THERMOACTIVE DENTAL COMPOSITE COMPOSITION

Abstract

The present invention relates to dental, light-curable, one-component composite compositions comprising (A) monomers, (B) fillers, and (C) initiators, the viscosity η.sub.20 of which at 20° C. is greater than 400 Pa*s, preferably greater than 800 Pa*s and more preferably greater than 1200 Pa*s, and the viscosity η.sub.50 of which at 50° C. is less than 150 Pa*s, preferably less than 120 Pa*s and more preferably less than 90 Pa*s, and wherein the quotient η.sub.50/.sub.η20 of the viscosity of the composite composition at 50° C. and the viscosity of the composite composition at 20° C. is less than 0.125, preferably less than 0.1. The invention is preferably directed to dental composite compositions selected from the group consisting of dental filling materials, lining materials, luting materials and fissure sealants.

Claims

1. Dental, light-curable, one-component composite composition, comprising: (A) monomers, (B) fillers, and (C) initiators, wherein: the viscosity η.sub.20 of the composite composition at 20° C. is greater than 400 Pa*s and the viscosity η.sub.50 of the composite composition at 50° C. is less than 150 Pa*s and the quotient η.sub.50/η.sub.20 of the viscosity of the composite composition at 50° C. and the viscosity of the composite composition at 20° C. is less than 0.125.

2. Dental, light-curable, one-component composite composition according to claim 1, wherein the viscosity η.sub.20 of the composite composition at 20° C. is greater than 800 Pa*s, and/or the viscosity η.sub.50 of the composite composition at 50° C. is less than 120 Pa*s, and/or the quotient η.sub.50/η.sub.20 of the viscosity of the composite composition at 50° C. and the viscosity of the composite composition at 20° C. is less than 0.1.

3. Dental, light-curable, one-component composite composition according to claim 1, wherein the viscosity η.sub.37 of the composite composition at 37° C. is greater than 400 Pa*s.

4. Dental, light-curable, one-component composite composition according to claim 1, selected from the group consisting of dental filling material, lining material, luting material and fissure sealant.

5. Dental, light-curable, one-component composite composition according to claim 1, comprising: (A) monomers in an amount of 6% to 35% by weight, based on the total amount of the composite composition, (B) fillers in an amount of 65% to 93% by weight, based on the total amount of the composite composition, (C) initiators in an amount of 0.001% to 3% by weight, based on the total amount of the composite composition, (D) further additives in an amount of 0.001% to 5% by weight, based on the total amount of the composite composition.

6. Dental, light-curable, one-component composite composition according to claim 1, wherein constituent (A) comprises a mixture of at least (A-i) one first monomer substance and (A-ii) one second monomer substance, wherein the viscosity η.sub.20 of the second monomer substance (A-ii) at 20° C. is greater than 100 Pa*s, the viscosity η.sub.20 of the first monomer substance (A-i) at 20° C. is greater than 100 mPa*s, the viscosity of the second monomer substance (A-ii) at 20° C. is greater than that of the first monomer substance (A-i) and the mass ratio of the first monomer substance (A-i) to the second monomer substance (A-ii) is in the range from 2:1 to 1:10, wherein the second monomer substance (A-ii) preferably contains at least 40% by weight of 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (bis-GMA) and/or light-curable derivatives of diisocyanatodiphenylmethane (MDI) and/or light-curable derivatives of tetramethyl-m-xylylene diisocyanate (TMXDI), where the percentage by weight is based on the total mass of the monomers (A).

7. Dental, light-curable, one-component composite composition according to claim 1, wherein the monomers (A) consist of (A1) 10% to 60% by weight, of light-curable bi- or tricyclic compounds Q(Y.sub.xZ.sub.e).sub.b wherein Q denotes a saturated or olefinically unsaturated bi- or tricyclic structural element, each index b is a natural number selected from the group of the natural numbers 1, 2, and 3, each Z denotes a light-curable group, each index e is a natural number selected from the group of the natural numbers 1, 2 and 3, each Y in the structure Q(Y.sub.xZ.sub.e).sub.b with x=1 denotes a structural element which connects the structural element Q to e structural elements Z and which denotes a straight or branched alkylene group, wherein the alkylene group may be interrupted by oxygen atoms, and each index x is 0 or 1, (A2) 40% to 90% by weight, of 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (bis-GMA) and/or light-curable derivatives of diisocyanatodiphenylmethane (MDI) and/or light-curable derivatives of tetramethyl-m-xylylene diisocyanate (TMXDI), (A3) 0% to 15% by weight, of further free-radically polymerizable monomers that cannot be assigned to (A1) or (A2), wherein the percentages by weight (A1), (A2) and (A3) are based on the total mass of the monomers (A).

8. Dental, light-curable, one-component composite composition according to claim 7, wherein Q is selected from the group of structural elements consisting of bicyclo[1.1.1]pentane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[2.2.1]heptene, bicyclo[3.1.1]heptane, bicyclo[2.2.2]octane, bicyclo[4.1.1]octane, bicyclo[3.2.1]octane, bicyclo[4.2.1]nonane, bicyclo[3.3.1]nonane, bicyclo[5.1.1]nonane, bicyclo[3.2.2]nonane, bicyclo[6.1.1]decane, bicyclo[5.2.1]decane, bicyclo[4.2.2]decane, bicyclo[3.3.2]decane, bicyclo[7.1.1]undecane, bicyclo[6.2.1]undecane, bicyclo[5.2.2]undecane, bicyclo[4.3.2]undecane, bicyclo[3.3.3]undecane, bicyclo[8.1.1]dodecane, bicyclo[7.2.1]dodecane, bicyclo[6.2.2]dodecane, bicyclo[5.3.2]dodecane, bicyclo[4.3.3]dodecane, bicyclo[4.4.2]dodecane, bicyclo[5.4.1]dodecane, bicyclic tridecanes, bicyclic tetradecanes, bicyclic pentadecanes, tricyclo[3.2.1.0.sup.2,6]octane, tricyclo[4.2.1.0.sup.2,6]nonane, tricyclo[5.2.1.0.sup.2,6]decane, tricyclo[6.2.1.0.sup.2,6]undecane, tricyclo[7.2.1.0.sup.2,6]dodecane, tricyclo[4.2.1.1.sup.2,5]decane, tricyclo[4.3.1.1.sup.2,5]decane, tricyclo[4.4.1.1.sup.2,5]decane, tricyclo[2.2.1.0.sup.2,6]heptane, tricyclo[2.2.2.0.sup.2,6]octane, tricyclo[3.2.2.0.sup.2,6]nonane, tricyclo[3.3.1.1.sup.3,7]decane, tricyclo[3.2.1.1.sup.3,7]nonane, tricyclo[4.2.2.2.sup.2,5]dodecane, tricyclo[4.3.2.2.sup.2,5]tridecane, tricyclo[4.4.2.2.sup.2,5]tetradecane, tricyclo[4.2.1.0.sup.3,7]nonane, tricyclo[4.4.1.1.sup.1,5]dodecane, tricyclo[6.2.1.0.sup.2,7]undecane, tricyclo[5.2.2.0.sup.2,6]undecane, tricyclo[6.2.2.0.sup.2,7]dodecane, tricyclo[4.3.2.0.sup.2,5]undecane, tricyclo[4.2.2.0.sup.2,5]decane and tricyclo[5.5.1.0.sup.3,11]tridecane, wherein Q is preferably selected from the group of structural elements consisting of bicyclo[2.2.1]heptane, bicyclo[2.2.1]hept-2-ene, tricyclo[3.3.1.1.sup.3,7]decane and tricyclo[5.2.1.0.sup.2,6]decane and wherein Q is more preferably tricyclo[5.2.1.0.sup.2,6]decane.

