Self-adhesive dental composite cements with good transparency based on acid-treated fillers

Abstract

To provide adhesive dental composite cements with good transparency based on acid-treated fillers.SOLUTION: A radically polymerizable dental material has at least one radically polymerizable monomer without acid groups, at least one radically polymerizable monomer containing an acid group, at least one fluoroaluminosilicate glass filler and / or radiopaque glass filler, and at least one initiator for the radical polymerization, wherein the filler is an acid-treated fluoroaluminosilicate glass filler and / or glass filler.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 the fabrication of inlays, onlays or crowns. [Background technology]

[0002] Composites are primarily used in dentistry to fabricate direct and indirect filling materials, i.e., as direct and indirect filling composites and as cements. The polymerizable organic matrix of a composite typically consists of a mixture of monomers, initiator components, and stabilizers. A mixture of dimethacrylates is typically used as the monomer, which may contain monofunctional and difunctional monomers. Commonly used dimethacrylates are 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropyl)phenyl]propane (bis-GMA), 1,6-bis[2-methacryloyloxyethoxycarbonylamino]-2,2,4-trimethylhexane (UDMA), which produce polymers with high viscosity, good mechanical properties, and low polymerization shrinkage. Other dimethacrylates include triethylene glycol dimethacrylate (TEGDMA), 1,10-decanediol dimethacrylate (D3MA), or bis(3-methacryloyloxymethyl)tricyclo[5.2.1.0]. 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, leading to a decrease in network density and increased 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 cause 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 pre-treatment 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, which 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, sculptability) of the material, and confer radiopacity.

[0005] Problems often arise when acidic adhesive monomers interact unfavorably with fillers. For example, they bind to the surface of the filler by forming insoluble salts, or form poorly soluble salts with ions released from the filler during storage. This results in a significant reduction in adhesive monomer concentration in the resin matrix, which is associated with a reduction or even loss of adhesive properties. Therefore, composites with 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 usually contain redox systems to ensure adequate cure even when light curing is not possible due to insufficient transparency. 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 also by strongly acidic adhesive monomers, redox initiator systems containing cumene hydroperoxide in combination with a thiourea, such as acetylthiourea, are preferred.

[0008] To ensure sufficient storage stability of the 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, barbiturate, thiourea, etc.) are incorporated as separate components. These are mixed together immediately before use. For mixing, a double-push syringe with separate cylindrical chambers for holding the components is preferably used. The components are simultaneously pushed out of the chambers by two interconnected pistons and mixed together in the nozzle. To obtain the most homogeneous mixture 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 even more difficult. Furthermore, glass ionomer cements have very low transparency and relatively poor mechanical properties.

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

[0011] Resin-modified glass ionomer cements (RMGI) contain additional 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] U.S. Patent No. 8,053,490 discloses a fluoride-releasing dental material containing a fluoroaluminosilicate glass filler (FAS) reacted with an aqueous solution of a monomer or oligomer containing acid groups. The acid-containing monomer or oligomer is said to bond to the filler surface and prevent reaction between the filler and reactive components of the cement. The material is characterized by poor transparency and unsatisfactory mechanical properties.

[0013] JP 2011-6030741 A discloses a dental material containing a fluoroboroaluminosilicate glass filler surface-modified with silane and polymeric carboxylic acid. The filler is spherical and is said to exhibit sustained release of fluoride ions and other ions. The dental material does not self-adhere to dentin and enamel and exhibits unsatisfactory mechanical properties.

[0014] U.S. Patent Application Publication No. 2016 / 0324729 discloses a filler for glass ionomer cement, the surface of which is first silanized and then modified with an unsaturated carboxylic acid, which bonds to the filler surface via the silicon atom. The carboxyl group of the carboxylic acid is said to interact with the components of the glass ionomer cement, thus stabilizing the cement. The material has moderate transparency and poor mechanical properties.

[0015] Chinese Patent Application Publication No. 102976618 discloses a low-cost glass filler for water-based glass ionomer cement containing 25-35 wt% Al2O3, 30-45 wt% SiO2, 2-8 wt% Na2O, 5-15 wt% CaF2, and 5-8 wt% SrO and / or CaO. The glass powder is treated with hydrochloric acid or acetic acid at room temperature and then dried. They are said to have stable quality, good mechanical properties, and continuously release fluoride ions. The glass ionomer cement has low transparency and poor mechanical properties.

[0016] Dai et al., Int. J. Nanomedicine 14 (2019) 9185, showed that surface treatment of basic ZrO2 fillers with 10-methacryloyloxydecyl dihydrogen phosphate (MDP) can improve the flexural strength of dental composites, and that pre-coating ZrO2 with Zr(OH)4 improves the bond between MDP and zirconia. Dental materials based on surface-treated fillers do not self-adhere and have poor transparency.

[0017] According to U.S. Patent No. 8,071,662, surface modification of basic fillers such as ZrO2 with strong acids such as 3-methacryloyloxypropylsulfonic acid is said to improve the storage stability of self-etching dental materials. The dental materials disclosed do not self-etch and have unsatisfactory transparency. German Patent Application No. 2446546 discloses the treatment of naturally occurring silica with aqueous mineral acid to remove acid-soluble impurities. The silica is said to be suitable as a filling material for dental purposes. Radiopaque or self-adhesive dental materials are not disclosed. US Patent Application Publication No. 2001 / 0034309 discloses the treatment of inorganic fillers with peracids or persalts to remove organic substances, such as carbon. The removal of organic substances is intended to improve the bonding between the silane coupling agent and the filler surface, and thus the incorporation of the filler into the organic matrix of the radically polymerizable dental material. No self-adhesive materials are disclosed. [Prior art documents] [Patent documents]

[0018] [Patent Document 1] U.S. Patent No. 8,053,490 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-6030741 [Patent Document 3] US Patent Application Publication No. 2016 / 0324729 [Patent Document 4] Chinese Patent Application Publication No. 102976618 [Patent Document 5] U.S. Patent No. 8,071,662 [Patent Document 5] DE 2446546 A1 [Patent Document 6] US Patent Application Publication No. 2001 / 0034309 [Non-patent literature]

[0019] [Non-Patent Document 1] Dai et al, Int. J. Nanomedicine 14 (2019) 9185 Summary of the Invention [Means for solving the problem]

[0020] 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 mixed and applied as a two-component system using a double-push syringe. The composite should be particularly suitable as a dental luting cement and should be radiopaque.

