Self-adhesive dental composite cements with good transparency

Abstract

To provide self-adhesive dental composite cements with good transparency.SOLUTION: A radically polymerizable composition has at least one acidic radically polymerizable monomer, at least one fluoroaluminosilicate glass filler and / or radiopaque glass filler, and at least one masking agent in solid form. Preferred masking agents are ethylenediaminetetraacetic acid (EDTA) and its disodium salt (disodium ethylenediaminetetraacetate), nitrilotriacetic acid, diethylenetriaminepentaacetic acid, tetrasodium iminodisuccinate, and the trisodium salt of methylglycinediacetic acid. Especially preferable one is EDTA.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a radically polymerizable self-adhesive composite with improved transparency, which is particularly suitable as a dental material, e.g. as a dental cement, filling composite or veneering material, and for producing inlays, onlays or crowns. [Background technology]

[0002] Composites are primarily used in dentistry to fabricate direct or indirect filling materials, i.e., as direct or indirect filling composites and as cements. The polymerizable organic matrix of a composite usually consists of a mixture of monomers, initiator components, and stabilizers. A mixture of dimethacrylates is usually used as the monomer, which may contain monofunctional and functionalized monomers. Commonly used dimethacrylates are 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropyl)phenyl]propane (bis-GMA), 1,6-bis[2-methacryloyloxyethoxycarbonylamino]-2-trimethylhexane, 2,4 (UDMA), which produce polymers with high viscosity, very good mechanical properties, and low polymerization shrinkage. Triethylene glycol dimethacrylate (TEGDMA), 1,10-decanediol dimethacrylate (D3MA), or bis(3-methacryloyloxymethyl)tricyclo[5.2.1.0] is also used. 2,6 Decane (DCP) is primarily used as a reactive diluent. Monofunctional methacrylates, such as p-cumylphenoxyethylene glycol methacrylate (CMP-1E), are also suitable for reducing viscosity, further reducing network density and increasing double bond conversion.

[0003] To produce self-adhesive composites, strong acidic adhesive monomers such as 10-methacryloyloxydecyl dihydrogen phosphate (MDP) are used, which etch the tooth structure and provide adhesion to the enamel / dentin through ionic relationships. The adhesive monomers impart self-adhesive properties to the composites, and therefore the composites can be used without pretreatment of the tooth structure with an enamel / dentin adhesive, making their use particularly attractive.

[0004] In addition to the organic matrix, composites contain one or more fillers that are usually surface-modified with a polymerizable coupling agent such as 3-methacryloyloxypropyltrimethoxysilane. The fillers improve the mechanical properties (strength, modulus, abrasion resistance) and processing characteristics (paste consistency, fillability) of the material, and confer radiopacity.

[0005] Acidic adhesive monomers are problematic because they often interact adversely with fillers. For example, they bond to the surface of the filler by forming insoluble salts, or they form poorly soluble salts with ions released from the filler during storage. This leads to a significant reduction in adhesive monomer concentration in the resin matrix, which is associated with a reduction or even loss of the adhesive properties of the cement. Therefore, composites containing acidic adhesive monomers have limited storage stability.

[0006] Methacrylate-based dental materials cure by radical polymerization using radical photoinitiators, thermal initiators, or redox initiator systems, depending on the application. Dual-cure systems contain a combination of photoinitiators and redox initiators.

[0007] Composite cements typically contain redox systems to ensure adequate cure even when photocuring is not possible due to insufficient transmittance. Redox initiator systems based on mixtures of dibenzoyl peroxide (DBPO) and tertiary aromatic amines, such as N,N-diethanol-p-toluidine (DEPT), N,N-dimethyl-sym.-xylidine (DMSX), or N,N-diethyl-3,5-di-tert-butylaniline (DABA), are typically used. Because radical formation in DBPO / amine-based redox initiator systems is significantly impaired by strong acids and therefore by strongly acidic adhesive monomers, cumene hydroperoxide-containing redox initiator systems in combination with thioureas, such as acetylthiourea, are preferred.

[0008] To ensure sufficient storage stability of redox initiators, materials based on redox initiator systems are usually used as so-called two-component systems (2C), in which the oxidizing agent (peroxide or hydroperoxide) and the reducing agent (amine, sulfinic acid, barbituric acid, thiourea, etc.) are incorporated into separate components, which are mixed together immediately before use. For mixing, double-push syringes with separate cylindrical chambers for holding the components are mainly used. The components are simultaneously pushed out of the chambers by two interconnected pistons and mixed together in a nozzle. To obtain a mixture as homogeneous as possible, it is advantageous to mix the components together in approximately equal volume proportions.

[0009] Conventional luting cements, such as ZnO eugenol cement, zinc phosphate cement, glass ionomer cement (GIC), and resin-modified glass ionomer cement (RMGI), are not suitable for use with double-push syringes because they contain powder components that make mixing of the components significantly more difficult. Furthermore, glass ionomer cements have low transparency and relatively poor mechanical properties.

[0010] Conventional glass ionomer cements (GICs) contain aqueous solutions of high-molecular-weight polyacrylic acid (PAA, number-average molar mass greater than 30,000 g / mol) or copolymers of equivalent molar masses of acrylic acid and itaconic acid as the liquid component and calcium fluoride aluminum glass as the powder component. After mixing, the components harden via purely ionic ionomer formation. The drawbacks of glass ionomer cements are their low transparency and poor mechanical properties.

[0011] Resin-modified glass ionomer cements (RMGI) also contain hydrophilic monomers, such as 2-hydroxyethyl methacrylate (HEMA). They cure both via acid-base reactions and radical polymerization. Compared to conventional GICs, they are characterized by improved flexural strength.

[0012] US Patent Application Publication No. 2004 / 0048226 discloses a method for root canal treatment using a liquid containing EDTA as a cleaning and sterilizing solution.

[0013] US Patent No. 8,648,062 discloses an EDTA-containing composition for cleaning prepared root canals. The composition is said to be capable of disinfecting and simultaneously removing the smear layer.

[0014] US Patent Application Publication No. 2014 / 0294742 describes peroxide-containing solutions for treating dental plaque, which may contain EDTA or an EDTA salt as a stabilizer.

[0015] JP 11060428 A discloses a dental adhesive containing an aqueous acid solution for pre-treating the tooth surface. Suitable acids are EDTA, phosphoric acid, and citric acid.

[0016] EP 3045160 A1 relates to dental composites based on (meth)acrylate monomers and fillers, which contain a barbiturate in combination with a peroxide compound as an initiator for radical polymerization. The composite further contains an aminocarboxylic acid chelating agent, such as EDTA or its salt, which is said to prevent the reaction of the barbiturate with metal ions and thus improve the storage stability of the material.

[0017] German Patent Application Publication No. 102005022172 discloses polymerizable EDTA derivatives in which EDTA is covalently bonded to ethylenically unsaturated monomers. The EDTA derivatives are immobilized during polymerization by integration into the organic matrix of the dental material, which is said to improve the adhesion of dental adhesives to teeth. EP 2065363 A1 discloses dental materials based on hydrolytically stable alkylenediamine-N,N,N',N'-tetraacetic acid (meth)acrylamide that exhibit good water solubility and improve the adhesion of the material to enamel and dentin. [Prior art documents] [Patent documents]

[0018] [Patent Document 1] US Patent Application Publication No. 2004 / 0048226 [Patent Document 2] U.S. Patent No. 8,648,062 [Patent Document 3] US Patent Application Publication No. 2014 / 0294742 [Patent Document 4] Japanese Patent Application Publication No. 11060428 [Patent Document 5] European Patent Application Publication No. 3045160 [Patent Document 6] German Patent Application Publication No. 102005022172 [Patent Document 7] European Patent Application Publication No. 2065363 Summary of the Invention [Means for solving the problem]

[0019] The object of the present invention is to provide a shelf-stable, self-adhesive dental composite with good transparency and good mechanical properties that can be easily mixed and applied as a two-component system using a double-push syringe. The composite should be particularly suitable as a dental luting cement.