9. Dental, light-curable, one-component composite composition according to claim 7, wherein the light-curable group Z denotes a structural element selected from the group consisting of —O—(C═O)—CH═CH.sub.2, —O—(C═O)—C(CH.sub.3)═CH.sub.2, —(C═O)—CH═CH.sub.2, —(C═O)—C(CH.sub.3)═CH.sub.2, —CH═CH.sub.2, —C(CH.sub.3)═CH.sub.2, —CH.sub.2—CH═CH.sub.2, —CH.sub.2—C(CH.sub.3)═CH.sub.2 and —O—CH═CH.sub.2.

10. Dental, light-curable, one-component composite composition according to claim 7, wherein component (A1) comprises or consists of bis(methacryloyloxymethyl)tricyclo[5.2.1.0.sup.2,6]decane and/or alkoxylated bis(methacryloyloxymethyl)tricyclo[5.2.1.0.sup.2,6]decane, preferably comprises or consists of bis(methacryloyloxymethyl)tricyclo[5.2.1.0.sup.2,6]decane, and/or component (A2) comprises or consists of bis-GMA.

11. Dental, light-curable, one-component composite composition according to claim 7, wherein (A3) comprises one or more di(meth)acrylate monomers selected from the group consisting of ethylene glycol di(meth)acrylate, alkoxylated ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, hexane-1,6-diol di(meth)acrylate, triethylene glycol di(meth)acrylate, dodecane-1,12-diol di(meth)acrylate, decane-1,10-diol di(meth)acrylate, bisphenol A di(meth)acrylate, alkoxylated bisphenol A di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 7,7,9-trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate, butanediol di(meth)acrylate, propanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, alkoxylated neopentyl glycol di(meth)acrylate, 2-hydroxypropyl 1,3-di(meth)acrylate, 3-hydroxypropyl 1,2-di(meth)acrylate, pentaerythritol di(meth)acrylate, alkoxylated pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, alkoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, alkoxylated dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, alkoxylated dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, alkoxylated dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, alkoxylated dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkoxylated dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, alkoxylated trimethylolpropane tri(meth)acrylate and cyclohexanedimethanol di(meth)acrylate.

12. Dental, light-curable, one-component composite composition according to claim 1, wherein the monomers (A) consist of (A4) 10% to 60% by weight of one or more compounds selected from the group consisting of light-curable bi- or tricyclic compounds Q(Y.sub.xZ.sub.e).sub.b wherein Q denotes a saturated or olefinically unsaturated bi- or tricyclic structural element, each index b is a natural number selected from the group of the natural numbers 1, 2, and 3, each Z denotes a light-curable group, each index e is a natural number selected from the group of the natural numbers 1, 2 and 3, each Y in the structure Q(Y.sub.xZ.sub.e).sub.b with x=1 denotes a structural element which connects the structural element Q to e structural elements Z and which denotes a straight or branched alkylene group, wherein the alkylene group may be interrupted by oxygen atoms, and each index x is 0 or 1, 7,7,9-trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate (UDMA), alkoxylated bisphenol A di(meth)acrylates having 2 to 6 alkoxy units, poly(meth)acrylates containing hydroxyl groups, selected from the group consisting of dipentaerythritol di(meth)acrylate, alkoxylated dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, alkoxylated dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, alkoxylated dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, alkoxylated dipentaerythritol penta(meth)acrylate, pentaerythritol di(meth)acrylate, alkoxylated pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, alkoxylated pentaerythritol tri(meth)acrylate, and light-curable, chain-like and/or cyclic and/or cage-type polysiloxanes, (A2) 40% to 90% by weight, preferably 50% to 80% by weight, more preferably 60% to 75% by weight, of 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (bis-GMA) and/or light-curable derivatives of diisocyanatodiphenylmethane (MDI) and/or light-curable derivatives of tetramethyl-m-xylylene diisocyanate (TMXDI), (A5) 0% to 15% by weight of further free-radically polymerizable monomers that cannot be assigned to (A4) or (A2), wherein the percentages by weight of (A4), (A2) and (A5) are based on the total mass of the monomers (A).

