align="right" /><entry align="right">35,13</entry><entry align="right">32,17</entry></row></tbody></tgroup></table></tables>

Synthesis of the compound of formula (2)

03030.95 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 catalyst solution (0.50 g dibutyltin (II) dilaurate dissolved in 9.50 g toluene) 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.

0304Examples 1 to 6 were repeated with the exchange of the TCD monomer used there in each case for the compound of the formula (2); these further examples are referred to as examples S1 to S6. All parameters determined in Examples 1 to 6 were also determined for Examples S1 to S6. The determined parameter values ​​for examples S1 to S6 are similar to those from examples 1 to 6 and partially exceed them. In addition to Example 7, 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.