[0021] This object is achieved by a radically polymerizable composition containing a filler, the filler comprising at least one radically polymerizable monomer, at least one acidic radically polymerizable monomer, at least one fluoroaluminosilicate glass filler and / or a radiopaque glass filler, and at least one initiator for radical polymerization. The composition is characterized in that the filler is pretreated with an acid. Surprisingly, it has been found that acid treatment of the filler significantly increases the storage stability of the composition. The present application provides, for example, the following items: (Reclaim) (Item 1) A radically polymerizable composition comprising at least one radically polymerizable monomer having no acid group, at least one radically polymerizable monomer having an acid group, at least one fluoroaluminosilicate glass filler and / or a radiopaque glass filler, and at least one radical polymerization initiator, wherein the fluoroaluminosilicate glass filler and / or the glass filler has been acid washed. (Item 2) Composition (wt%) a radiopaque glass filler which is preferably SiO2: 50-75; 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; and / or 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 based on the total weight of the glass and all components except fluorine being calculated as oxides. (Item 3) Item 10. The composition of any one of the preceding items, wherein the fluoroaluminosilicate glass filler or glass filler has been washed with hydrochloric acid, nitric acid, formic acid, and / or acetic acid. (Item 4) In each case relative to the total weight of the composition, a) 10 to 80% by weight, preferably 20 to 75% by weight, particularly preferably 30 to 70% by weight, of at least one acid-washed fluoroaluminosilicate glass filler and / or glass filler, b) optionally 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more further fillers, 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) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer having no acid groups, e) 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, f) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers having no acid groups, g) 0.1 to 8% by weight, preferably 0.5 to 6% by weight, particularly preferably 1 to 5% by weight, of a radical polymerization initiator, h) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and i) 0.01 to 5% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.1 to 2% by weight, of one or more additives Item 10. The composition of any one of the preceding items, comprising: (Item 5) Examples of radically polymerizable monomers without an acid group 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, UDMA (addition product of 2-hydroxyethyl methacrylate and 2,2,4-trimethylhexamethylene-1,6-diisocyanate), tetramethyloxy xylylene 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 (D3MA), bis(methacryloyloxymethyl)tricyclo[5.2.1.0]methylpropanol, ... 2,6decane (DCP), polyethylene glycol or polypropylene glycol dimethacrylates, such as polyethylene glycol 200-dimethacrylate (PEG-200-DMA) or polyethylene glycol 400-dimethacrylate (PEG-400-DMA), 1,12-dodecanediol dimethacrylate, urethanes of 2-(hydroxymethyl)acrylic acid with diisocyanates, such as urethanes of 2,2,4-trimethylhexamethylene diisocyanate or isophorone diisocyanate, pyrrolidine diisocyanate, methylpropional ... 1,4-bis(acrylamido)butane, or 1,4-bis(acryloyl)piperazine, and mixtures thereof. (Item 6) The composition according to any one of the preceding items, comprising, as the acid group-containing monomer (c), at least one monomer having a pKa at room temperature of 0.5 to 4.0, more preferably 1.0 to 3.5, and most preferably 1.5 to 2.5. (Item 7) Item 10. The composition according to any one of the preceding items, comprising as the acid group-containing monomer (c) at least one monomer containing a phosphate ester group or a phosphonic acid group, preferably selected from 2-methacryloyloxyethylphenyl hydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate (MDP), glycerol dimethacrylate dihydrogen phosphate, 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 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 (e) 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 a free-radically polymerizable monomer having no acid group, at least one monofunctional monomer (f) selected from benzil, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, p-cumyl-phenoxyethylene glycol methacrylate (CMP-1E), 2-([1,1'-biphenyl]-2-oxy)ethyl methacrylate (MA-836), tricyclodecanemethyl (meth)acrylate, 2-(2-biphenyloxy)ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxyethylpropyl (meth)acrylate, 2-acetoxyethyl methacrylate, and mixtures thereof. (Item 10) a catalyst paste and a base paste, the catalyst paste comprising in each case, relative to the total mass of the catalyst paste: a) 10 to 80% by weight, preferably 20 to 75% by weight, particularly preferably 30 to 70% by weight, of at least one acid-treated FAS and / or glass filler, b) 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more further fillers, 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) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer having no acid groups, e) 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, f) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers, g) 0.01 to 16% by weight, preferably 0.2 to 12% by weight, particularly preferably 0.5 to 10% by weight, of at least one peroxide and / or hydroperoxide and optionally at least one photoinitiator, h) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and i) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.0051 to 2% by weight, of one or more additives Including, The base paste comprises, in each case relative to the total mass of the base paste: a) 10 to 80% by weight, preferably 20 to 75% by weight, particularly preferably 30 to 70% by weight, of at least one acid-treated FAS and / or glass filler, b) 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more further fillers, d) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer having no acid groups, f) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers having no acid groups, g) 0.01 to 16% by weight, preferably 0.3 to 12% by weight, particularly preferably 1 to 10% by weight, of at least one suitable reducing agent and, if necessary, at least one photoinitiator, h) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and i) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.0051 to 2% by weight, of one or more additives Item 10. The composition of any one of the preceding items, comprising: (Item 11) 10. A composition according to any one of the preceding items for therapeutic use as a dental material, preferably as a dental cement, coating material, or veneering material, restorative composite, or luting cement. (Item 12) 10. Non-therapeutic use of a composition according to any one of the preceding items for preparing or repairing a dental restoration, in particular an inlay, onlay, crown or bridge. (Item 13) 1. A method for treating a fluoroaluminosilicate glass filler or glass filler with an acid, comprising: (i) the fluoroaluminosilicate glass filler or glass filler is dispersed in an aqueous solution of an organic and / or inorganic acid, preferably hydrochloric acid, nitric acid, formic acid, and / or acetic acid, the acid solution preferably having an acid concentration of 0.1 to 5 mol / l, particularly preferably 0.5 to 3 mol / l, (ii) the dispersion is stirred for preferably 0.5 to 24 hours, more preferably 1 to 5 hours; (iii) the filler is then separated and washed with deionized water; (iv) The method wherein the filler is separated and dried. (Item 14) Item 10. The method according to any one of the preceding items, wherein in step (iii), the filler is dispersed in deionized water, and then the dispersion is stirred for 1 to 60 minutes, preferably 2 to 20 minutes, and this process is preferably repeated 1 to 5 times, more preferably 3 times. (Item 15) Use of a fluoroaluminosilicate glass filler or glass filler preparable according to any one of the preceding paragraphs for stabilizing a dental radically polymerizable composition. DETAILED DESCRIPTION OF THE INVENTION