13. Dental, light-curable, one-component composite composition according to claim 1, wherein the monomers (A) consist of (A4) 10% to 60% by weight of one or more compounds selected from the group consisting of light-curable bi- or tricyclic compounds Q(Y.sub.xZ.sub.e).sub.b wherein Q denotes a saturated or olefinically unsaturated bi- or tricyclic structural element, each index b is a natural number selected from the group of the natural numbers 1, 2, and 3, each Z denotes a light-curable group, each index e is a natural number selected from the group of the natural numbers 1, 2 and 3, each Y in the structure Q(Y.sub.xZ.sub.e).sub.b with x=1 denotes a structural element which connects the structural element Q to e structural elements Z and which denotes a straight or branched alkylene group, wherein the alkylene group may be interrupted by oxygen atoms, and each index x is 0 or 1, 7,7,9-trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate (UDMA), 7,9,9-trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate 7,9-dimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate 3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate 1,5,5-trimethyl-1-[(2-methacryloyloxyethyl)carbamoylmethyl]-3-(2-methacryloyloxyethyl)carbamoylcyclohexane 7,7,9,9-tetramethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate 2,7,7,9,15-pentamethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate 2,7,9,9,15-pentamethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate 2,7,9,15-tetramethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate 2,15-dimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate 1,5,5-trimethyl-1-[(1-methacryloyloxypropan-2-yl)carbamoylmethyl]-3-(1-methacryloyloxypropan-2-yl)carbamoylcyclohexane 2,7,7,9,9,15-hexamethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate, alkoxylated bisphenol A di(meth)acrylates having 2 to 6 alkoxy units, poly(meth)acrylates containing hydroxyl groups, selected from the group consisting of dipentaerythritol di(meth)acrylate, alkoxylated dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, alkoxylated dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, alkoxylated dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, alkoxylated dipentaerythritol penta(meth)acrylate, pentaerythritol di(meth)acrylate, alkoxylated pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, alkoxylated pentaerythritol tri(meth)acrylate, and light-curable, chain-like and/or cyclic and/or cage-type polysiloxanes, (A2) 40% to 90% by weight of 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (bis-GMA) and/or light-curable derivatives of diisocyanatodiphenylmethane (MDI) and/or light-curable derivatives of tetramethyl-m-xylylene diisocyanate (TMXDI), (A5) 0% to 15% by weight, preferably 0% to 10% by weight, more preferably 0% to 5% by weight, most preferably 0% by weight, of further free-radically polymerizable monomers that cannot be assigned to (A4) or (A2), wherein the percentages by weight of (A4), (A2) and (A5) are based on the total mass of the monomers (A).

14. Dental, light-curable, one-component composite composition according to claim 1, wherein component (A) comprises more than 60% by weight of light-curable, chain-like and/or cyclic and/or cage-type polysiloxanes.

15. Dental, light-curable, one-component composite composition according to claim 1, wherein the fillers (B) consist of and/or are producible by mixing (B1) 2% to 25% by weight of inorganic filler having a D.sub.50 of 1 nm to 200 nm, and further filler constituents, preferably (B2) 40% to 90% by weight of inorganic filler having a D.sub.50 of greater than 1 μm to 10 μm, (B3) 8% to 50% by weight of inorganic filler in a size having a D.sub.50 of 0.4 μm to 1.0 μm and (B4) 0% to 25% by weight of further fillers that cannot be assigned to (B1), (B2) or (B3), wherein the percentages by weight of (B1), (B2), (B3) and (B4) are based on the total mass of the fillers (B).

16. Dental, light-curable, one-component composite composition according to claim 15, wherein the particles of the inorganic filler (B1) are not aggregated and not agglomerated and/or the inorganic filler (B1) is in a size having a D.sub.50 below 100 nm, preferably below 70 nm, and/or the inorganic filler (B2) is in a size having a D.sub.50 of 1.2 μm to 5.0 μm, and/or the inorganic filler (B3) is in a size having a D.sub.50 of 0.5 μm to 0.9 μm.

17. Dental, light-curable, one-component composite composition according to claim 15, wherein (B1) contains oxides or mixed oxides selected from the group consisting of the elements silicon, titanium, yttrium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, ytterbium, lanthanum, cerium, aluminium and mixtures thereof, preferably silica, and/or sulfides, selenides and tellurides of metals, mixed metals and mixtures thereof and/or salts of the rare earths, of scandium and of yttrium, preferably ytterbium fluoride, and/or salts of barium and of strontium, preferably barium sulfate and/or strontium fluoride, and/or mixed fluorides between ytterbium fluoride and strontium fluoride, preferably strontium fluoride-doped ytterbium fluoride and/or ytterbium fluoride-doped strontium fluoride.

18. Dental, light-curable, one-component composite composition according to claim 15, wherein constituents (B2) and (B3) comprise: materials based on oxides or mixed oxides of SiO.sub.2, ZrO.sub.2, TiO.sub.2 and/or quartz glass ceramic or glass powder, barium silicate glasses, barium fluorosilicate glasses, strontium silicate glasses, strontium borosilicates, Li/A1 silicate glasses, barium glasses, calcium silicates, sodium aluminium silicates, fluoroaluminium silicate glasses, oxides of aluminium or silicon, zeolites, apatite, zirconium silicates and/or metal salts, preferably barium sulfate or calcium fluoride, and/or ytterbium fluoride.

19. Dental, light-curable, one-component composite composition according to claim 15, wherein the ratio of the total mass of (B2) to (B3) is in the range from 1:1 to 12:1, and/or wherein the ratio of the average particle size of (B2) to the average particle size of (B3) is in the range from 1.5:1 to 10:1.

20. Dental, light-curable, one-component composite composition according to claim 15, wherein (B4) comprises reinforcing filler materials, preferably glass fibres or polyamide or carbon fibres and/or further inorganic fillers and/or splinter or bead polymers, preferably bead polymers of homo- or copolymers of organically curable monomers.

21. Dental, light-curable, one-component composite composition according to claim 15, wherein components (B1) and/or (B2) and/or (B3) and/or (B4) have been organically surface-modified.

22. Dental, light-curable, one-component composite composition according to claim 15, wherein components (B1) and/or (B2) and/or (B3) and/or (B4) have been surface-modified by compounds of the general formula X-Sp-V wherein “X” and “V” denote functional groups connected to one another by a linker “Sp” and wherein the functional group “X” is selected such that it can enter into a corresponding bond to the surface of the filler particle with complex formation, and is preferably a group of the silane, phosphate, phosphonate, carboxylate, dithiophosphate, dithiophosphonate, amine or amide type, and the linker “Sp” has linear or branched alkyl chains, aromatic systems or combinations of these groups, each of which may be interrupted by heteroatoms such as 0, N, or P or by a urethane group and the functional group “V” has light-curable groups.

23. Dental, light-curable, one-component composite composition according to claim 15, wherein components (B1) and/or (B2) and/or (B3) and/or (B4) have been silanized with a compound of the formula (1) or (2) ##STR00009## wherein R.sup.1 denotes a C1- to C4-alkyl group, and R.sup.2 denotes a C1- to C8-alkyl group, and R.sup.3 denotes a hydrogen atom or a methyl group, and a=1, 2 or 3, and b=3-a, and n=1 to 8, and m=1 to 8.

24. Cured composite composition, obtained by light curing of a dental, light-curable, one-component composite composition according to ecedig claim 1.