[0020] This problem is solved by a filler-containing radically polymerizable composition comprising at least one acidic radically polymerizable monomer, at least one fluoroaluminosilicate glass filler and / or radiopaque glass filler, and at least one solid masking agent. Surprisingly, it has been found that a masking agent present in at least partially undissolved form provides a significant increase in the storage stability of compositions containing an acidic monomer and at least one fluoroaluminosilicate glass filler and / or radiopaque glass filler. The present application provides, for example, the following items: (Reclaim) (Item 1) 1. A radically polymerizable composition comprising at least one acidic radically polymerizable monomer, at least one fluoroaluminosilicate glass filler, and / or a radiopaque glass filler, and at least one masking agent, wherein the masking agent is in solid form. (Item 2) Item 10. The composition of any one of the preceding items, wherein the masking agent is selected from ethylenediaminetetraacetic acid (EDTA) and its disodium salt (disodium ethylenediaminetetraacetate), nitrilotriacetic acid, diethylenetriaminepentaacetic acid, tetrasodium iminodisuccinate, and the trisodium salt of methylglycine diacetate. (Item 3) Item 10. A composition according to any one of the preceding items, wherein the masking agent is in particulate form and preferably has a volume average particle size (D50 value) of 300 to 350 μm, more preferably 200 to 250 μm, most preferably 100 to 170 μm, and also preferably has a D10 value of 130 to 150 μm, more preferably 80 to 100 μm, most preferably 70 to 55 μm. (Item 4) In each case relative to the total weight of the composition, from 5 to 60% by weight, preferably from 8 to 45% by weight, particularly preferably from 10 to 35% by weight, of at least one radically polymerizable monomer free of acid groups, from 1 to 15% by weight, preferably from 2 to 12% by weight and particularly preferably from 3 to 10% by weight, of at least one radically polymerizable monomer containing acid groups, from 25 to 80% by weight, preferably from 30 to 75% by weight, particularly preferably from 40 to 70% by weight, of at least one fluoroaluminosilicate glass filler and / or radiopaque glass filler, - 0.1 to 8% by weight, preferably 0.5 to 6% by weight, particularly preferably 1 to 5% by weight, of at least one initiator for radical polymerization, and - 0.5 to 6.0% by weight, preferably 0.7 to 5.0% by weight, particularly preferably 1.0 to 4.0% by weight, of at least one masking agent Item 10. The composition of any one of the preceding items, comprising: (Item 5) In each case relative to the total weight of the composition, (a) 0.5 to 6% by weight, preferably 0.7 to 5% by weight, particularly preferably 1.0 to 4.0% by weight, of at least one solid masking agent; b) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer free of acid groups, c) 1 to 15% by weight, preferably 2 to 12% by weight, particularly preferably 3 to 10% by weight, of at least one monomer containing acid groups, d) 0 to 10% by weight, preferably 0 to 8% by weight, particularly preferably 1 to 5% by weight, of one or more oligomeric carboxylic acids, e) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers free of acid groups, f) 25 to 80% by weight, preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight, of at least one fluoroaluminosilicate glass filler and / or radiopaque glass filler, g) 1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more additional fillers, h) 0.1 to 8% by weight, preferably 0.5 to 6% by weight, particularly preferably 1 to 5% by weight, of an initiator for radical polymerization, i) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and j) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.005 to 2% by weight of additives Item 10. The composition of any one of the preceding items, comprising: (Item 6) Examples of polyfunctional monomers (b) include bisphenol A dimethacrylate, bis-GMA (addition product of methacrylic acid and bisphenol A diglycidyl ether), ethoxylated or propoxylated bisphenol A dimethacrylate, such as bisphenol A dimethacrylate with three ethoxy groups or 2,2-bis[4-(2-methacryloyloxypropoxy)phenyl]propane, urethanes of 2-(hydroxymethyl)acrylic acid with diisocyanates, such as urethanes of 2,2,4-trimethylhexamethylene diisocyanate or isophorone diisocyanate, UDMA (2-hydroxyethyl methacrylate and 2,2,4-trimethyl hexamethylene diisocyanate), and the like. Addition products of methylhexamethylene-1,6-diisocyanate), tetramethylxylylenediurethane ethylene glycol di(meth)acrylate or tetramethylxylylenediurethane-2-methylethylene glycol diurethane di(meth)acrylate (V380), di-, tri-, or tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, and glycerol di- and trimethacrylate, 1,4-butanediol dimethacrylate, 1,10-decanediol dimethacrylate (D3MA), bis(methacryloyloxymethyl)tricyclo[5.2.1.0] 2,6] The composition of any one of the preceding items, comprising at least one monomer selected from decane (DCP), polyethylene glycol or polypropylene glycol dimethacrylate, such as polyethylene glycol 200-dimethacrylate (PEG-200-DMA) or polyethylene glycol 400-dimethacrylate (PEG-400-DMA), 1,12-dodecanediol dimethacrylate, radically polymerizable pyrrolidone, such as 1,6-bis(3-vinyl-2-pyrrolidonyl)-hexane, bisacrylamide, such as methylene or ethylene bisacrylamide, bis(meth)acrylamide, such as N,N'-diethyl-1,3-bis(acrylamido)propane, 1,3-bis(methacrylamido)propane, 1,4-bis(acrylamido)butane, or 1,4-bis(acryloyl)piperazine, and mixtures thereof. (Item 7) Item 10. The composition according to any one of the preceding items, wherein the acid group-containing monomer (c) is at least one monomer selected from the group consisting of a monomer containing a phosphate ester group or a phosphonic acid group, preferably 2-methacryloyloxyethylphenyl hydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate (MDP), glycerol dihydrogen dimethacrylate, dipentaerythritol pentamethacryloyloxyphosphate, 4-vinylbenzylphosphonic acid, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid, and / or 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid-2,4,6-trimethylphenyl ester, and / or a monomer containing a carboxy group, preferably 4-(meth)acryloyloxyethyltrimellitic anhydride, 10-methacryloyloxydecylmalonic acid, N-(2-hydroxy-3-methacryloyloxypropyl)-N-phenylglycine, and / or 4-vinylbenzoic acid. (Item 8) 10. The composition according to claim 1, comprising as oligomeric carboxylic acid (d) a polyacrylic acid having a number average molecular weight of less than 7,200 g / mol, preferably less than 7,000 g / mol, particularly preferably less than 6,800 g / mol. (Item 9) The composition according to any one of the preceding items, comprising as monofunctional monomer (e) at least one monomer selected from benzil, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, p-cumylphenoxyethylene glycol methacrylate (CMP-1E), and 2-[1,1'-biphenyl]-2-oxy)ethyl methacrylate (MA-836), tricyclodecanemethyl (meth)acrylate, 2-(2-biphenyloxy)ethyl (meth)acrylate, 2-hydroxyethyl (methacrylate), hydroxyethylpropyl (methacrylate), 2-acetoxyethyl methacrylate, and mixtures thereof. (Item 10) Composition (by weight) of: a radiopaque glass filler having SiO2: 20-80; B2O3: 2-15, BaO or SrO: 0-40; Al2O3: 2-20; CaO and / or MgO: 0-20; Na2O, K2O, Cs2O: 0-10 each; WO3: 0-20; ZnO: 0-20; La2O3: 0-10; ZrO2: 0-15; P2O5: 0-30; Ta2O5, Nb2O5 or Yb2O3: 0-5; and CaF2 and / or SrF2 0-10; or preferably SiO2: 50-75; B2O3: 2-15; BaO or SrO: 2-35; Al2O3: 2-15; CaO and / or MgO: 0-10; and Na2O: 0-10; Item 10. A composition according to any one of the preceding items, comprising a fluoroaluminosilicate glass filler having the following composition (wt%): SiO2: 20-35; Al2O3: 15-35; BaO or SrO: 10-25; CaO: 0-20; ZnO: 0-15; P2O5: 5-20; Na2O, K2O, Cs2O: 0-10 each; and CaF2: 0.5-20 wt%; or preferably SiO2: 20-30; Al2O3: 20-30; BaO or SrO: 10-25; CaO: 5-20; P2O5: 5-20; Na2O: 0-10; and CaF2: 5-20 wt%, all figures being relative to the total mass of the glass and all constituents except fluorine being calculated as oxides. (Item 11) Item 10. The composition of any one of the preceding items, comprising at least one redox initiator, or at least one redox initiator and at least one photoinitiator. (Item 12) a catalyst paste and a base paste, the catalyst paste comprising in each case, relative to the total mass of the catalyst paste: (a) 1.0 to 12% by weight, preferably 1.4 to 10% by weight, particularly preferably 2.0 to 8.0% by weight, of at least one solid masking agent; b) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer free of acid groups, c) 2 to 30% by weight, preferably 4 to 24% by weight, particularly preferably 6 to 20% by weight, of at least one monomer containing acid groups, d) 0.1 to 20% by weight, preferably 1 to 16% by weight, particularly preferably 2 to 10% by weight, of one or more oligomeric carboxylic acids, e) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers free of acid groups, f) 25 to 80% by weight, preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight, of at least one fluoroaluminosilicate glass filler and / or glass filler, g) 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more additional fillers, h) 0.01 to 16% by weight, preferably 0.02 to 12% by weight, particularly preferably 0.03 to 10% by weight, of at least one peroxide and / or hydroperoxide, and optionally at least one photoinitiator, i) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and j) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.0051 to 2% by weight of additives Including, The base paste comprises, in each case relative to the total mass of the base paste: a) Not applicable; b) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer free of acid groups, c) Not applicable; d) Not applicable; e) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers free of acid groups, f) 25 to 80% by weight, preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight, of at least one fluoroaluminosilicate glass filler and / or glass filler, g) 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more additional fillers, h) 0.01 to 16% by weight, preferably 0.02 to 12% by weight, particularly preferably 0.03 to 10% by weight, of at least one suitable reducing agent and, if necessary, a photoinitiator, i) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and j) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.0051 to 2% by weight of additives Including, The composition according to any one of the preceding items. (Item 13) Item 11. The composition of any one of the preceding items, wherein the catalyst paste and the base paste are each contained in different chambers of a dual push syringe. (Item 14) 10. A composition according to any one of the preceding items for therapeutic use as a dental material, preferably as a dental cement, coating or veneering material, restorative composite, or luting cement. (Item 15) 10. Non-therapeutic use of a composition according to any one of the preceding items for the manufacture or repair of a dental restoration, in particular an inlay, onlay, crown or bridge. DETAILED DESCRIPTION OF THE INVENTION