[0022] The present invention relates to a radically polymerizable dental material comprising at least one radically polymerizable monomer without an acid group, at least one radically polymerizable monomer containing an acid group, at least one fluoroaluminosilicate glass filler and / or radiopaque glass filler, and at least one initiator for radical polymerization, wherein the filler is an acid-washed fluoroaluminosilicate glass filler and / or glass filler.

[0023] The composition according to the invention contains at least one fluoroaluminosilicate glass filler (FAS filler) and / or a radiopaque glass filler. Compositions containing fillers are called composites.

[0024] A preferred radiopaque glass filler has the following composition (by weight): 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 or SrF2: 0-10. Particularly preferred is a radiopaque glass filler having the 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.

[0025] 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.

[0026] All percentages are relative to the total weight of the glass with the components excluding fluorine calculated as oxides, as is common in glasses and glass-ceramics.

[0027] The compositions according to the invention preferably contain from 10 to 80% by weight, more preferably from 20 to 75% by weight, most preferably from 30 to 70% by weight of FAS fillers and / or radiopaque glass fillers in each case relative to the total weight of the composition.

[0028] The FAS filler and the radiopaque glass filler preferably have an average particle size of 0.2 to 20 μm, particularly preferably 0.4 to 5 μm.

[0029] Unless otherwise indicated, all particle sizes herein are volume average particle sizes (D50 values), i.e., 50% of the total volume of all particles is contained in particles having a diameter smaller than the indicated value.

[0030] Particle size determination in the range of 0.1 μm to 1,000 μm is preferably performed 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). Here, 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 for the measurement of the entire particle size distribution of a sample in a single measurement run, which is performed 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. Scattered light analysis to calculate particle size and particle size distribution is performed 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 with a wavelength of 633 nm at a scattering angle of 90° and 25°C, for example with a Malvern Zetasizer Nano ZS (Malvern Instruments, Malvern UK).

[0031] For agglomerates and aggregates, the primary particle size can be determined using 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 50 Å thick carbon-coated copper grid (mesh size 300 mesh), followed by solvent evaporation. The particles are counted and the arithmetic mean is calculated.

[0032] The acid treatment of the granular FAS or glass filler is carried out by washing the filler with acid, preferably by the following process: (i) The granular FAS or glass filler is dispersed in an aqueous solution of an organic or, preferably, inorganic acid, preferably at a concentration of 0.1 to 5 mol / l, particularly preferably 0.5 to 3 mol / l. (ii) The dispersion from step (i) is then stirred, preferably for 0.5 to 24 hours, more preferably for 1 to 5 hours. (iii) After stirring in the acid solution, the filler is separated and washed with deionized water. For this purpose, it is preferably dispersed in water and stirred for 1 to 60 minutes, particularly preferably 2 to 20 minutes. (iv) After washing, the filler is separated and dried, preferably in a high vacuum drying oven at 20 to 80° C., particularly preferably 40 to 60° C. The filler is preferably dried to a constant weight. (v) After drying, the filler is preferably subjected to heat treatment if necessary. For this purpose, it is heated to a temperature sufficiently lower than the glass transition temperature of the filler, preferably 200 to 500°C, particularly preferably 300 to 400°C, for preferably 2 to 12 hours, particularly preferably 4 to 6 hours.

[0033] In the process according to the invention, the acid used to treat the filler is preferably completely removed from the filler after acid treatment. The filler is not coated with acid.

[0034] The acid treatment can be repeated once or several times. Steps (i) and (iii) are preferably carried out at a temperature of 5 to 50°C, particularly preferably at room temperature (23°C). The temperature is measured in each case on the solution or dispersion.

[0035] Acids that form soluble salts with Ca, Al, Sr, and Ba ions are preferred. Formic acid, acetic acid, and especially hydrochloric and nitric acids are particularly preferred. Alternatively, acids that form slightly soluble salts with Ca, Al, Sr, or Ba ions, such as phosphoric acid, may be used, but these are less preferred. Insufficiently soluble salts are defined as salts with a solubility of less than 0.1 g / L (in water at room temperature). According to the present invention, acidic organic monomers and polymers, as well as peracids and hydrofluoric acid, are not suitable as acids.

[0036] The washing step (iii) is preferably repeated 1 to 5 times, particularly preferably 3 times, so that the acid is completely removed from the filler. For this purpose, the filler is separated from the water after step (iii) and redispersed and stirred in deionized water. The washing is repeated until the pH of the water in the last washing step is ≥ 5.

[0037] After washing, the filler can be subjected to further acid treatment and washing. The acid treatment and washing procedure can be repeated one or several times.