25. Dental, light-curable, one-component composite composition according to claim 1, for use in a method of dental treatment, preferably for use in a method of dental treatment having the following steps: heating the composite composition to a temperature of 40° C. or more, preferably a temperature in the range from 40° C. to 80° C., contacting the composite composition that has been heated to a temperature of 40° C. or more with a patient's tooth to be treated, preferably as dental filling material, lining material, luting material and fissure sealant.

26. Use of a composite composition according to claim 1 for production of a dental product, wherein the production is not effected on the human or animal body.

27. Device for applying a composite composition, comprising a cavity filled at least partly with an amount of a composite composition according to claim 1 and an application tip connected to the cavity and having an exit opening for the composite composition.

28. Device according to claim 27, wherein the exit opening has a cross-sectional exit area in the range from 0.2 to 3.0 mm.sup.2.

29. Device according to claim 27, wherein the application tip is a cannula and/or the device is selected from the group consisting of compules and syringes.

30. Method of producing a composite composition according to claim 1 or for producing a device for application of the composite composition, having the following step: mixing the constituents (A) monomers in an amount of 6% to 35% by weight, based on the total amount of the composite composition, (B) fillers in an amount of 65% to 93% by weight, based on the total amount of the composite composition, (C) initiators in an amount of 0.001% to 3% by weight based on the total amount of the composite composition, (D) further additives in an amount of 0.001% to 5% by weight based on the total amount of the composite composition, to give the composite composition, wherein the constituents are selected such that the viscosity η.sub.20 of the composite composition at 20° C. is greater than 400 Pa*s and the viscosity η.sub.50 of the composite composition at 50° C. is less than 150 Pa*s and wherein the quotient η.sub.50/η.sub.20 of the viscosity of the composite composition at 50° C. and the viscosity of the composite composition at 20° C. is less than 0.125.

31. Method according to claim 30, wherein constituent (A) is produced by the following steps: providing at least (A-i) one first monomer substance and (A-ii) one second monomer substance, wherein the viscosity η.sub.20 of the second monomer substance (A-ii) at 20° C. is greater than 100 Pa*s, the viscosity η.sub.20 of the first monomer substance (A-i) at 20° C. is greater than 100 mPa*s, the viscosity of the second monomer substance (A-ii) at 20° C. is greater than that of the first monomer substance (A-i) and the mass ratio of the first monomer substance (A-i) to the second monomer substance (A-ii) is in the range from 2:1 to 1:10, wherein the second monomer substance (A-ii) preferably contains at least 40% by weight of 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (bis-GMA) and/or light-curable derivatives of diisocyanatodiphenylmethane (MDI) and/or light-curable derivatives of tetramethyl-m-xylylene diisocyanate (TMXDI), where the percentage by weight is based on the total mass of the monomers (A), and mixing the monomer substances (A-i) and (A-ii) provided, prior to the and/or in the course of mixing with constituents (B), (C) and (D), and/or wherein constituent (B) is produced by mixing (B1) 2% to 25% by weight of inorganic filler having a D.sub.50 of 1 nm to 200 nm, and further filler constituents of inorganic filler having a D.sub.50 of greater than 1 μm to 10 μm, (B3) 8% to 50% by weight of inorganic filler in a size having a D50 of 0.4 μm to 1.0 μm and (B4) 0% to 25% by weight of further fillers that cannot be assigned to (B1), (B2) or (B3), wherein the percentages by weight of (B1), (B2), (B3) and (B4) are based on the total mass of the fillers (B).

32. Method according to claim 30, having the following additional step for preparation of the device for application of a composite composition: introducing the composite composition that has been produced into a cavity of a previously unfilled device for application of a composite composition.

33. Method of preparing for a dental treatment of a patient, having the following step: heating a composite composition according to claim 1 or a device to a temperature of 40° C. or more in an oven and/or by irradiation, wherein the device comprises a cavity filled at least partly with an amount of the composite composition and an application tip connected to the cavity and having an exit opening for the composite composition.

Description

EXAMPLES

Abbreviations

[0315] TEGDMA: triethylene glycol dimethacrylate [0316] GDMA: glycerol 1,3-dimethacrylate [0317] DODMA: dodecane-1,12-diol dimethacrylate [0318] TCDDMA: bis(methacryloyloxymethyl)tricyclo[5.2.1.0.sup.2,6]decane [0319] TCD-2EO-DMA: bis(methacryloyl-2-oxyethyloxymethyl)tricyclo[5.2.1.0.sup.2,6]decane [0320] BCHDMA: bis(hydroxymethyl)bicyclo[2.2.1]heptane [0321] UDMA: 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane 1,16-dioxydimethacrylate [0322] BisEMA: ethoxylated bisphenol A dimethacrylate having an average of 2.6 ethylene oxide units [0323] BisGMA: 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropyloxy)phenyl]propane) [0324] MDI-HEMA: addition product of diisocyanatodiphenylmethane (MDI) with HEMA (hydroxyethyl methacrylate) [0325] TMXDI-HEMA: addition product of tetramethylxylylene diisocyanate (TMXDI) with HEMA (hydroxyethyl methacrylate) [0326] Polysiloxane 1: condensation product of 3-methacryloyloxypropyldimethoxymethylsilane (for synthesis see further up) [0327] Dental glass 1: barium aluminium borosilicate glass (D50 0.8 μm/D25 0.5 μm/D75 1.0 μm), silanized with γ-methacryloyloxypropyltrimethoxysilane [0328] Dental glass 2: barium aluminium borosilicate glass (D50 2.7 μm/D25 1.4 μm/D75 6.1 μm), silanized with γ-methacryloyloxypropyltrimethoxysilane [0329] Dental glass 3: barium aluminium borosilicate glass (D50 0.8 μm/D25 0.5 μm/D75 1.0 μm), silanized with 2-(methacryloyloxy)ethyl [3-(triethoxysilyl)propyl]-carbamate [0330] Dental glass 4: barium aluminium borosilicate glass (D50 2.7 μm/D25 1.4 μm/D75 6.1 μm), silanized with 2-(methacryloyloxy)ethyl [3-(triethoxysilyl)propyl]-carbamate [0331] Nano-SiO.sub.21: non-agglomerated, non-aggregated silica (D50 40 nm), silanized with γ-methacryloyloxypropyltrimethoxysilane [0332] Nano-SiO.sub.22: non-agglomerated, non-aggregated silica (D50 40 nm), silanized with 2-(methacryloyloxy)ethyl [3-(triethoxysilyl)propyl]carbamate [0333] Fumed SiO.sub.2: Aerosil R709

[0334] Preparation of the Resins:

[0335] The appropriate methacrylate monomers were homogenized at room temperature with the aid of a precision glass stirrer. The initiators and inhibitors were already dissolved directly in the resin.