[0021] The present invention relates to a radically polymerizable composition comprising at least one acidic radically polymerizable monomer, at least one fluoroaluminosilicate glass filler, and / or a radiopaque glass filler, and at least one masking agent in solid form.

[0022] Preferred masking agents according to the present invention are ethylenediaminetetraacetic acid (EDTA) and its disodium salt (disodium ethylenediaminetetraacetate), nitrilotriacetic acid, diethylenetriaminepentaacetic acid, tetrasodium iminodisuccinate, and the trisodium salt of methylglycine diacetate. EDTA is particularly preferred.

[0023] The one or more masking agents are preferably added in a total amount of 0.5 to 6.0 wt.%, more preferably 0.7 to 5 wt.%, and most preferably 1.0 to 4.0 wt.%. All percentages herein refer to the total weight of the composition unless otherwise stated.

[0024] The one or more masking agents are preferably used in granular form, which then behaves like a filler, which is advantageous in terms of mechanical properties. The particles preferably have an average size (D50 value) of 300 to 350 μm, more preferably 200 to 250 μm, and most preferably 100 to 170 μm. According to a particularly preferred embodiment of the present invention, the D10 value of the particles is in the range of 130 to 150 μm, more preferably 80 to 100 μm, and most preferably 70 to 55 μm. The D50 value indicates the average particle size. D50 means that 50% of the particles are smaller than the specified value. Another important parameter is the D10 value as a measure of the smallest particles. D10 means that 10% of the particles are smaller than the specified value.

[0025] Unless otherwise stated, all particle sizes in this specification are volume-average particle sizes (D50 values), i.e., 50% of the total volume of all particles is contained in particles with a diameter smaller than the specified value. The D10 value also refers to the volumetric diameter.

[0026] The determination of particle sizes in the range of 0.1 μm to 1000 μm is preferably carried out using static light scattering (SLS), for example, with an LA-960 static laser scattering particle size analyzer (Horiba, Japan) or a Microtrac S100 particle size analyzer (Microtrac, USA). A laser diode with a wavelength of 655 nm and an LED with a wavelength of 405 nm are used as light sources. The use of two light sources with different wavelengths allows the measurement of the entire particle size distribution of a sample in a single measurement run, which is carried out as a wet measurement. For this purpose, an aqueous dispersion of the filler is prepared, and its scattered light is measured in a flow cell. The scattered light analysis for calculating particle size and particle size distribution is carried out according to the Mie theory according to DIN / ISO 13320. Measurement of particle sizes in the range of 1 nm to 0.1 μm is preferably carried out by dynamic light scattering (DLS) of aqueous particle dispersions, preferably with a He-Ne laser at a wavelength of 633 nm and a scattering angle of 90° at 25°C, e.g., with a Malvern Zetasizer Nano ZS (Malvern Instruments, Malvern UK).

[0027] For agglomerates and aggregates, the primary particle size can be determined from TEM images. Transmission electron microscopy (TEM) is preferably performed using a Philips CM30 TEM at an accelerating voltage of 300 kV. For sample preparation, a droplet of the particle dispersion is deposited on a carbon-coated copper grid (50 Å thick, 300 mesh), followed by solvent evaporation. Particles are counted and the arithmetic mean is calculated.

[0028] The composition according to the present invention contains at least one radically polymerizable monomer, preferably one or more mono- and / or polyfunctional monomers. Polyfunctional monomers are understood to be compounds having two or more, preferably two to four, especially two radically polymerizable groups. Monofunctional monomers therefore have only one radically polymerizable group. Polyfunctional monomers have crosslinking properties and are therefore also called crosslinking monomers. Preferred radically polymerizable groups are (meth)acrylate, (meth)acrylamide, and vinyl groups.

[0029] According to the present invention, a distinction is made between monomers containing acid groups and monomers not containing acid groups. The composition according to the present invention contains at least one monomer without an acid group and at least one monomer and / or oligomer with an acid group. The composition according to the present invention preferably contains the monomer with an acid group and the monomer without an acid group in a weight ratio of 1:5 to 1:36, more preferably 1:6 to 1:25, and most preferably 1:7 to 1:20.

[0030] Monomers without acid groups Preferred are compositions comprising at least one (meth)acrylate, more preferably at least one mono- or polyfunctional methacrylate, most preferably at least one mono- or difunctional methacrylate, or mixtures thereof.

[0031] Preferred monofunctional (meth)acrylates are benzyl, tetrahydrofurfuryl, or isobornyl (meth)acrylate, p-cumylphenoxyethylene glycol methacrylate (CMP-1E), 2-([1,1'-biphenyl]-2-oxy)ethyl methacrylate (MA-836), tricyclodecanemethyl (meth)acrylate, and 2-(2-biphenyloxy)ethyl (meth)acrylate. CMP-1E and MA-836 are particularly preferred.

