Sulphate-containing or phosphate-containing self-adhesive dental composite cement with good transparency

Abstract

To provide sulphate-containing or phosphate-containing self-adhesive dental composite cements with good transparency.SOLUTION: A radical polymerizable composition has at least one acidic radical polymerizable monomer, at least one fluoroaluminosilicate glass filler and / or radiopaque glass filler, and at least one water-soluble sulfate and / or phosphate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to storage-stable, radically polymerizable, self-adhesive composites with improved transparency that are particularly suitable as dental materials, e.g. as dental cements, filling composites, or veneering materials, and for the production of inlays, onlays, or crowns. [Background technology]

[0002] Composites are primarily used in dentistry for the fabrication of direct and indirect filling materials, i.e., as direct and indirect filling composites and as cements. The polymerizable organic matrix of the 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]-2,2,4-trimethylhexane (UDMA), which have high viscosity and provide the polymer with 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]dimethacrylate are 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, leading to a decrease in network density and increased double bond conversion.

[0003] To produce self-adhesive composites, strongly acidic adhesive monomers such as 10-methacryloyloxydecyl dihydrogen phosphate (MDP) are used to etch tooth structure and cause bonding to enamel / dentin through ionic relationships. The adhesive monomers impart self-adhesive properties to the composites, thus allowing them to be used without pretreatment of tooth structure with enamel / dentin adhesives, making their use particularly attractive.

[0004] In addition to the organic matrix, composites contain one or more fillers, 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] The problem is that acidic adhesive monomers often interact adversely with fillers. For example, they bind 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 the adhesive monomer concentration in the resin matrix, which is also associated with a reduction or loss of adhesive properties. Therefore, composites containing acidic adhesive monomers have very limited storage stability.

[0006] Methacrylate-based dental materials cure by radical polymerization using radical photoinitiators, thermal initiators, or redox initiator systems, depending on the field of 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) with 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, 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 initiator, materials based on redox initiator systems are usually used as so-called two-component (2C) systems, in which the oxidizing agent (peroxide or hydroperoxide) and the reducing agent (amine, sulfinic acid, barbiturate, thiourea, etc.) are incorporated into separate components, which are mixed together immediately before use. For mixing, a double-push syringe with separate cylindrical chambers holding the components is preferably used. The components are simultaneously pushed out of the chambers by two interconnected pistons and mixed together in a nozzle. To obtain as homogeneous a mixture 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 much more difficult. Furthermore, glass ionomer cements have low transparency and relatively poor mechanical properties. German Patent Application Publication No. 10021605 discloses a dental filling material based on an epoxy resin containing an ammonium salt, such as ammonium sulfate or ammonium hydrogen sulfate, in combination with a basic calcium salt. Preferred calcium salts are calcium oxide and calcium hydroxide. Upon contact with moisture, the ammonium salt reacts with the basic calcium salt to form ammonia, hardening the epoxy resin. Plaster of stone is also formed, which is said to improve marginal sealing of dental and root canal fillings by expanding during crystallization. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] DE 10021605 Summary of the Invention [Means for solving the problem]

[0011] It is an object of the present invention to provide a shelf-stable, self-adhesive dental composite with good transparency and good mechanical properties, which can be mixed and applied satisfactorily as a two-component system using a double-push syringe, and which is particularly suitable as a dental luting cement.