[0336] Production of the Composites

[0337] For production of the composites, the monomer mixtures with the initiators and inhibitors dissolved therein were initially charged in each case, the fillers were added stepwise and the mixture was homogenized in a Hauschild mixer. Subsequently, the finished composite was degassed at room temperature under reduced pressure (−0.85 bar).

[0338] Rheometer Measurement:

[0339] The standard method of rheometer measurement was on an Anton Paar rheometer of the Physica MCR 301 type with a 12 mm measurement plate (plate/plate), gap margin 1 mm and 450 mg of substance.

[0340] The method of measuring the viscosities of the composites at 20° C. and at 50° C. comprises three successive sections. Prior to the measurement, the plate is equilibrated to a temperature of 20° C. In Phase I of the measurement, measurement is effected at 20° C. for five minutes at a deformation of 1% and an oscillation frequency of 300 rad/s. The last point at the temperature at which the viscosity of the composite reaches its final value is used for evaluation. In Phase II, measurement is likewise effected under the same deformation and oscillation conditions at a temperature of 50° C. for five minutes and, analogously to Phase I, the last point is used for evaluation. Phase III corresponds to Phase I again, in which the viscosity of the composite then gradually approaches the original value again.

[0341] Analogously, for some examples, the viscosities were determined at 37° C. and 68° C., with measurement in the three sections at temperatures of 37° C., 68° C. and 37° C. rather than 20° C., 50° C. and 20° C.

[0342] Flexural strength (FS): Flexural strengths were determined in accordance with ISO 4049:2009. The composite pastes were applied in moulds of dimensions 25 mm×2 mm×2 mm and light-cured with a Celalux 2 lamp (VOCO GmbH) in sections for 40 seconds each. Flexural strength is determined at an advance rate of 0.75 mm/min using a Zwick universal tester (Zwick GmbH & Co. KG, Ulm).

[0343] For fixing of the limits:

[0344] FIG. 1 shows, by way of example, the temperature dependence of viscosity for Example 1. A material having a viscosity of more than 400 Pa*s (at room temperature) is malleable. The material is still just modellable at a temperature of 37° C. (intraoral temperature). At 50° C., a viscosity below 150 Pa*s is attained and the material begins to flow. In the dental practice, the composites, according to the model and type of heating unit, are preheated to a temperature of about 70° C. The inventive composition from Example 1 reaches a viscosity of 54.8 Pa*s at 68° C. and is thus exceptionally free-flowing since a viscosity corresponding to that of the commercially available free-flowing composite GrandioSO Heavy Flow is attained here. This flow composite serves as a reference for demonstration of flowability of formerly malleable composite materials. If it is assured that the composites at 50° C. have a viscosity below 150 Pa*s, the flowability thereof on preheating corresponds exactly to that of a material developed for flowability at room temperature.

[0345] The thermal efficacy or thermal effect of a dental composite composition can be illustrated by the following relationship:

[00001]$\mathrm{Thermal}\mathrm{effect}=\frac{\eta \left(20°C.\right)-\eta \left({50}^{°}C.\right)}{\eta \left(20^{°}C.\right)}\times 100\%$

[0346] A quotient η.sub.50/η.sub.20 of 0.125 thus corresponds to a thermal effect of 87.5%, and a quotient η.sub.50/η.sub.20 of 0.1 corresponds to a thermal effect of 90%. Thus, the greater the difference in its viscosities at the two temperatures stipulated, the greater the thermal effect of a dental composite composition. These values reflect the property of the composite composition according to the invention of attaining a maximum viscosity at the preparation temperature and a minimum viscosity at the treatment temperature. For the dental composite composition, this means: [0347] 1.) a clean, reliable, contamination-free approach prior to application, [0348] 2.) application at an exact location with rapid, complete adaptation to the cavity margins, [0349] 3.) transformation of the free-flowing phase back to malleability and hence excellent modellability for the dentist.

[0350] Thus, malleability is sufficient especially when both the viscosity η.sub.20 at 20° C. and the viscosity η.sub.37 at 37° C. are greater than 400 Pa*s. This is because, in that case, the composite compositions according to the invention can both be handled cleanly and without contamination at room temperature and modelled efficiently at intraoral temperature.

[0351] Table 1 contains, by way of example, the numerical values for the thermal efficacy of commercially available dental composites.

[0352] No commercially available dental composites have a sufficient thermal effect and the required values of viscosity before and after heating, and so there are no malleable products on the market to date that have a viscosity that decreases disproportionately on heating, and so adapt efficiently to the prepared cavity margins in the heated state—in a comparable manner to the flow composites—in order to switch back to the malleable state with increasing cooling, to have good modellability and then, after light curing, to have the excellent mechanical properties of highly filled dental composites.

[0353] Dental compositions with light-curable bi- or tricyclic systems are known from the prior art.

[0354] Published specification DE 28 16 823 describes curable dental compounds for dental fillings, dental prostheses and as sealing compounds that comprise di(meth)acrylates of bis(hydroxymethyl)tricyclo[5.2.1.0.sup.2,6]decane. Example 9 describes a two-component paste/paste system composed of the diacrylate of bis(hydroxymethyl)tricyclo[5.2.1.0.sup.2,6]decane with the propoxylated dimethacrylate of bisphenol A. Examples 12 and 13 disclose light-curable, one-component composite compositions which include, as organic matrix, diacrylates of bis(hydroxymethyl)tricyclo[5.2.1.0.sup.2,6]decane. Example 15 discloses a light-curable coating compound based on the dimethacrylate of bis(hydroxymethyl)tricyclo[5.2.1.0.sup.2,6]decane in combination with hexanediol dimethacrylate.

[0355] Published specification DE 29 31 926 describes the (meth)acrylates of alkoxylated bis(hydroxymethyl)tricyclo[5.2.1.0.sup.2,6]decane as a suitable binder for curable dental compounds. These tricyclic systems are said to be suitable as diluent monomers for high-viscosity dental standard monomers such as bis-GMA (bisphenol A glycidyl methacrylate). For production of mixed binders, the (meth)acrylates of alkoxylated bis(hydroxymethyl)tricyclo[5.2.1.0.sup.2,6]decane can be used together with ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetraacrylate, butane-1,3-diol di(meth)acrylate and hexane-1,6-diol di(meth)acrylate.