[0032] According to one embodiment, the composition according to the invention preferably comprises at least one functionalized monofunctional (meth)acrylate. A functionalized monomer is understood to be a monomer that, in addition to at least one radically polymerizable group, also carries at least one functional group, preferably a hydroxyl group. Preferred functionalized mono(meth)acrylates are 2-hydroxyethyl and hydroxyethylpropyl (methacrylate) and 2-acetoxyethyl methacrylate. Hydroxyethyl methacrylate is particularly preferred. The monomers containing acid groups mentioned below are not functionalized monomers within the meaning of the present invention.

[0033] Preferred di- or polyfunctional (meth)acrylates are bisphenol-A-dimethacrylate, bis-GMA (addition product of methacrylic acid and bisphenol-A-diglycidyl ether), ethoxylated or propoxylated bisphenol-A-dimethacrylate, such as bisphenol-A dimethacrylate SR-348c (Sartomer) with three ethoxy groups or 2,2-bis[4-(2-methacryloyloxypropoxy)phenyl]propane, urethanes of 2-(hydroxymethyl)acrylic acid methyl ester with diisocyanates, such as urethanes of 2,2,4-trimethylhexamethylene diisocyanate or isophorone diisocyanate, UDMA (2-hydroxymethyl)acrylic acid methyl ester with diisocyanates, such as urethanes of 2,2,4-trimethylhexamethylene diisocyanate or isophorone diisocyanate, addition products of hydroxyethyl methacrylate and 2,2,4-trimethylhexamethylene-1,6-diisocyanate), tetramethylxylylene diurethane ethylene di(meth)acrylate or tetramethylxylylene diurethane-2-methylethylene glycol di(meth)acrylate (V380), di-, tri-, or tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, and glycerol di- and trimethacrylate, 1,4-butanediol dimethacrylate, 1,10-decanediol dimethacrylate (D3MA), bis(methacryloyloxymethyl)tricyclo[5.2.1.0] 2,6] decane (DCP), polyethylene glycol or polypropylene glycol dimethacrylate, such as polyethylene glycol 200-dimethacrylate or polyethylene glycol 400-dimethacrylate (PEG-200- or PEG-400-DMA) or 1,12-dodecanediol dimethacrylate. Bis-GMA, UDMA, V-380, triethylene glycol dimethacrylate (TEGDMA) and PEG-400-DMA (NK ester 9G) are particularly preferred.

[0034] The monomers tetramethylxylylene diurethane ethylene glycol di(meth)acrylate and tetramethylxylylene diurethane 2-methylethylene glycol di(meth)acrylate (V380) are respectively represented by the following formula: [ka] It has.

[0035] In the above formula, the R radicals are independently H or CH3, and the radicals may have the same or different meanings. Preferably, mixtures are used containing molecules in which both radicals are H, molecules in which both radicals are CH3, and molecules in which one radical is H and the other radical is CH3, preferably in a ratio of H to CH3 of 7:3. Such mixtures can be obtained, for example, by reacting 1,3-bis(1-isocyanato-1-methylethyl)benzene with 2-hydroxypropyl methacrylate and 2-hydroxyethyl methacrylate.

[0036] Other preferred bifunctional monomers include radically polymerizable pyrrolidones, such as 1,6-bis(3-vinyl-2-pyrrolidonyl)-hexane, or commercially available bisacrylamides, such as methylene or ethylenebisacrylamide, and bis(meth)acrylamides, such as N,N'-diethyl-1,3-bis(acrylamido)propane, 1,3-bis(methacrylamido)propane, 1,4-bis(acrylamido)butane, or 1,4-bis(acryloyl)piperazine, which can be synthesized from the corresponding diamines by reaction with (meth)acrylic acid chloride. N,N'-diethyl-1,3-bis(acrylamido)propane (V-392) is particularly preferred. These monomers are characterized by high hydrolytic stability.

[0037] Monomers and oligomers containing acid groups The composition according to the present invention contains at least one acidic radical polymerizable monomer and / or at least one acidic oligomer. The acidic monomer and oligomer are understood to mean a monomer and oligomer, respectively, that contain at least one acid group, preferably a phosphate ester, a phosphonic acid, or a carboxyl group, with phosphate ester being particularly preferred. The acidic monomer and oligomer are also referred to herein as adhesive components, adhesive monomers, or adhesive oligomers.

[0038] Preferred monomers containing acid groups are phosphate esters and phosphonate monomers. 2-Methacryloyloxyethylphenyl hydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate (MDP), glycerol dihydrogen phosphate, or dipentaerythritol pentamethacryloyloxyphosphate are particularly preferred. 4-Vinylbenzylphosphonic acid, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid, or hydrolysis-stable esters such as 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid 2,4,6-trimethylphenyl ester are particularly preferred. MDP, 2-methacryloyloxyethylphenyl hydrogen phosphate, and glycerol dihydrogen phosphate are particularly preferred.

[0039] Other preferred monomers containing an acid group are polymerizable monomers containing a COOH group, with 4-(meth)acryloyloxyethyltrimellitic anhydride, 10-methacryloyloxydecylmalonic acid, N-(2-hydroxy-3-methacryloyloxypropyl)-N-phenylglycine, and 4-vinylbenzoic acid being particularly preferred.

[0040] The oligomer has a degree of polymerization P n It is understood that the polymer is a polymer having a P n =M n / M u ;M n : number average polymer molecular weight, M u (where m is the molecular weight of the monomer unit). The acidic radically polymerizable oligomer has at least one acid group, preferably a carboxyl group, and at least one radically polymerizable group, preferably at least one (meth)acrylate group, in particular at least one methacrylate group.

[0041] Preferred acid group-containing oligomers according to the present invention are oligomerized carboxylic acids, such as polyacrylic acids, preferably having a number average molecular weight M nis less than 7,200 g / mol, more preferably less than 7,000 g / mol, and most preferably less than 6,800 g / mol, where M n is preferably in the range of 800 to 7,200 g / mol, particularly preferably 500 to 7,000 g / mol, and most preferably 500 to 6,800 g / mol. Oligomeric carboxylic acids containing (meth)acrylate groups are particularly preferred. These can be obtained, for example, by reacting oligomeric polyacrylic acids with glycidyl methacrylate or 2-isocyanatoethyl methacrylate.

[0042] Unless otherwise stated, the molar masses of oligomers and polymers herein are number-average molar masses, the absolute values ​​of which can be determined by known methods of freezing point depression (cryoscopy), boiling point elevation (ebullioscopy), or through vapor pressure depression (vapor pressure osmometry). Preferably, the number-average molecular weights of oligomers and polymers are determined by gel permeation chromatography (GPC), a relative method in which molecules are separated based on their size, more specifically, their hydrodynamic volume. Absolute molar masses are determined by calibration with known standards.

[0043] The compositions according to the invention preferably also contain water. It has been found that a water content of 1 to 7% by weight, particularly preferably 1 to 5% by weight, in each case relative to the total mass of the composition, leads to an improved bonding effect with dentin and enamel, but also does not lead to complete dissolution of the masking agent.

[0044] The composition according to the present invention further comprises at least one initiator, preferably a photoinitiator, for initiating radical polymerization. Preferred photoinitiators are benzophenone, benzoin, and their derivatives, α-diketones or their derivatives, such as 9,10-phenanthrenequinone, 1-phenyl-propane-1,2-dione, diacetyl, and 4,4'-dichlorobenzyl. Camphorquinone (CC) and 2,2-dimethoxy-2-phenyl-acetophenone are particularly preferred, and most preferably, α-diketones are used in combination with amines, such as 4-(dimethylamino)benzoic acid ethyl ester (EDMAB), N,N-dimethylaminoethyl methacrylate, N,N-dimethyl-sym.-xylidine, or triethanolamine, as reducing agents. Norrish Type I photoinitiators, especially acyl or bisacylphosphine oxides, are more preferred, with monoacyltrialkylgermanium, diacyldialkylgermanium, and tetraacylgermanium compounds, such as benzoyltrimethylgermane, dibenzoyldiethylgermane, bis(4-methoxybenzoyl)-diethylgermane (Ivocerin®), tetrabenzoylgermane, or tetrakis(o-methylbenzoyl)germane, being most preferred. Mixtures of various photoinitiators can also be used, such as bis(4-methoxybenzoyl)diethylgermane or tetrakis(o-methylbenzoyl)germane in combination with camphorquinone and 4-(dimethylamino)benzoic acid ethyl ester.