[0012] This object is achieved 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 sulfate and / or phosphate salt that is water soluble at 20° C. Surprisingly, it has been found that the water-soluble sulfate or phosphate salt in combination with at least one fluoroaluminosilicate glass filler and / or radiopaque glass filler results in a significant increase in the storage stability of compositions containing acidic monomers. The present application provides, for example, the following items: (Reclaim) (Item 1) A radically polymerizable composition comprising at least one acidic radically polymerizable monomer and at least one fluoroaluminosilicate glass filler and / or radiopaque glass filler, and further comprising at least one water-soluble sulfate and / or phosphate salt. (Item 2) 10. The composition according to claim 1, comprising, as a water-soluble sulfate salt, at least one inorganic salt of sulfuric acid having a water solubility of at least 100 g / l, preferably from 110 to 1,000 g / l at 20°C, and / or, as a water-soluble phosphate salt, at least one inorganic salt of orthophosphoric acid having a water solubility of at least 100 g / l, preferably from 110 to 1,000 g / l at 20°C. (Item 3) The composition according to any one of the preceding items, comprising as a water-soluble sulfate salt potassium sulfate, sodium sulfate, ammonium sulfate, or a mixture thereof, and / or as a water-soluble phosphate salt potassium phosphate, sodium phosphate, ammonium phosphate, or a mixture thereof. (Item 4) 10. The composition according to any one of the preceding items, comprising from 0.3 to 9.0 wt. %, preferably from 0.4 to 6.0 wt. %, particularly preferably from 0.7 to 4.0 wt. % of at least one water-soluble sulfate and / or phosphate salt, relative to the total weight of the composition. (Item 5) 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 having no 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 having 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 - 0.3 to 9% by weight, preferably 0.4 to 6% by weight, particularly preferably 0.7 to 4.0% by weight, of at least one water-soluble sulfate and / or phosphate salt Item 10. The composition of any one of the preceding items, comprising: (Item 6) in each case relative to the total weight of the composition, a) 0.3 to 9% by weight, preferably 0.4 to 6% by weight, particularly preferably 0.7 to 4.0% by weight, of at least one water-soluble sulfate and / or phosphate, b) 5 to 40% by weight, preferably 8 to 35% by weight, particularly preferably 10 to 30% by weight, of at least one polyfunctional monomer having no 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 radically polymerizable monomer containing acid groups, d) 0 to 10% by weight, preferably 0 to 8% by weight, particularly preferably 0 to 5% by weight, of one or more oligomeric carboxylic acids, e) optionally 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight, of one or more monofunctional monomers having no 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 and / or radiopaque glass filler, g) optionally 1 to 50% by weight, preferably 1.5 to 40% by weight, particularly preferably 2 to 30% by weight, of one or more additional fillers, h) 0.1 to 8% by weight, preferably 0.5 to 6%, 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) 0.01 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 7) 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 8) 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 9) Item 10. The composition according to any one of the preceding items, comprising at least one oligomeric carboxylic acid (d) selected from polyacrylic acids 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 10) The composition of any one of the preceding items, comprising at least one monofunctional monomer (e) 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 11) Composition (wt%): 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; or a fluoroaluminosilicate glass filler having the composition (by weight): 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; 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, all figures being based on the total weight of the glass and all constituents except fluorine being calculated as oxides. (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) 0.3 to 9% by weight, preferably 0.4 to 6% by weight, particularly preferably 0.7 to 4.0% by weight, of at least one water-soluble sulfate and / or phosphate, b) 5 to 40% by weight, preferably 8 to 35% by weight, particularly preferably 10 to 30% by weight, of at least one polyfunctional monomer having no acid groups, c) 2 to a maximum of 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 to 20% by weight, preferably 0 to 16% by weight, particularly preferably 0 to 10% by weight, of one or more oligomeric carboxylic acids, e) optionally 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight, of one or more monofunctional monomers having no 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 and / or glass filler, g) optionally 1 to 50% by weight, preferably 1.5 to 40% by weight, particularly preferably 2 to 30% 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 0.03 to 3% by weight, particularly preferably 0.05 to 2% by weight, of one or more additives, 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 35% by weight, particularly preferably 10 to 30% by weight, of at least one polyfunctional monomer having no acid groups, c) Not applicable; d) Not applicable; e) optionally 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight, of one or more monofunctional monomers having no 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 and / or glass filler, g) optionally 1 to 50% by weight, preferably 1.5 to 40% by weight, particularly preferably 2 to 30% 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) containing from 0.001 to 5% by weight, preferably from 0.03 to 3% by weight, particularly preferably from 0.05 to 2% by weight, of one or more additives; 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 material, 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

[0013] 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 radiopaque glass filler, and at least one water-soluble sulfate and / or phosphate salt.