[0356] Example 14 discloses a two-component chemical curable dental composite composition, the resin matrix of which consists of 70 parts bis(hydroxymethyl)tricyclo[5.2.1.0.sup.2,6]decane and 30 parts bis-GMA. Example 19 reports a one-component, radiation-curable composite composition including, as resin matrix, the propoxylated dimethacrylate of bis(hydroxymethyl)tricyclo[5.2.1.0.sup.2,6]decane.

[0357] Published specification DE 29 31 925—like the above-cited DE 29 31 926—relates to (meth)acrylates of tricyclic decanediols containing ether groups. The alkoxylated tricyclic systems are suitable for use for production of adhesives and sealants and for production of dental repair materials.

[0358] U.S. Pat. No. 4,131,729 also specifies dental, light-curable composite compositions of the (meth)acrylates of bis(hydroxymethyl)tricyclo[5.2.1.0.sup.2,6]decane (Examples 12, 13 and 15). The tricyclic system can be used alone or in combination with other monomers. The text says “Known bifunctional monomers which are particularly suitable for novel combinations with the monomers of the invention are the di(meth)acrylates of hexanediol, bis(p-hydroxyethoxy)phenylpropane, or bis-[p-(gamma-hydroxypropoxy)phenyl]propane.”

[0359] DE 2 200 021, entitled “Acrylic esters of tricyclic decanols containing OH groups”, claims tricyclodecane derivatives for use in curable adhesives for production of heat-resistant bonds. Further (meth)acrylates of tricyclic decanols are described in documents DE 24 06 557, DE 35 22 005, DE 35 22 006 and DE 37 03 120.

[0360] DE 10 2005 021 332 A1 claims dental composite materials having low shrinkage. The resin matrix of the curable composition comprises bis-GMA or the tricyclic derivative TCD-di-HEMA or the tricyclic derivative TCD-di-HEA in an amount of 60-80% by weight, 10% to 18% by weight of UDMA (urethane dimethacrylate) and the balance TEDMA and/or multifunctional crosslinkers, where the percentages by weight are based on the resin phase.

[0361] DE 10 2007 034 457 A1 claims dental composite materials having low shrinkage stress and high flexural strength. The resin matrix of the curable composition contains bis-GMA and a member from the group of TCD-di-HEMA and TCD-di-HEA in an amount of 60-80% by weight, 10-18% by weight of UDMA and as the balance TEDMA and/or multifunctional crosslinkers, where the percentages by weight are based on the resin phase.

[0362] EP 2 436 366 B1 is directed to a composite material which comprises a monomer having a polyalicyclic structural element and is used as sealing material. In Examples 3 and 4 (Table 1), bis(methacryloyloxymethyl)tricyclo[5.2.1.0.sup.2,6]decane is used together with bis-GMA.

[0363] However, the total filler content is well below 70% by weight based on the composite composition and the proportion of the tricyclodecane derivative far exceeds the proportion of bis-GMA.

TABLE-US-00001 TABLE 1   Commercial composite η(20° C.) [Pa .Math. s] η(50° C.) [Pa .Math. s] [00002]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ [00003]$\frac{\eta \left(20^{\circ }C.\right)-\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}\times 100\%$ Filtek Supreme XTE 2045 869 0.42 57.5% (3M Espe) Clearfil Majesty Posterior 3147 2135 0.68 32.2% (Kuraray) Ceram X 1422 368 0.26 74.1% (Dentsply) Sonic Fill (Kerr) 419 257 0.61 38.7% Sonic Fill 2 (Kerr) 1019 683 0.67 33.0% Ecosite Universal Bulk Fill 460 221 0.48 51.9% (DMG) Esthet-X (Dentsply) 923 250 0.27 73.2% GrandioSO Heavy Flow 53.3 n.d. n.d. n.d. (VOCO)

TABLE-US-00002 TABLE 2 Example 1 2 3 (A) Monomers (A1) TCDDMA 4.23 4.63 6.04 (A2) BisGMA 16.90 10.87 9.11 (A3) UDMA (B) Fillers (B1) Nano-SiO.sub.2 1 6.28 14.76 14.56 (B2) Dental glass 2 60.33 58.02 58.49 (B3) Dental glass 1 12.04 11.59 11.68 (C) Initiators (C1) CQ 0.06 0.04 0.04 (C2) DABE 0.10 0.07 0.07 (D) Others (D1) BHT 0.06 0.02 0.01 Total 100.00 100.00 100.00 Viscosity η(20° C.) [Pa .Math. s] 2290.2 1974.1 1405.9 Viscosity η(37° C.) [Pa .Math. s] 505.8 473.3 449.7 Viscosity η(50° C.) [Pa .Math. s] 142.3 134.1 136.7 Viscosity η(68° C.) [Pa .Math. s] 54.8 54.1 53.5 [00004]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ 0.06 0.07 0.10 [00005]$\mathrm{Thermal}\mathrm{effect}\frac{\begin{array}{c}\eta \left(20^{\circ }C.\right)-\\ \eta \left(50^{\circ }C.\right)\end{array}}{\eta \left(20^{\circ }C.\right)}\times 100\%$ 93.8% 93.2% 90.3% Flexural strength [MPa] 155.4 149.6 154.8

TABLE-US-00003 TABLE 3 Example 4 5 6 (A) Monomers (A1) TCDDMA 6.34 5.21 4.56 (A2) BisGMA 14.79 12.17 10.71 (A3) UDMA (B) Fillers (B1) Nano-SiO.sub.2 1 6.28 9.26 16.67 (B2) Dental glass 2 60.33 61.02 58.24 (B3) Dental glass 1 12.04 12.19 9.69 (C) Initiators (C1) CQ 0.06 0.05 0.05 (C2) DABE 0.10 0.08 0.07 (D) Others (D1) BHT 0.06 0.02 0.01 Total 100.00 100.00 100.00 Viscosity η(20° C.) [Pa .Math. s] 1502.3 1253.4 1817.7 Viscosity η(50° C.) [Pa .Math. s] 123.9 134.5 142.3 [00006]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ 0.08 0.11 0.08 [00007]$\mathrm{Thermal}\mathrm{effect}\frac{\begin{array}{c}\eta \left(20^{\circ }C.\right)-\\ \eta \left(50^{\circ }C.\right)\end{array}}{\eta \left(20^{\circ }C.\right)}\times 100\%$ 91.8% 89.3% 92.2% Flexural strength [MPa] 141.0 134.9 152.4