[0038] After drying and, if necessary, heat treatment, the filler according to the invention is preferably surface-modified, particularly preferably silanized. The silanization is preferably carried out with a radically polymerizable silane, in particular with, for example, 3-methacryloyloxypropyltrimethoxysilane (MEMO). The filler is easily miscible with the other components of the composite material.

[0039] Surprisingly, it has been found that acid treatment of the filler significantly improves the storage stability of the composition according to the present invention, and the content of radically polymerizable monomers containing acid groups only slowly decreases. The composition exhibits high adhesion to tooth structures, especially dentin, even after long-term storage. Thus, acid treatment allows for a significant improvement in the properties of dental compositions with self-adhesive properties in a simple manner. After hardening, the composition according to the present invention is also characterized by high transparency compared to glass ionomer cements.

[0040] In addition to the FAS and radiopaque glass fillers described above, compositions according to the present invention may contain additional fillers.

[0041] Preferred additional fillers are metal oxides, particularly mixed oxides, containing 60-80% by weight of SiO2 and at least one of the metal oxides ZrO2, Yb2O3, ZnO, Ta2O5, Nb2O5, and / or La2O3, preferably ZrO2, Yb2O3, and / or ZnO, totaling 100%. Mixed oxides, such as SiO2-ZrO2, can be obtained, for example, by hydrolytic co-condensation of metal alkoxides. The metal oxide preferably has an average particle size of 0.05-10 μm, particularly preferably 0.1-5 μm. The metal oxide(s) are also preferably treated with acid in the manner described above.

[0042] Other preferred additional fillers are pyrogenic or precipitated silica with a primary particle size of 0.01 to 0.15 μm, quartz or glass-ceramic powder with a particle size of 0.1 to 15 μm, preferably 0.2 to 5 μm, and ytterbium trifluoride, preferably with a particle size of 80 to 900 nm, particularly preferably 100 to 300 nm. These fillers are preferably used in amounts of 0.1 to 25 wt. %, more preferably 0.2 to 20 wt. %, and most preferably 0.3 to 15 wt. %, in each case based on the total mass of the composition.

[0043] Furthermore, so-called composite fillers are preferred as further fillers. They are also called isofillers. These are splinter-like polymers containing fillers, preferably pyrogenic SiO2, glass fillers, and / or ytterbium trifluoride. Dimethacrylate-based polymers are preferred. In the production of isofillers, the filler(s) are incorporated into, for example, a dimethacrylate resin matrix, and the resulting composite paste is then thermally polymerized and then ground.

[0044] 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%), followed by grinding the cured material to the desired particle size. All percentages refer to the total mass of the composite filler.

[0045] 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.

[0046] 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.

[0047] The compositions according to the invention preferably contain 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more further fillers, preferably one or more metal oxides, pyrogenic silica and / or precipitated silica, in each case based on the total weight of the composition.

[0048] 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, particularly preferably two radically polymerizable groups. Thus, monofunctional monomers 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.

[0049] 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 not containing an acid group and at least one monomer and / or oligomer containing an acid group. The composition according to the present invention preferably contains the monomers containing an acid group and the monomers not containing 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.

[0050] 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.

[0051] Preferred monofunctional (meth)acrylates are benzyl, tetrahydrofurfuryl, or isobornyl (meth)acrylate, p-cumylphenoxyethylene glycol methacrylate (CMP-1E), and 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.

[0052] 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.

[0053] Preferred di- and 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- ..., UDMA (2-hydroxymethyl)acrylic acid methyl ester with diisocyanates, such as urethanes of 2,2,4-trimethylhexamethylene diisocyanate, UDMA (2-hydroxymethyl)acrylic acid methyl ester with diisocyanates, such as urethanes of 2,2,4-trimethylhexamethylene diisocyanate, UDMA (2-hydroxymethyl)acrylic acid methyl ester with diisocyanates, such Addition products of hydroxyethyl methacrylate and 2,2,4-trimethylhexamethylene-1,6-diisocyanate), tetramethylxylylene diurethane ethylene glycol 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.

[0054] The monomer tetramethylxylylene diurethane ethylene glycol di(meth)acrylate or tetramethylxylylene diurethane 2-methylethylene glycol diurethane di(meth)acrylate (V380) has the following formula: [ka] It has.

[0055] In the formula shown, each R radical is independently H or CH3, and these 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.

[0056] 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.

[0057] Monomers and oligomers containing acid groups The compositions according to the present invention contain at least one acidic radically polymerizable monomer and / or at least one acidic oligomer. Acidic monomers and oligomers are understood to mean monomers and oligomers, respectively, containing at least one acid group, preferably a phosphate ester, phosphonic acid, or carboxyl group. Acidic monomers and oligomers are also referred to herein as adhesive components, adhesive monomers, or adhesive oligomers. According to the present invention, those compositions containing at least one strongly acidic monomer are particularly preferred. The strongly acidic monomer is a monomer having a pKa value at room temperature of 0.5 to 4.0, more preferably 1.0 to 3.5, and most preferably 1.5 to 2.5.

[0058] Suitable monomers containing an acid group are COOH group-containing polymerizable monomers, preferably those with a pKa value in the range of 2.0 to 4.0. 4-(meth)-acryloyloxyethyltrimellitic anhydride, 10-methacryloyloxydecylmalonic acid, N-(2-hydroxy-3-methacryloyloxypropyl)-N-phenylglycine, and 4-vinylbenzoic acid are preferred. Methacrylic acid (pKa=4.66) is excluded due to its poor adhesion to tooth structure.

[0059] Preferred monomers containing acid groups are phosphate ester and phosphonic acid monomers, preferably those with pKa values ​​in the range of 0.5 to 3.5. 2-Methacryloyloxyethylphenyl hydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate (MDP), glycerol dihydrogen phosphate, or dipentaerythritol pentamethacryloyloxyphosphate, 4-vinylbenzylphosphonic acid, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]acrylic acid, or hydrolytically 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 even more preferred.