[0045] Further preferred are compositions containing a redox initiator for initiating radical polymerization, preferably a redox initiator based on an oxidizing agent and a reducing agent. Preferred oxidizing agents are, in particular, peroxides and hydroperoxides. A particularly preferred peroxide is benzoyl peroxide. Preferred hydroperoxides are the low-odor cumene hydroperoxide derivatives disclosed in EP 3692976 A1, and the oligomeric CHP derivatives disclosed in EP 21315089.9, in particular 4-(2-hydroperoxypropan-2-yl)phenylpropionate and cumene hydroperoxide (CHP).

[0046] Preferred reducing agents for combination with peroxides are tertiary amines, such as N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidine, p-dimethylaminobenzoic acid ethyl ester, or other aromatic dialkylamines, ascorbic acid, sulfinic acids, thiols, and / or hydrogen silanes.

[0047] Preferred reducing agents for combination with hydroperoxides are thiourea derivatives, in particular the compounds listed in paragraph

[0009] of EP1754465A1. Particular preference is given to methyl, ethyl, allyl, butyl, hexyl, octyl, benzyl, 1,1,3-trimethyl, 1,1-diallyl, 1,3-diallyl, 1-(2-pyridyl-2-thiourea, acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, benzoylthiourea, and mixtures thereof. Very particular preference is given to acetyl, allyl, pyridyl, and phenylthiourea, and hexanoylthiourea, and mixtures thereof, as well as polymerizable thiourea derivatives, such as N-(2-methacryloyloxyethoxysuccinoyl)thiourea and N-(4-vinylbenzoyl)thiourea. Furthermore, a combination of one or more of the abovementioned thiourea derivatives with one or more imidazoles may be advantageously used. A preferred imidazole is 2-mercapto-1-methylimidazole or 2-mercaptobenzimidazole.

[0048] In addition to at least one hydroperoxide and at least one thiourea derivative, the composition according to the present invention may further comprise at least one transition metal compound to accelerate curing. Transition metal compounds suitable according to the present invention are, in particular, compounds derived from transition metals having at least two stable oxidation states. Compounds of the elements copper, iron, cobalt, nickel, and manganese are particularly preferred. These metals have the following stable oxidation states: Cu(I) / Cu(II), Fe(II) / Fe(III), Co(II) / Co(III), Ni(II) / Ni(III), and Mn(II) / Mn(III). Compositions containing at least one copper compound are particularly preferred. The transition metal compound is preferably used in catalytic amounts, particularly preferably in amounts of 10 to 200 ppm. These amounts do not cause discoloration of the dental material. Due to their good monomer solubility, the transition metals are preferably used in the form of their acetylacetonate, 2-ethylhexanoate, or THF adduct. Their complexes with polydentate ligands, such as 2-(2-aminoethylamino)ethanol, triethylenetetramine, dimethylglyoxime, 8-hydroxyquinoline, 2,2'-bipyridine, or 1,10-phenanthroline, are more preferred. A particularly suitable initiator according to the present invention is a mixture of cumene hydroperoxide (CHP) with at least one of the above-mentioned thiourea derivatives and copper(II) acetylacetonate. Compositions free of vanadium compounds are preferred according to the present invention.

[0049] The compositions of the present invention preferably do not contain barbiturates or barbituric acid derivatives, such as 1,3,5-trimethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-butylbarbituric acid, or 1-cyclohexyl-5-ethylbarbituric acid. Compositions containing barbiturates have poor storage stability because barbiturates form polymerization-initiating radicals upon oxidation with atmospheric oxygen. Furthermore, barbiturates have adverse physiological effects, such as bradycardia, hypotension, or blood disorders.

[0050] The composition according to the present invention contains at least one inorganic filler. A composition containing a filler is called a composite. A composition containing at least one fluoroaluminosilicate glass filler (FAS filler) and / or a radiopaque glass filler is preferred.

[0051] A preferred radiopaque glass filler has the following composition (wt %): SiO2: 20-80; B2O3: 2-15, BaO or SrO: 0-40; Al2O3: 2-20; CaO and / or MgO: 0-20; Na2O, K2O, Cs2O: 0-10 each; WO3: 0-20; ZnO: 0-20; La2O3: 0-10; ZrO2: 0-15; P2O5: 0-30; Ta2O5, Nb2O5 or Yb2O3: 0-5; and CaF2 and / or SrF2: 0-10. Particularly preferred is a radiopaque glass filler having the following composition (wt%): SiO2: 50-75; B2O3: 2-15; BaO or SrO: 2-35; Al2O3: 2-15; CaO and / or MgO: 0-10; and Na2O: 0-10.

[0052] Particularly preferred FAS fillers have the following composition (wt%): SiO2: 20-35; Al2O3: 15-35; BaO or SrO: 10-25; CaO: 0-20; ZnO: 0-15; P2O5: 5-20; Na2O, K2O, Cs2O: 0-10 each; and CaF2: 0.5-20. Particularly preferred are FAS fillers having the composition (wt%): SiO2: 20-30; Al2O3: 20-30; BaO or SrO: 10-25; CaO: 5-20; P2O5: 5-20; Na2O: 0-10; and CaF2: 5-20.

[0053] All data refer to the total mass of the glass, and as is common in glasses and glass-ceramics, all constituents other than fluorine are calculated as oxides.

[0054] The FAS fillers and radiopaque glass fillers preferably have an average particle size of 0.2 to 20 μm, particularly preferably 0.4 to 5 μm.

[0055] The compositions according to the invention preferably contain from 25 to 80% by weight, more preferably from 30 to 75% by weight, most preferably from 40 to 70% by weight of FAS fillers and / or radiopaque glass fillers, in each case relative to the total weight of the composition.

[0056] In addition to the aforementioned FAS and radiopaque glass fillers, compositions according to the present invention may contain further fillers.

[0057] Further preferred fillers are metal oxides, particularly mixed oxides containing 60 to 80 wt. % SiO and at least one of the metal oxides ZrO, YbO, ZnO, TaO, NbO, and / or LaO, totaling 100%. Mixed oxides such as SiO-ZrO can be obtained, for example, by hydrolytic co-condensation of metal alkoxides. The metal oxide preferably has an average particle size of 0.05 to 10 μm, particularly preferably 0.1 to 5 μm.

[0058] Other preferred additional fillers are fumed or precipitated silica with a primary particle size of 0.01 to 0.15 μm, quartz or glass-ceramic powders with a particle size of 0.1 to 15 μm, preferably 0.2 to 5 μm, and ytterbium trifluoride, which preferably has a particle size of 80 to 900 nm, particularly preferably 100 to 300 nm.

[0059] Furthermore, so-called composite fillers are preferred as further fillers. These are also called isofillers. These are splinter-like polymers that also contain fillers, preferably the pyrogenic SiO2 and / or ytterbium trifluoride as defined above. Dimethacrylate-based polymers are preferred. To produce isofillers, one or more fillers are incorporated into, for example, a dimethacrylate resin matrix, and the resulting composite paste is subsequently thermally polymerized and then ground.

[0060] A preferred composite filler according to the present invention can be prepared, for example, by thermally curing a mixture of bis-GMA (8.80 wt%), UDMA (6.60 wt%), 1,10-decanediol dimethacrylate (5.93 wt%), dibenzoyl peroxide and 2,6-di-tert-butyl-4-methylphenol (together 0.67 wt%), glass filler (average particle size 0.4 μm; 53.0 wt%), and YbF (25.0 wt%) before grinding the cured material to the desired particle size. All percentages refer to the total mass of the composite filler.