TABLE-US-00004 TABLE 4 Example 7 8 9 (A) Monomers (A1) TCDDMA 7.38 5.74 8.55 (A2) BisGMA 17.23 13.39 8.11 (A3) UDMA 2.00 (B) Fillers (B1) Nano-SiO.sub.2 1 3.00 6.28 14.16 (B2) Dental glass 2 60.17 60.33 57.55 (B3) Dental glass 1 12.01 12.04 11.51 (C) Initiators (C1) CQ 0.07 0.06 0.04 (C2) DABE 0.11 0.10 0.07 (D) Others (D1) BHT 0.03 0.06 0.02 Total 100.00 100.00 100.00 Viscosity η(20° C.) [Pa .Math. s] 1387.2 1465.2 1203.1 Viscosity η(50° C.) [Pa .Math. s] 112.8 118.1 145.4 [00008]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ 0.08 0.08 0.12 [00009]$\mathrm{Thermal}\mathrm{effect}\frac{\begin{array}{c}\eta \left(20^{\circ }C.\right)-\\ \eta \left(50^{\circ }C.\right)\end{array}}{\eta \left(20^{\circ }C.\right)}\times 100\%$ 91.9% 91.9% 87.9% Flexural strength [MPa] 128.2 135.0 123.7

TABLE-US-00005 TABLE 5 Example 10 11 12 (A) Monomers (A1) TCDDMA 7.51 TCD-2EO-DMA 4.63 BDHDMA 4.63 (A2) BisGMA 17.43 10.87 10.87 (A3) UDMA (B) Fillers (B1) Fumed SiO.sub.2 2.20 Nano-SiO.sub.2 1 14.76 14.76 (B2) Dental glass 2 60.57 58.02 58.02 (B3) Dental glass 1 12.11 11.59 11.59 (C) Initiators (C1) CQ 0.06 0.04 0.04 (C2) DABE 0.10 0.07 0.07 (D) Others (D1) BHT 0.02 0.02 0.02 Total 100.00 100.00 100.00 Viscosity η(20° C.) [Pa .Math. s] 1488.6 1966.3 1908.4 Viscosity η(50° C.) [Pa .Math. s] 143.6 139.8 142.1 [00010]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ 0.10 0.07 0.07 [00011]$\mathrm{Thermal}\mathrm{effect}\frac{\begin{array}{c}\eta \left(20^{\circ }C.\right)-\\ \eta \left(50^{\circ }C.\right)\end{array}}{\eta \left(20^{\circ }C.\right)}\times 100\%$ 90.4% 92.9% 92.6% Flexural strength [MPa] 127.0 142.1 135.6

TABLE-US-00006 TABLE 6 Example 13 14 15 (A) Monomers (A1) TCDDMA 4.63 6.20 5.03 (A2) BisGMA 10.87 MDI-HEMA 9.30 TMXDI-HEMA 10.47 (A3) UDMA (B) Fillers (B1) Nano-SiO.sub.2 1 14.76 14.76 Nano-SiO.sub.2 2 14.76 (B2) Dental glass 2 58.02 58.02 Dental glass 4 58.02 (B3) Dental glass 1 11.59 11.59 Dental glass 3 11.59 (C) Initiators (C1) CQ 0.04 0.04 0.04 (C2) DABE 0.07 0.07 0.07 (D) Others (D1) BHT 0.02 0.02 0.02 Total 100.00 100.00 100.00 Viscosity η(20° C.) [Pa .Math. s] 2344.5 1641.1 1588.7 Viscosity η(50° C.) [Pa .Math. s] 117.3 148.7 147.3 [00012]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ 0.05 0.09 0.09 [00013]$\mathrm{Thermal}\mathrm{effect}\frac{\begin{array}{c}\eta \left(20^{\circ }C.\right)-\\ \eta \left(50^{\circ }C.\right)\end{array}}{\eta \left(20^{\circ }C.\right)}\times 100\%$ 95.0% 90.9% 90.7% Flexural strength [MPa] 153.1 128.4 123.5

TABLE-US-00007 TABLE 7 Example 16 (A) Monomers (A1) TCDDMA 7.21 (A2) BisGMA 16.81 (A3) UDMA (B) Fillers (B1) Nano-SiO.sub.2 1 6.28 (B2) Dental glass 2 57.92 (B3) Dental glass 1 11.56 (C) Initiators (C1) CQ 0.06 (C2) DABE 0.10 (D) Others (D1) BHT 0.06 Total 100.00 Viscosity η(20° C.) [Pa .Math. s] 502.2 Viscosity η(50° C.) [Pa .Math. s] 62.5 [00014]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ 0.124 [00015]$\mathrm{Thermal}\mathrm{effect}\frac{\begin{array}{c}\eta \left(20^{\circ }C.\right)-\\ \eta \left(50^{\circ }C.\right)\end{array}}{\eta \left(20^{\circ }C.\right)}\times 100\%$ 87.6% Flexural strength [MPa] 127.2

TABLE-US-00008 TABLE 8 Example 17 18 19 (A) (A4) UDMA 3.84 4.48 5.17 Monomers (A2) BisGMA 11.01 11.28 11.64 (A5) TEGDMA 2.62 2.15 1.66 (B) Fillers (B1) Nano-SiO.sub.2 1 10.00 10.00 10.00 (B2) Dental glass 2 60.33 59.97 59.50 (B3) Dental glass 1 12.07 11.99 11.90 (C) Initiators (C1) CQ 0.04 0.04 0.04 (C2) DABE 0.07 0.07 0.07 (D) Others (D1) BHT 0.02 0.02 0.02 Total 100.00 100.00 100.00 Viscosity η(20° C.) [Pa .Math. s] 708 1069 1211 Viscosity η(37° C.) [Pa .Math. s] 322 402 431 Viscosity η(50° C.) [Pa .Math. s] 128 133 145 Viscosity η(68° C.) [Pa .Math. s] 51 52 54 [00016]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ 0.181 0.124 0.120 [00017]$\mathrm{Thermal}\mathrm{effect}\frac{\begin{array}{c}\eta \left(20^{\circ }C.\right)-\\ \eta \left(50^{\circ }C.\right)\end{array}}{\eta \left(20^{\circ }C.\right)}\times 100\%$ 81.9% 87.6% 88.0% Flexural strength [MPa] 136.4 137.2 137.9