[0014] According to the present invention, preferred sulfates are inorganic salts of sulfuric acid, and preferred phosphates are inorganic salts of orthophosphoric acid (H3PO4). The water-soluble sulfates or phosphates are preferably those having a water solubility of at least 100 g / L, preferably 110 to 1,000 g / L, and particularly preferably 150 to 800 g / L. Preferred water-soluble sulfates are potassium sulfate (K2SO4; water solubility 111 g / L), sodium sulfate (Na2SO4; water solubility 170 g / L), and particularly preferred ammonium sulfate ((NH4)2SO4; water solubility 754 g / L). Preferred water-soluble phosphates are potassium phosphate (K3PO4; water solubility 508 g / L), sodium phosphate (Na3PO4; water solubility 285 g / L), and particularly preferred ammonium phosphate ((NH4)3PO4; water solubility 580 g / L). All solubility data refer to solubility in water at 20°C.

[0015] The one or more water-soluble sulfates and / or water-soluble phosphates are preferably added in a total amount of at least 0.3% by weight, particularly at least 0.4% by weight. According to the present invention, a composition containing at most 0.3 to 9.0% by weight, more preferably 0.4 to 6.0% by weight, and most preferably 0.7 to 4.0% by weight of at least one water-soluble sulfate and / or phosphate is preferred. Unless otherwise specified, all percentages herein are based on the total weight of the composition. The sulfate or phosphate may be present in dissolved or, preferably, solid form. According to the present invention, sulfate is preferred.

[0016] The composition according to the present invention contains at least one radically polymerizable monomer, preferably one or more monofunctional and / or polyfunctional monomers. A polyfunctional monomer is understood to be a compound having two or more, preferably two to four, particularly preferably two radically polymerizable groups. Thus, a monofunctional monomer has 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.

[0017] According to the invention, a distinction is made between monomers containing acid groups and monomers not containing acid groups. The compositions according to the invention contain at least one monomer not containing acid groups and at least one monomer and / or oligomer containing acid groups. According to the invention, compositions are preferred which contain the monomers containing acid groups and the monomers not containing acid groups in a weight ratio of 1:5 to 1:36, particularly preferably 1:6 to 1:25, most preferably 1:7 to 1:20. Monomers without acid groups

[0018] 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.

[0019] 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.

[0020] 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 having at least one radically polymerizable group and at least one functional group, preferably a hydroxyl group. Preferred functionalized mono(meth)acrylates are 2-hydroxyethyl- and hydroxyethylpropyl (methacrylate), as well as 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.

[0021] 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-dimethacrylates, such as bisphenol-A dimethacrylate SR-348c (Sartomer) having three ethoxy groups or 2,2-bis[4-(2-methacryloyloxypropoxy)phenyl]propane, urethanes of 2-(hydroxymethyl)acrylic acid with diisocyanates, such as urethanes with 2,2,4-trimethylhexamethylene diisocyanate or isophorone diisocyanate, UDMA (2-hydroxyethyl acrylate), addition products of methacrylate and 2,2,4-trimethylhexamethylene-1,6-diisocyanate), tetramethylxylylenediurethane ethylene glycol di(meth)acrylate or tetramethylxylylenediurethane-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.

[0022] The monomer tetramethylxylylenediurethane ethylene glycol di(meth)acrylate or tetramethylxylylenediurethane 2-methylethylene glycol diurethane di(meth)acrylate (V380) has the following formula: [ka] It has.

[0023] In the formula shown, each R radical is 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, or molecules in which one radical is H and the other radical is CH3, with the ratio of H to CH3 preferably being 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.