[0060] The oligomer has a degree of polymerization P n 2 to 100 (P n =M n / M u ;M n : number average polymer molecular weight, M u (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.

[0061] Preferred acid group-containing oligomers according to the present invention are oligomeric carboxylic acids, such as polyacrylic acids, preferably having a number average molecular weight M n is 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 nis preferably in the range of 800 to 7,200 g / mol, more 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 acid with glycidyl methacrylate or 2-isocyanatoethyl methacrylate.

[0062] Unless otherwise stated, the molar mass of oligomers and polymers herein is the number-average molar mass, the absolute value of which can be determined by the known methods of freezing point depression (cryoscopy), boiling point elevation (ebullioscopy), or vapor pressure depression (vapor pressure osmometry). Preferably, the number-average molecular weight of oligomers and polymers is determined by gel permeation chromatography (GPC), a relative method in which molecules are separated based on their size, more precisely, on their hydrodynamic volume. Absolute molar mass is determined by calibration with known standards.

[0063] The compositions according to the invention preferably also contain water. It has been found that a water content of 1 to 7% by weight, preferably 1 to 5% by weight, relative in each case to the total mass of the composition, results in an improved bonding effect on dentin and enamel.

[0064] 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-phenylpropane-1,2-dione, diacetyl, and 4,4'-dichlorobenzil. Camphorquinone (CQ) and 2,2-dimethoxy-2-phenylacetophenone are particularly preferred, and α-diketones in combination with amines as reducing agents, such as 4-(dimethylamino)benzoic acid ethyl ester (EDMAB), N,N-dimethylaminoethyl methacrylate, N,N-dimethyl-sym.-xylidine, or triethanolamine, are most preferred. Norrish Type I photoinitiators, especially acyl or bisacylphosphine oxides, are more preferred, with monoacyltrialkylgermanium, diacyldialkylgermanium, and tetraacylgermanium compounds, such as benzoyltriethylgermane, 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, which are combinations of camphorquinone and 4-dimethylaminobenzoic acid ethyl ester.

[0065] Further preferred is a composition 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 peroxides, particularly 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, particularly 4-(2-hydroperoxypropan-2-yl)phenylpropionate and cumene hydroperoxide (CHP).

[0066] 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.

[0067] Preferred reducing agents for combination with hydroperoxides are thiourea derivatives, particularly the compounds listed in paragraph

[0009] of EP 1 754 465 A1. 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 are particularly preferred. 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, are particularly preferred. In addition, a combination of one or more of the above-mentioned thiourea derivatives with one or more imidazoles may be advantageously used. Preferred imidazoles are 2-mercapto-1-methylimidazole or 2-mercaptobenzimidazole.

[0068] 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. Suitable transition metal compounds according to the present invention are, in particular, compounds derived from transition metals having at least two stable oxidation states. Compounds of elemental 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 result in 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. Further preferred are complexes with polydentate ligands such as 2-(2-aminoethylamino)ethanol, triethylenetetramine, dimethylglyoxime, 8-hydroxyquinoline, 2,2'-bipyridine, or 1,10-phenanthroline. A particularly preferred 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.

[0069] The compositions of the present invention preferably do not contain barbiturates or barbiturate derivatives, such as 1,3,5-trimethylbarbiturate, 1-benzyl-5-phenylbarbiturate, 5-butylbarbiturate, or 1-cyclohexyl-5-ethylbarbiturate. 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.

[0070] According to a preferred embodiment, the composition of the present invention preferably further contains a masking agent. According to the present invention, preferred masking agents are ethylenediaminetetraacetic acid (EDTA) and its sodium salt (disodium ethylenediaminetetraacetate), nitrilotriacetic acid, diethylenetriaminepentaacetic acid, tetrasodium iminodisuccinate, and the trisodium salt of methylglycinediacetic acid. EDTA is particularly preferred. Polymerizable derivatives of the aforementioned masking agents are also included. Polymerizable derivatives are masking agents having a radically polymerizable group. Preferred radically polymerizable masking agents are EDTA derivatives bearing a polymerizable (meth)acrylic or methacrylamide group. Polymerizable EDTA derivatives disclosed in DE 10 2005 022 172 A1 and alkylenediamine-N,N,N',N'-tetraacetic acid (meth)acrylamide disclosed in EP 2 065 363 A1, in which EDTA is covalently bonded to an ethylenically unsaturated monomer, are particularly preferred. The masking agent may be in a dissolved or, preferably, undissolved form.

[0071] 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%. Unless otherwise stated, all percentages herein refer to the total weight of the composition.

[0072] The compositions according to the invention may contain additional additives, in particular stabilizers, colorants, phase transfer catalysts, bactericides, fluoride ion-releasing additives, such as fluoride salts, in particular NaF or ammonium fluoride, or fluorosilanes, optical brighteners, plasticizers, and / or UV absorbers.

[0073] According to the invention, particular preference is given to compositions which comprise the following components, in each case relative to the total weight of the composition: a) 10 to 80% by weight, preferably 20 to 75% by weight, particularly preferably 30 to 70% by weight, of at least one acid-treated FAS and / or glass filler, b) optionally 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more further fillers, 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) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer having no acid groups, e) 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, f) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers having no acid groups, g) 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, h) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and i) 0.01 to 5% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.1 to 2% by weight, of one or more additives.

[0074] The initiator can be a redox initiator, a photoinitiator, or a dual-cure initiator. The amounts mentioned include all initiator components, i.e., the initiator itself and, if present, the reducing agent, 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.

[0075] 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. 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.

[0076] If the composition contains a masking agent, preferably a strongly acidic adhesive monomer, an FAS filler, and / or a radiopaque glass filler is added to the component located within.

[0077] According to the present invention, two-component systems are preferred. They are preferably self-hardening or dual-hardening. The pastes are mixed together shortly before use, preferably with a double-push syringe.