[0061] So-called inert fillers can also be used as further fillers. These are glass fillers whose surface is coated with a diffusion barrier layer, for example, based on sol-gel, or with a polymer layer, for example, PVC. Preferred fillers are those described in EP 2 103 296 A1.

[0062] To improve the bond between the filler and the matrix, the filler is preferably surface modified with a methacrylate-functionalized silane, such as 3-methacryloyloxypropyltrimethoxysilane.

[0063] The composition according to the invention preferably contains from 0.1 to 25% by weight, more preferably from 1 to 20% by weight, most preferably from 2 to 15% by weight of one or more further fillers, preferably one or more metal oxides, fumed silica, and / or precipitated silica, in each case relative to the total weight of the composition.

[0064] The compositions according to the invention may contain additional additives, in particular stabilizers, colorants, bactericides, fluoride ion-releasing additives, such as fluoride salts, in particular NaF, or ammonium fluoride, or fluorosilanes, optical brighteners, plasticizers, and / or UV absorbers.

[0065] Preferably, the composition according to the invention comprises: from 5 to 60% by weight, preferably from 8 to 45% by weight, particularly preferably from 10 to 35% by weight, of at least one radically polymerizable monomer free of acid groups, - 1 to 15% by weight, preferably 2 to 12% by weight and particularly preferably 3 to 10% by weight of at least one acid group-containing, radically polymerizable monomer, - 25 to 80% by weight, preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight, of at least one FAS filler and / or radiopaque glass filler, - 0.1 to 8% by weight, preferably 0.5 to 6% by weight, particularly preferably 1 to 5% by weight, of at least one initiator for radical polymerization, and - 0.5 to 6.0% by weight, preferably 0.7 to 5.0% by weight, particularly preferably 1.0 to 4.0% by weight, of at least one masking agent Includes.

[0066] Unless otherwise stated, all percentages herein refer to the total weight of the composition. All amounts relating to radically polymerizable monomers (poly- and mono-functional) refer only to monomers without acid groups and do not include monomers containing acid groups.

[0067] The initiator can be a redox initiator, a photoinitiator, or an initiator for dual curing. The amounts mentioned include all initiator components, i.e., the initiator itself, and, if present, the reducing agent, the transition metal compound, etc. According to the present invention, compositions containing at least one redox initiator, or at least one redox initiator and at least one photoinitiator, are preferred.

[0068] According to the invention, particular preference is given to such compositions which contain the following components, in each case relative to the total weight of the composition: a) 0.5 to 6% by weight, preferably 0.7 to 5% by weight, particularly preferably 1.0 to 4.0% by weight, of at least one solid masking agent, b) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer free of acid groups, c) 1 to 15% by weight, preferably 2 to 12% by weight, particularly preferably 3 to 10% by weight, of at least one monomer containing acid groups, d) 0 to 10% by weight, preferably 0 to 8% by weight, particularly preferably 1 to 5% by weight, of one or more oligomeric carboxylic acids, e) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers free of acid groups, f) 25 to 80% by weight, preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight, of at least one FAS filler and / or radiopaque glass filler, g) 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more additional fillers, h) 0.1 to 8% by weight, preferably 0.5 to 6% by weight, particularly preferably 1 to 5% by weight, of initiators for radical polymerization, i) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and j) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.005 to 2% by weight, of additives.

[0069] Compositions containing redox initiators are self-curing. They are preferably used in the form of two spatially separated components, i.e., two-component systems (2C systems). The oxidizing and reducing agents are incorporated into separate components of the composition. One component, the so-called catalyst paste, contains an oxidizing agent, preferably a peroxide or hydroperoxide, and the second component, the so-called base paste, contains the corresponding reducing agent and, optionally, a photoinitiator and, optionally, a catalytic amount of a transition metal compound. Polymerization is initiated by mixing the components. Compositions containing both redox initiators and photoinitiators are dual-curing.

[0070] In two-component compositions, the masking agent is preferably added to the component containing the strongly acidic adhesive monomer, the FAS filler, and / or the radiopaque glass filler.

[0071] According to the invention, two-component systems are preferred. They are preferably self-curing or dual-curing. The pastes are mixed together shortly before use, preferably with a double-push syringe.

[0072] The catalyst paste preferably has the following composition, in each case relative to the total mass of the catalyst paste: a) 1.0 to 12% by weight, preferably 1.4 to 10% by weight, particularly preferably 2.0 to 8.0% by weight, of at least one solid masking agent, b) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer free of acid groups, c) 2 to 30% by weight, preferably 4 to 24% by weight, particularly preferably 6 to 20% by weight, of at least one monomer containing acid groups, d) 0.1 to 20% by weight, preferably 1 to 16% by weight, particularly preferably 2 to 10% by weight, of one or more oligomeric carboxylic acids, e) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers free of acid groups, f) 25 to 80% by weight, preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight, of at least one FAS filler and / or glass filler, g) 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more additional fillers, h) 0.01 to 16% by weight, preferably 0.02 to 12% by weight, particularly preferably 0.03 to 10% by weight, of at least one peroxide and / or hydroperoxide, and optionally at least one photoinitiator, i) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and j) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.005 to 2% by weight, of additives.

[0073] The base paste preferably has the following composition, in each case relative to the total mass of the base paste: a) Not applicable; b) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer free of acid groups, c) Not applicable; d) Not applicable; e) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers free of acid groups, f) 25 to 80% by weight, preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight, of at least one fluoroaluminosilicate glass filler and / or glass filler, g) 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more additional fillers, h) 0.01 to 16% by weight, preferably 0.02 to 12% by weight, particularly preferably 0.03 to 10% by weight, of at least one suitable reducing agent and optionally a photoinitiator, i) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and j) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.005 to 2% by weight, of additives.

[0074] For application, the catalyst and base paste are preferably mixed together in approximately equal proportions and are therefore particularly suitable for application with a double-push syringe.

[0075] The double-push syringe has two separate cylindrical chambers for holding the base paste and the catalyst paste. The components are simultaneously pushed out of the chambers by two interconnected pistons, preferably through a mixing cannula, where they are mixed together. To push the pastes out, the syringe can be inserted into a so-called hand dispenser, which facilitates handling of the syringe.

[0076] The composition according to the present invention is characterized by high storage stability and improved transparency, preferably improved by more than 10%, and good self-adhesion to enamel / dentin.It is particularly suitable as a dental material for intraoral use by dentists to repair damaged teeth, especially as a dental cement, coating material, or veneer material, filling composite, most especially as a luting cement (therapeutic use).Transparency is determined by the method described in the examples.

[0077] For the treatment of damaged teeth, they are preferably prepared by dentists in the first step.Then, at least one composition according to the present invention is applied to the prepared tooth or inside the tooth.Then, the composition can be directly hardened, preferably by irradiation with light of an appropriate wavelength, for example, when repairing a dental cavity.Alternatively, a dental restoration, such as an inlay, an onlay, a veneer, a crown, a bridge, a framework, or a dental ceramic, is placed inside the prepared tooth or applied to the tooth.The subsequent hardening of the composition is preferably carried out by light and / or self-hardening.The dental restoration is attached to the tooth in this process.

[0078] The compositions according to the invention can also be used as extraoral materials (non-therapeutic), for example in the manufacture or repair of dental restorations. They are also suitable as materials for the manufacture and repair of inlays, onlays, crowns or bridges.

[0079] For the production of dental restorations such as inlays, onlays, crowns or bridges, at least one composition according to the invention is formed into the desired dental restoration in a manner known per se and then hardened, which can be done by light, self-hardening or preferably by heat.