[0024] Other preferred bifunctional monomers are 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. Monomers and oligomers containing acid groups

[0025] The composition according to the present invention contains at least one acidic radically polymerizable monomer. The acidic radically polymerizable monomer is a monomer that contains, in addition to at least one radically polymerizable group, at least one acid group, preferably a phosphate ester, phosphonic acid, or carboxyl group, particularly preferably at least one phosphate ester group. The acidic monomer is also referred to herein as an adhesive component or adhesive monomer. Adhesive monomers that contain at least one (meth)acrylate, particularly a methacrylate group, as a radically polymerizable group are preferred.

[0026] Preferred monomers containing at least one acid group are phosphate esters and phosphonate monomers. 2-methacryloyloxyethylphenyl hydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate (MDP), glycerol dihydrogen phosphate dimethacrylate, or dipentaerythritol pentamethacryloyloxyphosphate, 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 dimethacrylate are particularly preferred.

[0027] Other preferred monomers containing an acid group are polymerizable monomers containing at least one COOH group, with 4-(meth)acryloyloxyethyltrimellitic anhydride, 10-methacryloyloxydecylmalonic acid, N-(2-hydroxy-3-methacryloyloxypropyl)-N-phenylglycine, and 4-vinylbenzoic acid being particularly preferred.

[0028] According to a further preferred embodiment, the composition according to the invention further comprises at least one acidic radically polymerizable oligomer, the oligomer having a degree of polymerization P n from 2 to 100 (P n =M n / M u ;Mn : number average polymer molar mass, M u It is understood that the acidic radically polymerizable oligomer is a polymer having at least one acid group, preferably a carboxyl group, and at least one radically polymerizable group, preferably a (meth)acrylate group, in particular a methacrylate group.

[0029] Preferred acid group-containing oligomers according to the present invention are oligomeric carboxylic acids, e.g., preferably having a number average molecular weight M n polyacrylic acid having a M of less than 7,200 g / mol, preferably less than 7,000 g / mol, particularly preferably less than 6,800 g / mol, n is preferably in the range of 800 to 7,200 g / mol, more preferably 500 to 7,000 g / mol, and most particularly 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.

[0030] 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 via 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, or more precisely, their hydrodynamic volume. Absolute molar masses are determined by calibration with known standards.

[0031] 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 on dentin and enamel.

[0032] 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 its derivatives, α-diketones and their derivatives, such as 9,10-phenanthrenequinone, 1-phenyl-propane-1,2-dione, diacetyl, and 4,4'-dichlorobenzyl. Camphorquinone (CQ) and 2,2-dimethoxy-2-phenyl-acetophenone are particularly preferred, and α-diketones are most preferably used in combination with amines, such as ethyl 4-(dimethylamino)benzoate (EDMAB), N,N-dimethylaminoethyl methacrylate, N,N-dimethyl-sym.-xylidine, or triethanolamine, as reducing agents. Norrish Type I photoinitiators are more preferred, especially acyl or bisacylphosphine oxides, and most preferably monoacyltrialkyl, diacyldialkylgermanium, and tetraacylgermanium compounds, such as benzoyltrimethylgermane, dibenzoyldiethylgermane, bis(4-methoxybenzoyl)diethylgermane (Ivoserin®), tetrabenzoylgermane, or tetrakis(o-methylbenzoyl)germane. 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-dimethylaminobenzoic acid ethyl ester.

[0033] 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. The preferred oxidizing agent is a peroxide, particularly a hydroperoxide. A particularly preferred peroxide is benzoyl peroxide. Preferred hydroperoxides are the low-odor cumene hydroperoxide derivatives disclosed in EP 3 692 976 A1, the oligomeric CHP derivatives disclosed in EP 21315089.9, particularly 4-(2-hydroperoxypropan-2-yl)phenylpropionate, and cumene hydroperoxide (CHP).

[0034] 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.

[0035] Preferred reducing agents for combination with hydroperoxides are thiourea derivatives, in particular 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. Furthermore, one or more of the aforementioned thiourea derivatives can be advantageously used in combination with one or more imidazoles. Preferred imidazoles are 2-mercapto-1-methylimidazole or 2-mercaptobenzimidazole.