[0078] The catalyst paste preferably has the following composition, in each case based on the total mass of the catalyst paste: a) 10 to 80% by weight, preferably 20 to 75% by weight, particularly preferably 30 to 70% by weight, of at least one acid-treated FAS and / or glass filler, b) optionally 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more further fillers, 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) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer having no acid groups, e) 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, f) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers having no acid groups, g) 0.01 to 16% by weight, preferably 0.2 to 12% by weight, particularly preferably 0.5 to 10% by weight, of at least one peroxide and / or hydroperoxide and optionally at least one photoinitiator, h) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and i) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.0051 to 2% by weight, of one or more additives.

[0079] The base paste preferably has the following composition, in each case based on the total mass of the base paste: a) 10 to 80% by weight, preferably 20 to 75% by weight, particularly preferably 30 to 70% by weight, of at least one acid-treated FAS and / or glass filler, b) 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more further fillers, d) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer having no acid groups, f) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers having no acid groups, g) 0.01 to 16% by weight, preferably 0.3 to 12% by weight, particularly preferably 1 to 10% by weight, of at least one suitable reducing agent and, if necessary, at least one photoinitiator, h) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and i) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.0051 to 2% by weight, of one or more additives.

[0080] 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.

[0081] The double-push syringe has two separate cylindrical chambers for holding the base paste and the catalyst paste. The components are simultaneously pushed by two interconnected pistons and preferably forced through a mixing cannula, where they are mixed together. To push the pastes, the syringe can be inserted into a so-called hand dispenser, which makes handling the syringe easier.

[0082] The compositions according to the present invention are characterized by high storage stability and improved transparency, preferably greater than 10%, and good self-adhesion to enamel / dentin.They are particularly suitable as dental materials for intraoral use by dentists, especially for the repair of damaged teeth (therapeutic use), and as dental cements, coating or veneer materials, filling composites, and most especially luting cements.Transparency is determined by the method described in the examples.

[0083] For the treatment of damaged teeth, they are preferably prepared by dentists in the first step. Subsequently, at least one composition according to the present invention is applied to or inside the prepared tooth. After that, 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, onlay, veneer, crown, bridge, framework, or dental ceramic, is placed inside or attached to the surface of the prepared tooth. The subsequent hardening of the composition is preferably carried out by light and / or self-hardening. In this process, the dental restoration is attached to the tooth.

[0084] 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.

[0085] 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, via self-hardening or preferably by heat.

[0086] In the repair of dental restorations, the composition according to the invention is placed on the restoration to be repaired, for example to repair a gap or to join fragments, and then allowed to harden.

[0087] The invention will now be explained in more detail with reference to the figures and examples. [Brief explanation of the drawings]

[0088] [Figure 1] Figures 1 and 2 show the decrease in the concentration of the acidic monomer MDP as a function of storage time in the composite paste, respectively, with the acid-treated ( [ka] ) or non-acid-treated glass filler ( [ka] ) [Figure 2] Figures 1 and 2 show the decrease in the concentration of the acidic monomer MDP as a function of storage time in the composite paste, respectively, with the acid-treated ( [ka] ) or non-acid-treated glass filler ( [ka] ) [Example]

[0089] Example 1 Preparation of Acid-Treated Filler (General Procedure) Two 1-liter plastic centrifuge vessels were filled with 150 g of the filler to be treated and 350 g of 1.0 M hydrochloric acid, which were then stirred for 1 hour on a magnetic stirrer at room temperature. After removing the magnetic stirrer, the mixture was centrifuged at 3,000 rpm for 5 minutes in a Hettich Silenta RS centrifuge, during which the filler settled. The liquid separated, and a sample was taken for X-ray fluorescence (XRF) analysis. The pH of the liquid was then 1-2. The separated filler was then dispersed in 400 ml of deionized water, and the dispersion was again centrifuged at 3,000 rpm for 5 minutes. The washing solution was then separated by decantation. The washing procedure was repeated (approximately 3 times) until the pH rose to 5 or higher during the final washing step. After washing, the acid-treated filler was dried in a vacuum oven at 50 °C until a constant weight was reached, and then silanized. For silanization, 12 g of 3-methacryloyloxypropyltrimethoxysilane (Silane A-174, Sigma Aldrich) was added to the filler (185 g) and mixed for 15 minutes (Turbola mixer, Willy A. Bachofen AG). 5 g of deionized water was then added and mixed again for 15 minutes. The filler was then sieved through a 90 μm plastic sieve, left for 24 hours, and then dried in a drying oven at 50 °C for 3 days until no free silane was detectable (gas chromatography).

[0090] Example 2 Investigation of storage stability of composites based on filler GM27884 (with and without acid treatment).

[0091] Radiopaque dental glass filler (GM 27884, Schott, average particle size 1 μm, specific surface area (BET DIN ISO 9277) 3.9 m 2 / g, composition (wt%): Al2O3:10, BO3:10, BaO:25, and SiO2:55) was treated with acid and silanized as described in Example 1. Aluminum and barium ions were primarily detected in the acid treatment solution by XRF analysis. For comparison purposes, a portion of the filler was silanized without prior acid treatment.

[0092] Composite pastes were prepared with acid-treated filler (Paste 1) and untreated filler (Paste 2) with the following composition (wt%): filler: 65.39, 10-methacryloyloxydecyl dihydrogen phosphate (MDP, Orgentis): 3.67, triethylene glycol dimethacrylate (TEGDMA): 9.52, NK Ester 9G (polyethylene glycol 400 dimethacrylate, Kowa Europa GmbH): 2.12, V-392 (N,N'-diethyl-1,3-bis(acrylamido)-propane, Ivoclar Vivadent AG): 13.04, BHT (2,6-di-tert-butyl-p-cresol): 0.04, and deionized water: 6.23.