[0080] In modifying a dental restoration, a composition according to the invention is placed on the restoration to be modified, for example to repair a gap or to bond fragments, and then allowed to harden.

[0081] The invention will be explained in more detail below with reference to figures and examples. [Brief explanation of the drawings]

[0082] [Figure 1] FIG. 1 shows the decrease in the concentration of the acidic monomer MDP as a function of storage time for composite pastes with (inverted triangles; circles) and without EDTA (squares).

[0083] [Figure 2] FIG. 2 shows the decrease in shear bond strength of composite cements containing EDTA (inverted triangles; circles) and not containing EDTA (squares) as a function of storage time. [Example]

[0084] Example 1 Investigation of storage stability of self-adhesive composites with and without EDTA

[0085] Composite pastes C-1 to C-3 were prepared with the compositions shown in Table 1 (all data in wt%) from the following components: experimental radiopaque glass filler 1 (composition (wt%): Al2O3: 6; B2O3: 5; Na2O: 8; CaO, BaO, K2O: approximately 2–3 each; CaF2; MgO, approximately 1 each; and SiO2: 70; non-silanized), 10-methacryloyloxydecyl dihydrogen phosphate (MDP, Orgentis), triethylene glycol dimethacrylate (TEGDMA), NK Ester 9G (polyethylene glycol-400-dimethacrylate, Kowa Europa GmbH), V-392 (N,N'-diethyl-1,3-bis(acrylamido)-propane, Ivoclar Vivadent). AG), BHT (2,6-di-tert-butyl-p-cresol):deionized water, and ethylenediaminetetraacetic acid (EDTA, Aldrich). Table 1: Composition of composite paste (wt%) [Table 1-1] *) Comparative Example

[0086] Pastes C-1 (EDTA-free), C-2 (3.66% EDTA), and C-3 (1.26% EDTA) were stored at room temperature, and the MDP content was determined by HPLC at intervals of several weeks. For HPLC measurements, an HPLC Ultimate 3000 instrument (ThermoFisher Scientific) equipped with a 125 × 4 Nucleodur 100-5 C18ec column and a UV / VIS detector (220 nm) was used. The samples were dissolved in methanol and eluted with 0.01 mol / L H3PO4 in water (A), methanol (B), and acetonitrile (C) according to the following program. The results are shown in Figure 1. Gradient Program [Table 1-2]

[0087] The results, shown in Figure 1, demonstrate the significantly improved storage stability of the EDTA-containing composite pastes C-2 and C-3. The EDTA-free composite paste C-1 (square shape) showed a significant decrease in available MDP already after 3–4 weeks, whereas for the EDTA-containing composite pastes C-2 (triangle shape) and C-3 (circular shape), more than two-thirds of the original MDP was still available after 24 weeks.

[0088] Example 2 Preparation of dual-cure self-adhesive composite cement Similar to Example 1, catalyst pastes CP-1 (without EDTA), CP-2, and CP-3 (with EDTA), and base pastes were prepared with the compositions shown in Table 2. The dentin adhesion of the materials was determined as a function of storage time. For dentin adhesion studies, bovine teeth were embedded in plastic cylinders so that the dentin and plastic were in the same plane. After etching with 37% phosphoric acid for 15 seconds, they were thoroughly rinsed with water. The acid etching opened the dentinal tubules. The catalyst pastes were then separately mixed with the base pastes in a 1:1 ratio to form cements. A layer of the mixture to be tested was then applied to the teeth with a microbrush and exposed to a halogen lamp (Astralis 7, Ivoclar Vivadent AG) for 40 seconds. Composite cylinders made of dental composite material (Tetric® Ceram; Ivoclar Vivadent AG) were polymerized onto the cement layer in two layers of 1-2 mm each, each of which was cured by 40 seconds of exposure to an Astralis 7 halogen lamp. The specimens were then stored in water at 37°C for 24 hours, and the shear bond strength was determined. The results are shown in Figure 2.

[0089] For cements based on the base paste and EDTA-free paste CP-1 (square shape), a dentin bond strength value of 3.21 MPa was determined after 28 days. In contrast, cements based on the base paste and EDTA-containing pastes CP-2 (downward-pointing triangular shape) and CP-3 (circular shape) yielded significantly higher dentin bond strength values ​​of 5.76 MPa (CP-2) and 4.42 MPa (CP-3), respectively, at room temperature after 4 weeks of storage. Table 2: Composition of base and catalyst paste (wt%) [Table 2] * ) Comparative Example 1) TEMPO: 2,2,6,6-tetramethylpiperidinyloxyl, CAS number 2564-83-2 2) Composition (wt%): Al2O3: 24; SiO2: 23; CaO: 16.5; CaF2: 16; BaO: 11.5; P2O5: 8; Na2O: 2; 5% silane; average particle size 1 μm (Schott AG, Mainz) 3) Composition (wt%): Al2O3: 24; SiO2: 23; CaO: 16.5; CaF2: 16; BaO: 11.5; P2O5: 8; Na2O: 2; 5% silane; average particle size 7 μm (Schott AG, Mainz) 4) Pyrogenic silica; trimethylsiloxy surface modified; BET surface area (DIN ISO 9277 DIN 66132) unsilanized: approx. 200 m 2 / g;Density (SiO2;DIN 51757):2.2g / cm 3 ;Residual silanol content (approximately 2 SiOH / nm 2 Relative silanol content based on non-silanized silica: 25% (Wacker Chemie AG) 5) 2,5-Dihydroxyterephthalic acid diethyl ester (Riedel-de Haen AG)

[0090] The transparency of the composite cements was measured in transmission on 1 mm thick test specimens polished to a high brightness using a spectrophotometer (Konika-Minolta Spectrophotometer CM-5). Determination of the transparency of the base paste and cements based on catalyst pastes CP-1 to CP-3 gave the following transparency values: CP-1: 21.1%; CP-2: 16.7%; CP-3: 18.8%. Although the transparency of the cements based on catalyst pastes CP-2 and CP-3 was somewhat reduced by the addition of EDTA compared to the cement based on CP-1, the transparency values ​​of the composite cements according to the invention are significantly higher than those of classic glass ionomer cements such as Vivaglass CEM PL (Ivoclar Vivadent AG), which has a transparency of 6.7%.

Claims

1. 1. A radically polymerizable composition comprising at least one acidic radically polymerizable monomer, at least one fluoroaluminosilicate glass filler, and / or a radiopaque glass filler, and at least one masking agent, wherein the masking agent is in solid form.

2. 2. The composition of claim 1, wherein the masking agent is selected from ethylenediaminetetraacetic acid (EDTA) and its disodium salt (disodium ethylenediaminetetraacetate), nitrilotriacetic acid, diethylenetriaminepentaacetic acid, tetrasodium iminodisuccinate, and the trisodium salt of methylglycine diacetate.

3. 3. The composition of claim 2, wherein the masking agent is in particulate form and has a volume average particle size (D50 value) of preferably from 300 to 350 μm, more preferably from 200 to 250 μm, most preferably from 100 to 170 μm, and also a D10 value of preferably from 130 to 150 μm, more preferably from 80 to 100 μm, most preferably from 70 to 55 μm.