[0036] According to a preferred embodiment, the composition according to the present invention may further comprise, in addition to at least one hydroperoxide and at least one thiourea derivative, at least one transition metal compound for accelerating curing. Preferred transition metal compounds according to the present invention are 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 cause discoloration of the dental material. Due to their good monomer solubility, transition metals are preferably used in the form of their acetylacetonate, 2-ethylhexanoate, or THF adduct. Further preferred are their 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 invention is a mixture of cumene hydroperoxide (CHP) with at least one of the above-mentioned thiourea derivatives and copper(II) acetylacetonate.

[0037] 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.

[0038] 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.

[0039] 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 and / 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.

[0040] 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.

[0041] All data refer to the total mass of the glass, and all constituents other than fluorine are calculated as oxides, as is common in glasses and glass-ceramics.

[0042] 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.

[0043] 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 fillers, in each case relative to the total weight of the composition.

[0044] In addition to the aforementioned FAS and radiopaque glass fillers, compositions according to the present invention may contain additional fillers.

[0045] 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.

[0046] 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 powder 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. These fillers are preferably used in an amount of 0.1 to 40 wt. %, more preferably 0.2 to 35 wt. %, and very particularly preferably 0.3 to 25 wt. %, in each case based on the total mass of the composition.

[0047] Furthermore, so-called composite fillers are preferred as additional fillers. These are also called isofillers. These are splinter-like polymers containing fillers, preferably pyrogenic SiO2 and / or ytterbium trifluoride. 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.

[0048] A preferred composite filler according to the present invention can be prepared, for example, by heat curing a mixture of bis-GMA (8.80 wt%), UDMA (6.60 wt%), 1,10-decanediol dimethacrylate (5.93 wt%), dibenzoyl peroxide + 2,6-di-tert-butyl-4-methylphenol (0.67 wt% combined), 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.

[0049] So-called inert fillers can also be used as further fillers.These are glass fillers whose surface is coated with, for example, a sol-gel-based diffusion barrier layer or with a polymer layer, for example, PVC.Preferred fillers are those described in EP 2 103 296 A1.

[0050] 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.

[0051] The composition according to the invention preferably contains from 1 to 50% by weight, more preferably from 1.5 to 40% by weight, most preferably from 2 to 30% by weight of one or more further fillers, preferably one or more metal oxides, pyrogenic silica, and / or precipitated silica, in each case relative to the total weight of the composition.

[0052] Unless otherwise stated, all particle sizes in this specification are the volume average particle size (D50 value), i.e., 50% of the total volume common to all particles is contained in particles having a diameter smaller than the stated value. Thus, the D10 value is the volume diameter at which 10% of the total filler volume is smaller than the specified value.

[0053] Particle size determination 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). In this case, 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 operation, and the measurement 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 to calculate 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 at a wavelength of 633 nm, a scattering angle of 90°, and 25°C with a He-Ne laser, for example a Malvern Zetasizer Nano ZS (Malvern Instruments, Malvern UK).

[0054] For agglomerates and aggregates, the primary particle size can be determined from TEM images. Transmission electron microscopy (TEM) is preferably performed on a Philips CM30 TEM using an accelerating voltage of 300 kV. To prepare the sample, a droplet of the particle dispersion is deposited on a 50 Å thick carbon-coated copper grid (mesh size 300 mesh), followed by evaporation of the solvent. The particles are counted and the arithmetic mean is calculated.

[0055] The compositions according to the invention may also contain additional additives, in particular stabilizers, colorants, phase transfer catalysts, bactericides, fluoride ion-donating additives such as fluoride salts, in particular NaF or ammonium fluoride, or fluorosilanes, optical brighteners, plasticizers, and / or UV absorbers.

[0056] Preferably, the composition according to the invention comprises: 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 having no 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 having acid groups, - 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 - 0.3 to 9% by weight, preferably 0.4 to 6% by weight, particularly preferably 0.7 to 4.0% by weight, of at least one water-soluble sulfate and / or phosphate salt Includes.