[0093] The paste was stored at room temperature, and the MDP content was determined by HPLC at intervals of several weeks. For HPLC measurements, an HPLC Ultimate 3000 (ThermoFisher Scientific) instrument equipped with a 125x4 Nucleodur 100-5 C18ec column and a UV / VIS detector (220 nm) was used. The sample was 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. [Table 3]

[0094] The results, shown in Figure 1, demonstrate the significantly improved storage stability of pastes based on acid-treated fillers. In pastes containing untreated fillers, MDP was no longer detectable after only one week.

[0095] Example 3 Preparation of dual-cure self-adhesive composite cement Dual-cure composite cements were prepared. Each cement contained a catalyst paste and a base paste. The paste compositions are shown in Tables 1 and 2. The glass filler used to prepare catalyst paste 1 was acid-treated using the procedure described in Example 1. All fillers were silanized. Dentin adhesion was determined as a function of storage time. To investigate dentin adhesion, bovine teeth were embedded in plastic cylinders with addition-cure vinyl polysiloxane (Dreve) so that the dentin and plastic were in one plane. The tooth surfaces were ground with abrasive paper (grit 400), then rinsed with warm water and pre-tempered to 37°C. The dentin surfaces were blotted dry, and the catalyst pastes were mixed with the corresponding base pastes in a 1:1 ratio and then applied to the tooth surfaces. Simultaneously, the underside of a plug made of hardened dental composite material (Tetric Evo-Ceram, Ivoclar Vivadent AG) was wetted with cement and centered on the dentin surface. The tooth was then clamped with the composite plug facing upward in an Ultradent clamping device, with the fixed mandrel centered on the Tetric Evo-Ceram plug. Excess luting cement was then carefully removed immediately, and the Ultradent attachment device with the clamped tooth was stored in a drying cabinet at 37°C for 15 minutes. The plug was then loosened and placed in water at 37°C for 24 hours, then stored in a drying cabinet at 37°C for 24 hours. To measure shear bond strength, the plug was sheared at 23°C using a Zwick testing machine according to the Ultradent method (EN ISO 29022, 2013). The shear bond strength was calculated as the quotient of the breaking load and the bond area.

[0096] An initial dentin bond strength value of 12.0 MPa was determined for a cement according to the invention consisting of Base Paste 1 and Catalyst Paste 1. After two weeks of storing the paste at room temperature, the value was 10.3 MPa. In contrast, a cement containing untreated filler consisting of Base Paste 2 and Catalyst Paste 2 gave an initial value of only 1.9 MPa, which dropped to a value of 0 MPa after two weeks of storage at room temperature. Table 1: Composition of the base paste (data in wt. %) [Table 1] *)Comparative example 1 Phase transfer catalyst 2 TEMPO: 2,2,6,6-tetramethylpiperidinyloxy, CAS number 2564-83-2 3 24 wt% Al2O3, 23 wt% SiO2, 16.5 wt% CaO, 16 wt% CaF2, 11.5 wt% BaO, 8 wt% P2O5, 2 wt% Na2O, 5% silane; weight average particle size 7 μm (Schott AG, Mainz) 4 24 wt% Al2O3, 23 wt% SiO2, 16.5 wt% CaO, 16 wt% CaF2, 11.5 wt% BaO, 8 wt% P2O5, 2 wt% Na2O, 5% silane; weight average particle size 1 μm (Schott AG, Mainz) 5 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 to non-silanized silica: 25% (Wacker Chemie AG) 6. 2,5-Dihydroxyterephthalic acid diethyl ester (Riedel-de Haen AG) Table 2: Composition of catalyst paste (data in wt.%) [Table 2] *) Comparative example 1 See Example 2

[0097] Example 4 Examination of the Transparency of the Composite of Example 3 After complete hardening, the transparency of Composite 1, consisting of Catalyst Paste 1 and Base Paste 1, was measured on 1 mm thick specimens polished to high brightness in transmission using a spectrophotometer (Konika-Minolta Spectrophotometer CM-5). The transparency was 19.2%. The transparency value of Composite Cement 1 is significantly higher than that of classic glass ionomer cements such as Vivaglass CEM PL (Ivoclar Vivadent AG), which has a transparency value of 6.7%.

[0098] Example 5 Investigation of storage stability of composites based on radiopaque glass fillers (with and without acid treatment)

[0099] Experimental radiopaque glass fillers (average particle size 3 μm; composition (wt%): Al2O3:6; BO3:5; Na2O:8; CaO, BaO, KO:2-3 each; CaF2, MgO:1 each; and SiO2:70) were treated with acid and silanized as described in Example 1. For comparison purposes, some of the fillers were silanized without prior acid treatment. In the acid treatment solution, mainly Al, Ba, Ca, Na, and K ions were detected by XRF analysis. Both acid-treated and untreated fillers were used to produce a composite paste with the following composition (wt%): filler: 65.00, MDP: 3.29, TEGDMA: 8.53, NK-ester 9G: 1.90, V-392: 11.68, BHT: 0.03, deionized water: 5.58, and pyrogenic silica HDK 2000 (Wacker Chemie AG): 4.00.

[0100] Pastes containing acid-treated and untreated fillers were stored at room temperature, and the MDP content was determined by HPLC at intervals of several weeks, as in Example 2. The results are shown in Figure 2. The results shown in Figure 2 demonstrate the significantly improved storage stability of pastes based on acid-treated fillers. A clear decrease in MDP content was observed after two weeks in pastes containing untreated fillers, whereas no decrease in MDP content was observed in pastes containing acid-treated fillers, even after eight weeks. The results indicate that acid treatment of fillers significantly improves storage stability.

Claims

1. A radically polymerizable composition comprising at least one radically polymerizable monomer having no acid group, at least one radically polymerizable monomer having an acid group, at least one fluoroaluminosilicate glass filler and / or a radiopaque glass filler, and at least one radical polymerization initiator, wherein the fluoroaluminosilicate glass filler and / or the glass filler has been acid washed.