4. In each case relative to the total weight of the composition, from 5 to 60% by weight, preferably from 8 to 45% by weight and particularly preferably from 10 to 35% by weight, of at least one radically polymerizable monomer free of acid groups, from 1 to 15% by weight, preferably from 2 to 12% by weight and particularly preferably from 3 to 10% by weight, of at least one radically polymerizable monomer containing acid groups, from 25 to 80% by weight, preferably from 30 to 75% by weight, particularly preferably from 40 to 70% by weight, of at least one fluoroaluminosilicate and / or radiopaque glass filler, - 0.1 to 8% by weight, preferably 0.5 to 6% by weight, particularly preferably 1 to 5% by weight, of at least one initiator for radical polymerization, and - 0.5 to 6.0% by weight, preferably 0.7 to 5.0% by weight, particularly preferably 1.0 to 4.0% by weight, of at least one masking agent The composition of any one of claims 1 to 3, comprising:

5. In each case relative to the total weight of the composition, a) 0.5 to 6% by weight, preferably 0.7 to 5% by weight, particularly preferably 1.0 to 4.0% by weight, of at least one solid masking agent, b) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer free of acid groups, c) 1 to 15% by weight, preferably 2 to 12% by weight, particularly preferably 3 to 10% by weight, of at least one monomer containing acid groups, d) 0 to 10% by weight, preferably 0 to 8% by weight, particularly preferably 1 to 5% by weight, of one or more oligomeric carboxylic acids, e) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers free of acid groups, f) 25 to 80% by weight, preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight, of at least one fluoroaluminosilicate glass filler and / or radiopaque glass filler, g) 1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more additional fillers, h) 0.1 to 8% by weight, preferably 0.5 to 6% by weight, particularly preferably 1 to 5% by weight, of an initiator for radical polymerization, i) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and j) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.005 to 2% by weight of additives The composition of claim 4 comprising:

6. Examples of polyfunctional monomers (b) include bisphenol A dimethacrylate, bis-GMA (an addition product of methacrylic acid and bisphenol A diglycidyl ether), ethoxylated or propoxylated bisphenol A dimethacrylate, such as bisphenol A dimethacrylate having three ethoxy groups or 2,2-bis[4-(2-methacryloyloxypropoxy)phenyl]propane, urethanes of 2-(hydroxymethyl)acrylic acid with diisocyanates, such as urethanes of 2,2,4-trimethylhexamethylene diisocyanate or isophorone diisocyanate, UDMA (2-hydroxyethyl methacrylate), acrylate and 2,2,4-trimethylhexamethylene-1,6-diisocyanate), tetramethylxylylene diurethane ethylene glycol di(meth)acrylate or tetramethylxylylene diurethane-2-methylethylene glycol diurethane di(meth)acrylate (V380), di-, tri-, or tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, and glycerol di- and trimethacrylate, 1,4-butanediol dimethacrylate, 1,10-decanediol dimethacrylate (D ３ MA), bis(methacryloyloxymethyl)tricyclo[5.2.1.0 ２，６ 10. The composition of claim 4, comprising at least one monomer selected from 1,3-dimethyl-2,4-diol (DMSO), 1,3-dimethyl-2,4-diol (DMSO), 1,4 ...

7. 4. The composition according to claim 1, wherein the acid group-containing monomer is at least one monomer selected from the group consisting of 2-methacryloyloxyethylphenyl hydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate (MDP), glycerol dihydrogen dimethacrylate, dipentaerythritol pentamethacryloyloxyphosphate, 4-vinylbenzylphosphonic acid, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid, and / or 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid-2,4,6-trimethylphenyl ester, and / or carboxy group-containing monomers, preferably 4-(meth)acryloyloxyethyltrimellitic anhydride, 10-methacryloyloxydecylmalonic acid, N-(2-hydroxy-3-methacryloyloxypropyl)-N-phenylglycine, and / or 4-vinylbenzoic acid.

8. 6. The composition according to claim 5, comprising as oligomeric carboxylic acid (d) a polyacrylic acid having a number average molecular weight of less than 7,200 g / mol, preferably less than 7,000 g / mol, particularly preferably less than 6,800 g / mol.

9. 6. The composition of claim 5, comprising, as the monofunctional monomer (e), at least one monomer selected from benzyl, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, p-cumylphenoxyethylene glycol methacrylate (CMP-1E), and 2-[1,1'-biphenyl]-2-oxy)ethyl methacrylate (MA-836), tricyclodecanemethyl (meth)acrylate, 2-(2-biphenyloxy)ethyl (meth)acrylate, 2-hydroxyethyl (methacrylate), hydroxyethylpropyl (methacrylate), 2-acetoxyethyl methacrylate, and mixtures thereof.

10. Composition (by weight) of: SiO ２ : 20 to 80; B ２ O ３ : 2 to 15, BaO or SrO: 0 to 40; Al ２ O ３ : 2 to 20; CaO and / or MgO: 0 to 20; Na ２ O.K. ２ O, Cs ２ O: 0 to 10; WO ３ : 0-20; ZnO: 0-20; La ２ O ３ : 0 to 10; ZrO ２ : 0 to 15; P ２ O ５ : 0 to 30; Ta ２ O ５ , Nb ２ O ５ Or Yb ２ O ３ : 0 to 5; and CaF ２ and / or SrF ２ 0 to 10; or preferably SiO ２ : 50 to 75; B ２ O ３ : 2 to 15; BaO or SrO: 2 to 35; Al ２ O ３ : 2 to 15; CaO and / or MgO: 0 to 10; and Na ２ O: Radiopaque glass filler having 0-10; and / or the following composition (wt%): SiO ２ : 20 to 35; Al ２ O ３ : 15 to 35; BaO or SrO: 10 to 25; CaO: 0-20; ZnO: 0 to 15; P ２ O ５ : 5 to 20; Na ２ O.K. ２ O, Cs ２ O: 0-10 respectively; and CaF ２ : 0.5 to 20 wt%; or preferably SiO ２ : 20 to 30; Al ２ O ３ : 20 to 30; BaO or SrO: 10 to 25; CaO: 5-20; P ２ O ５ : 5 to 20; Na ２ O: 0-10; and CaF ２ 5. The composition of claim 4, comprising 5 to 20 weight percent of a fluoroaluminosilicate glass filler, all values ​​being relative to the total mass of the glass, and all components other than fluorine being calculated as oxides.

11. 4. The composition of claim 1, comprising at least one redox initiator, or at least one redox initiator and at least one photoinitiator.

12. a catalyst paste and a base paste, the catalyst paste comprising in each case, relative to the total mass of the catalyst paste: a) 1.0 to 12% by weight, preferably 1.4 to 10% by weight, particularly preferably 2.0 to 8.0% by weight, of at least one solid masking agent, b) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer free of acid groups, c) 2 to 30% by weight, preferably 4 to 24% by weight, particularly preferably 6 to 20% by weight, of at least one monomer containing acid groups, d) 0.1 to 20% by weight, preferably 1 to 16% by weight, particularly preferably 2 to 10% by weight, of one or more oligomeric carboxylic acids, e) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers free of acid groups, f) 25 to 80% by weight, preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight, of at least one fluoroaluminosilicate glass filler and / or glass filler, g) 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more additional fillers, h) 0.01 to 16% by weight, preferably 0.02 to 12% by weight, particularly preferably 0.03 to 10% by weight, of at least one peroxide and / or hydroperoxide, and optionally at least one photoinitiator; i) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and j) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.0051 to 2% by weight of additives Including, The base paste comprises, in each case relative to the total mass of the base paste: a) Not applicable; b) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer free of acid groups, c) Not applicable; d) Not applicable; e) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers free of acid groups, f) 25 to 80% by weight, preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight, of at least one fluoroaluminosilicate glass filler and / or glass filler, g) 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more additional fillers, h) 0.01 to 16% by weight, preferably 0.02 to 12% by weight, particularly preferably 0.03 to 10% by weight, of at least one suitable reducing agent and, if desired, a photoinitiator; i) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and j) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.0051 to 2% by weight of additives Including, The composition of claim 4.

13. 13. The composition of claim 12, wherein the catalyst paste and the base paste are each contained in a different chamber of a dual push syringe.

14. 4. A composition according to any one of claims 1 to 3 for therapeutic use as a dental material, preferably as a dental cement, coating or veneering material, restorative composite or luting cement.

15. 4. Non-therapeutic use of a composition according to any one of claims 1 to 3 for the manufacture or repair of a dental restoration, in particular an inlay, onlay, crown or bridge.

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