[0057] Unless otherwise stated, all percentages herein refer to the total weight of the composition. All amounts relating to radically polymerizable monomers (polyfunctional and monofunctional) refer only to monomers without acid groups and do not include monomers containing acid groups.

[0058] 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 necessary, reducing agents, transition metal compounds, 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.

[0059] 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) 0.3 to 9% by weight, preferably 0.4 to 6% by weight, particularly preferably 0.7 to 4.0% by weight, of at least one water-soluble sulfate and / or phosphate, b) 5 to 40% by weight, preferably 8 to 35% by weight, particularly preferably 10 to 30% by weight, of at least one polyfunctional monomer having no 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 radically polymerizable monomer having an acid group, d) 0 to 10% by weight, preferably 0 to 8% by weight, particularly preferably 0 to 5% by weight, of one or more oligomeric carboxylic acids, e) optionally 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight, of one or more monofunctional monomers having no 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) optionally 1 to 50% by weight, preferably 1.5 to 40% by weight, particularly preferably 2 to 30% 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 at least one 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) 0.01 to 5% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.1 to 2% by weight, of one or more additives.

[0060] Compositions containing redox initiators are also called 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, while the second component, the so-called base plate, 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 called dual-curing.

[0061] In two-component compositions, the water-soluble sulfate and / or phosphate salts are preferably added to the component containing the strongly acidic adhesive monomer, the FAS filler, and / or the radiopaque glass filler.

[0062] According to the present 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.

[0063] The catalyst paste preferably has the following composition, in each case based on the total mass of the catalyst paste: a) 0.3 to 9% by weight, preferably 0.4 to 6% by weight, particularly preferably 0.7 to 4.0% by weight, of at least one water-soluble sulfate and / or phosphate, b) 5 to 40% by weight, preferably 8 to 35% by weight, particularly preferably 10 to 30% by weight, of at least one polyfunctional monomer, 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 to 20% by weight, preferably 0 to 16% by weight, particularly preferably 0 to 10% by weight, of one or more oligomeric carboxylic acids, e) optionally 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight, of one or more monofunctional monomers, f) 25 to 80% by weight, preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight, of at least one FAS and / or glass filler, g) optionally 1 to 50% by weight, preferably 1.5 to 40% by weight, particularly preferably 2 to 30% 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 0.03 to 3% by weight, particularly preferably 0.05 to 2% by weight, of one or more additives.

[0064] The base paste preferably has the following composition, in each case based on the total mass of the base paste: a) Not applicable; b) 5 to 40% by weight, preferably 8 to 35% by weight, particularly preferably 10 to 30% by weight, of at least one polyfunctional monomer, c) Not applicable; d) Not applicable; e) optionally 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight, of one or more monofunctional monomers, f) 25 to 80% by weight, preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight, of at least one FAS and / or glass filler, g) optionally 1 to 50% by weight, preferably 1.5 to 40% by weight, particularly preferably 2 to 30% 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 0.03 to 3% by weight, particularly preferably 0.05 to 2% of one or more additives.

[0065] For application, the catalyst and base paste are preferably mixed together in approximately equal proportions and are therefore particularly suitable for application by double-push syringe.

[0066] 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 and preferably forced 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 improves syringe handling.

[0067] 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 (therapeutic use) by dentists to repair damaged teeth, especially as dental cements, coating materials, or veneer materials, filling composites, especially as luting cements.Transparency is determined by the method described in the examples.

[0068] 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.Then, when, for example, repairing a dental cavity, the composition can be directly hardened, preferably by irradiating with light of an appropriate wavelength.Alternatively, dental restorations, such as inlays, onlays, veneers, crowns, bridges, frameworks, or dental ceramics, are placed inside or applied to the surface of the prepared tooth.The subsequent hardening of the composition is preferably carried out by light and / or self-hardening.Dental restorations are attached to the tooth in this process.