2. Composition (wt%) 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 a value of 0 to 10; and / or 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 10. The composition of claim 1, comprising 5 to 20 weight percent of a fluoroaluminosilicate glass filler, all values ​​being based on the total mass of the glass and all components except fluorine being calculated as oxides.

3. The composition of claim 2 , wherein the fluoroaluminosilicate glass filler or glass filler has been washed with hydrochloric acid, nitric acid, formic acid, and / or acetic acid.

4. In each case relative to the total weight of the composition, a) 10 to 80% by weight, preferably 20 to 75% by weight, particularly preferably 30 to 70% by weight, of at least one acid-washed fluoroaluminosilicate glass filler and / or glass filler, b) optionally 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more further fillers, 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) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer having no acid groups, e) 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, f) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers having no acid groups, g) 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, h) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and i) 0.01 to 5% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.1 to 2% by weight, of one or more additives The composition of any one of claims 1 to 3, comprising:

5. Examples of radically polymerizable monomers without an acid group include bisphenol A-dimethacrylate, bis-GMA (an addition product of methacrylic acid and bisphenol A-diglycidyl ether), ethoxylated or propoxylated bisphenol A-dimethacrylate, for example bisphenol A-dimethacrylate or 2,2-bis[4-(2-methacryloyloxypropoxy)phenyl]propane having three ethoxy groups, UDMA (2-hydroxyethyl methacrylate and 2,2,4-trimethylhexamethylene-1,6-diisocyanate), addition products of ethylene glycol di(meth)acrylate), 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 ]decane (DCP), polyethylene glycol or polypropylene glycol dimethacrylate, for example polyethylene glycol 200-dimethacrylate (PEG-200-DMA) or polyethylene glycol 400-dimethacrylate (PEG-400-DMA), 1,12-dodecanediol dimethacrylate, urethanes of 2-(hydroxymethyl)acrylic acid with diisocyanates, for example urethanes of 2,2,4-trimethylhexamethylene diisocyanate or isophorone diisocyanate, pyrrolidine diisocyanate, 4. The composition of claim 1, further comprising at least one polyfunctional monomer selected from the group consisting of 1,6-bis(3-vinyl-2-pyrrolidonyl)-hexane, bisacrylamides such as methylene or ethylene bisacrylamide, 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, and mixtures thereof.

6. The composition according to any one of claims 1 to 3, comprising, as an acid group-containing monomer, at least one monomer having a pKa at room temperature of 0.5 to 4.0, more preferably 1.0 to 3.5, and most preferably 1.5 to 2.

5.

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 dimethacrylate dihydrogen phosphate, 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 4-(meth)acryloyloxyethyltrimellitic anhydride, 10-methacryloyloxydecylmalonic acid, N-(2-hydroxy-3-methacryloyloxypropyl)-N-phenylglycine, and / or 4-vinylbenzoic acid.

8. 5. The composition according to claim 4, comprising as oligomeric carboxylic acid 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. 4. The composition according to claim 1, comprising, as a free-radically polymerizable monomer having no acid group, at least one monofunctional monomer selected from the group consisting of benzyl, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, p-cumyl-phenoxyethylene glycol methacrylate (CMP-1E), 2-([1,1'-biphenyl]-2-oxy)ethyl methacrylate (MA-836), tricyclodecanemethyl (meth)acrylate, 2-(2-biphenyloxy)ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxyethylpropyl (meth)acrylate, 2-acetoxyethyl methacrylate, and mixtures thereof.

10. a catalyst paste and a base paste, the catalyst paste comprising in each case, relative to the total mass of the catalyst paste: a) 10 to 80% by weight, preferably 20 to 75% by weight, particularly preferably 30 to 70% by weight, of at least one acid-treated FAS and / or glass filler, b) 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more further fillers, 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) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer having no acid groups, e) 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, f) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers, g) 0.01 to 16% by weight, preferably 0.2 to 12% by weight, particularly preferably 0.5 to 10% by weight, of at least one peroxide and / or hydroperoxide and optionally at least one photoinitiator, h) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and i) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.0051 to 2% by weight, of one or more additives Including, The base paste comprises, in each case relative to the total mass of the base paste: a) 10 to 80% by weight, preferably 20 to 75% by weight, particularly preferably 30 to 70% by weight, of at least one acid-treated FAS and / or glass filler, b) 0.1 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of one or more further fillers, d) 5 to 40% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 25% by weight, of at least one polyfunctional monomer having no acid groups, f) 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight, of one or more monofunctional monomers having no acid groups, g) 0.01 to 16% by weight, preferably 0.3 to 12% by weight, particularly preferably 1 to 10% by weight, of at least one suitable reducing agent and, if necessary, at least one photoinitiator; h) 0 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 1 to 7% by weight, of water, and i) 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.0051 to 2% by weight, of one or more additives The composition of claim 4 comprising:

11. 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 material or veneering material, restorative composite or luting cement.

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

13. 1. A method for treating a fluoroaluminosilicate glass filler or glass filler with an acid, comprising: (i) the fluoroaluminosilicate glass filler or glass filler is dispersed in an aqueous solution of an organic and / or inorganic acid, preferably hydrochloric acid, nitric acid, formic acid, and / or acetic acid, the acid solution preferably having an acid concentration of 0.1 to 5 mol / l, particularly preferably 0.5 to 3 mol / l; (ii) the dispersion is stirred for preferably 0.5 to 24 hours, more preferably 1 to 5 hours; (iii) the filler is then separated and washed with deionized water; (iv) the filler is separated and dried.

14. 14. The method of claim 13, wherein in step (iii), the filler is dispersed in deionized water and then the dispersion is stirred for 1 to 60 minutes, preferably 2 to 20 minutes, and this process is preferably repeated 1 to 5 times, more preferably 3 times.

15. 15. Use of a fluoroaluminosilicate glass filler or glass filler preparable according to claim 13 or 14 for stabilizing a dental radically polymerizable composition.

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