[0069] The compositions according to the invention can also be used as extraoral materials (non-therapeutic), for example for the fabrication or repair of dental restorations. They are also suitable as materials for the fabrication and repair of inlays, onlays, crowns or bridges.

[0070] 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, through self-hardening or preferably by heat.

[0071] In the repair of dental restorations, the composition according to the invention is placed on the restoration to be repaired, for example to repair gaps or to join fragments, and then allowed to harden.

[0072] The invention will be explained in more detail below with reference to figures and example embodiments. [Brief explanation of the drawings]

[0073] [Figure 1] FIG. 1 shows the decrease in the concentration of the acidic monomer MDP as a function of storage time in composite pastes with (--triangles--; --diamonds--) and without ammonium sulfate (--squares--). [Example]

[0074] Example 1 Investigation of the storage stability of self-adhesive composites with and without ammonium sulfate

[0075] Composite pastes C-1 to C-3 with the compositions shown in Table 1 (all data in wt.%) were prepared from the following constituents: glass filler GM27884, silanized (Schott AG; average particle size 1 μm; specific surface area (BET DIN ISO 9277) 3.9 m 2 / g; composition (wt%): Al2O3:10, B2O3:10, BaO:25, and SiO2:55), pyrogenic silica HDK2000 (Wacker Chemie AG; BET surface area 120 m 2 / g), 10-methacryloyloxydecyl dihydrogen phosphate (MDP, Orgentis), triethylene glycol dimethacrylate (TEGDMA), NK Ester 9G (polyethyleneglyco-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), and ammonium sulfate (NH4)2SO4 (Aldrich). [Table 1] * ) Comparative Example

[0076] Pastes C-1 (without (NH4)2SO4), C-2 (1.41% (NH4)2SO4), and C-3 (0.456% (NH4)2SO4) were stored at room temperature for 16 weeks, and the MDP content was 31 Repeated determination was made by P-NMR spectroscopy. 31For P-NMR measurements, 1.5 g of each sample to be analyzed was weighed into a centrifuge tube and mixed with 1.5 ml of a solution of 0.1 g of triphenylphosphine in 10 ml of deuterated acetone (acetone-d6) as an internal standard. The resulting suspension was shaken for at least 5 minutes using a platform shaker (Vibramax, Heidolph Instruments GmbH & Co. KG, Schwabach, Germany) and then centrifuged at 3,500 rpm for 15 minutes. The supernatant was transferred to an NMR sample tube using a disposable pipette. Measurements were performed using an Avance DPX400 (Bruker Spectrospin) 400 MHz nuclear magnetic resonance spectrometer. The MDP concentration was calculated from the peak area ratio relative to the internal standard. Figure 1 shows the change over time in the MDP content in composite pastes with and without (NH4)2SO4.

[0077] The results, shown in Figure 1, demonstrate the significantly improved storage stability of composites C-2 and C-3 containing (NH4)2SO4. Composite C-1 without (NH4)2SO4 showed a near complete reduction in available MDP after only 10 weeks, while in composite pastes C-2 and C-3 containing (NH4)2SO4, adequate contents of MDP were still detectable after 16 weeks.

Claims

1. 1. A radically polymerizable composition comprising at least one acidic radically polymerizable monomer and at least one fluoroaluminosilicate glass filler and / or radiopaque glass filler, and further comprising at least one water-soluble sulfate and / or phosphate salt.

2. 2. The composition according to claim 1, comprising, as water-soluble sulfate salt, at least one inorganic salt of sulfuric acid having a water solubility of at least 100 g / l, preferably from 110 to 1,000 g / l at 20°C, and / or, as water-soluble phosphate salt, at least one inorganic salt of orthophosphoric acid having a water solubility of at least 100 g / l, preferably from 110 to 1,000 g / l at 20°C.

3. The composition according to claim 1, comprising as a water-soluble sulfate salt potassium sulfate, sodium sulfate, ammonium sulfate, or a mixture thereof, and / or as a water-soluble phosphate salt potassium phosphate, sodium phosphate, ammonium phosphate, or a mixture thereof.

4. 4. The composition according to claim 1, comprising from 0.3 to 9.0% by weight, preferably from 0.4 to 6.0% by weight, particularly preferably from 0.7 to 4.0% by weight, of at least one water-soluble sulfate and / or phosphate salt, relative to the total weight of the composition.

5. 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 having no acid groups, from 1 to 15% by weight, preferably from 2 to 12% by weight, particularly preferably from 3 to 10% by weight, of at least one radically polymerizable monomer having an acid group, 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 - 0.3 to 9% by weight, preferably 0.4 to 6% by weight, particularly preferably 0.7 to 4.0% by weight, of at least one water-soluble sulfate and / or phosphate salt The composition of claim 4 comprising:

6. in each case relative to the total weight of the composition, a) 0.3 to 9% by weight, preferably 0.4 to 6% by weight, particularly preferably 0.7 to 4.0% by weight, of at least one water-soluble sulfate and / or phosphate, b) 5 to 40% by weight, preferably 8 to 35% by weight, particularly preferably 10 to 30% by weight, of at least one polyfunctional monomer having no 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 radically polymerizable monomer containing acid groups, d) 0 to 10% by weight, preferably 0 to 8% by weight, particularly preferably 0 to 5% by weight, of one or more oligomeric carboxylic acids, e) optionally 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight, of one or more monofunctional monomers having no 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) optionally 1 to 50% by weight, preferably 1.5 to 40% by weight, particularly preferably 2 to 30% by weight, of one or more additional fillers; h) 0.1 to 8% by weight, preferably 0.5 to 6%, 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) 0.01 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 claim 5 comprising:

7. 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 methyl acrylate), and the like. addition products of ethylene glycol di(meth)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 6, comprising at least one monomer selected from 1,3-dimethyl-2,4-diol (DMSO), 1,3-dimethyl-2,4-diol (DMSO), 1,4 ...

8. 7. The composition according to claim 6, 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.

9. 7. The composition according to claim 6, comprising at least one oligomeric carboxylic acid (d) selected from polyacrylic acids 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.

10. 7. The composition of claim 6, comprising at least one monofunctional monomer (e) 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.

11. 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: 0-10; 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 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; 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 4. The composition of claim 1, further comprising a fluoroaluminosilicate glass filler having a % fluorine content of 5 to 20, all values ​​being relative to the total weight of the glass and all components other than fluorine being calculated as oxides.

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) 0.3 to 9% by weight, preferably 0.4 to 6% by weight, particularly preferably 0.7 to 4.0% by weight, of at least one water-soluble sulfate and / or phosphate, b) 5 to 40% by weight, preferably 8 to 35% by weight, particularly preferably 10 to 30% by weight, of at least one polyfunctional monomer having no acid groups, c) 2 to a maximum of 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 to 20% by weight, preferably 0 to 16% by weight, particularly preferably 0 to 10% by weight, of one or more oligomeric carboxylic acids, e) optionally 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight, of one or more monofunctional monomers having no 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 and / or glass filler, g) optionally 1 to 50% by weight, preferably 1.5 to 40% by weight, particularly preferably 2 to 30% 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 0.03 to 3% by weight, particularly preferably 0.05 to 2% by weight, of one or more additives, 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 35% by weight, particularly preferably 10 to 30% by weight, of at least one polyfunctional monomer having no acid groups, c) Not applicable; d) Not applicable; e) optionally 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight, of one or more monofunctional monomers having no 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 and / or glass filler, g) optionally 1 to 50% by weight, preferably 1.5 to 40% by weight, particularly preferably 2 to 30% 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) containing 0.001 to 5% by weight, preferably 0.03 to 3% by weight, particularly preferably 0.05 to 2% by weight, of one or more additives; The composition of claim 6.

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 material, 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.

Images