TABLE-US-00009 TABLE 9 Example 20 21 22 (A) (A4) BisEMA 5.83 5.22 4.66 Monomers (A2) BisGMA 10.82 12.18 13.99 (A5) TEGDMA (B) Fillers (B1) Nano-SiO.sub.2 1 9.00 9.00 9.00 (B2) Dental glass 2 61.85 61.22 60.18 (B3) Dental glass 1 12.37 12.24 12.04 (C) Initiators (C1) CQ 0.04 0.04 0.04 (C2) DABE 0.07 0.07 0.07 (D) Others (D1) BHT 0.02 0.02 0.02 Total 100.00 100.00 100.00 Viscosity η(20° C.) [Pa .Math. s] 1045 1233 1568 Viscosity η(50° C.) [Pa .Math. s] 125 137 147 [00018]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ 0.120 0.111 0.094 [00019]$\mathrm{Thermal}\mathrm{effect}\frac{\begin{array}{c}\eta \left(20^{\circ }C.\right)-\\ \eta \left(50^{\circ }C.\right)\end{array}}{\eta \left(20^{\circ }C.\right)}\times 100\%$ 88.0% 88.9% 90.6% Flexural strength [MPa] 135.3 142.1 139.9

TABLE-US-00010 TABLE 10 Example 23 24 25 (A) (A4) DIPENTA 4.19 4.83 5.54 Monomers (A2) BisGMA 11.01 11.28 11.64 (A5) TEGDMA 2.27 1.79 1.29 (B) Fillers (B1) Nano-SiO.sub.2 1 10.00 10.00 10.00 (B2) Dental glass 2 60.33 59.97 59.50 (B3) Dental glass 1 12.07 11.99 11.90 (C) Initiators (C1) CQ 0.04 0.04 0.04 (C2) DABE 0.07 0.07 0.07 (D) Others (D1) BHT 0.02 0.02 0.02 Total 100.00 100.00 100.00 Viscosity η(20° C.) [Pa .Math. s] 941 1156 1311 Viscosity η(50° C.) [Pa .Math. s] 131 139 147 [00020]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ 0.139 0.120 0.112 [00021]$\begin{array}{c}\mathrm{Thermal}\\ \mathrm{effect}\end{array}\frac{\begin{array}{c}\eta \left(20^{\circ }C.\right)-\\ \eta \left(50^{\circ }C.\right)\end{array}}{\eta \left(20^{\circ }C.\right)}\times 100\%$ 86.1% 88.0% 88.8% Flexural strength [MPa] 121.4 125.3 122.1

TABLE-US-00011 TABLE 11 Example 26 27 28 (A) (A4) TCDDMA 3.13 2.28 1.59 Monomers UDMA 3.88 3.73 3.58 (A2) BisGMA 13.58 13.88 13.91 (A5) TEGDMA 0.97 0.83 0.79 (B) Fillers (B1) Nano-SiO.sub.2 1 4.72 4.36 4.00 (B2) Dental glass 2 61.33 54.67 48.00 (B3) Dental glass 1 12.27 20.13 28.00 (C) Initiators (C1) CQ 0.04 0.04 0.04 (C2) DABE 0.07 0.07 0.07 (D) Others (D1) BHT 0.02 0.02 0.02 Total 100.00 100.00 100.00 Viscosity η(20° C.) [Pa .Math. s] 1570 1588 1592 Viscosity η(50° C.) [Pa .Math. s] 149 128 102 [00022]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ 0.095 0.081 0.064 [00023]$\begin{array}{c}\mathrm{Thermal}\\ \mathrm{effect}\end{array}\frac{\begin{array}{c}\eta \left(20^{\circ }C.\right)-\\ \eta \left(50^{\circ }C.\right)\end{array}}{\eta \left(20^{\circ }C.\right)}\times 100\%$ 90.5% 91.9% 93.6% Flexural strength [MPa] 141.1 137.7 140.5

TABLE-US-00012 TABLE 12 Example 29 30 31 (A) (A4) UDMA 5.17 5.17 5.27 Monomers (A2) BisGMA 5.82 5.75 MDI-HEMA 5.82 11.64 TMXDI-HEMA 5.75 (A5) TEGDMA 1.66 1.66 1.70 (B) Fillers (B1) Nano-SiO.sub.2 1 10.00 10.00 10.00 (B2) Dental glass 2 59.50 59.50 59.50 (B3) Dental glass 1 11.90 11.90 11.90 (C) Initiators (C1) CQ 0.04 0.04 0.04 (C2) DABE 0.07 0.07 0.07 (D) Others (D1) BHT 0.02 0.02 0.02 Total 100.00 100.00 100.00 Viscosity η(20° C.) [Pa .Math. s] 1723 1952 1984 Viscosity η(50° C.) [Pa .Math. s] 147 150 143 [00024]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ 0.085 0.077 0.072 [00025]$\mathrm{Thermal}\mathrm{effect}\frac{\begin{array}{c}\eta \left(20^{\circ }C.\right)-\\ \eta \left(50^{\circ }C.\right)\end{array}}{\eta \left(20^{\circ }C.\right)}\times 100\%$ 91.5% 92.3% 92.8% Flexural strength [MPa] 129 133 138

TABLE-US-00013 TABLE 13 Example 32 33 34 (A) (A4) Polysiloxane 1 6.17 9.57 18.12 Monomers (A2) BisGMA 11.64 9.57 (A5) TEGDMA 0.66 (B) Fillers (B1) Nano-SiO.sub.2 1 9.00 8.99 8.99 (B2) Dental glass 2 60.33 59.78 60.63 (B3) Dental glass 1 12.07 11.96 12.13 (C) Initiators (C1) CQ 0.04 0.04 0.04 (C2) DABE 0.07 0.07 0.07 (D) Others (D1) BHT 0.02 0.02 0.02 Total 100.00 100.00 100.00 Viscosity η(20° C.) [Pa .Math. s] 1665 2029 1789 Viscosity η(50° C.) [Pa .Math. s] 149 147 143 [00026]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ 0.089 0.072 0.080 [00027]$\mathrm{Thermal}\mathrm{effect}\frac{\begin{array}{c}\eta \left(20^{\circ }C.\right)-\\ \eta \left(50^{\circ }C.\right)\end{array}}{\eta \left(20^{\circ }C.\right)}\times 100\%$ 91.1% 92.8% 92.0% Flexural strength [MPa] 132.2 131.0 134.7

TABLE-US-00014 TABLE 14 Comparative Example V1 V2 V3 (A) Monomers (A1) TCDDMA 12.47 5.92 (A2) BisGMA 5.34 (A3) UDMA 13.67 8.89 BisEMA (B) Fillers (B1) Nano-SiO.sub.2 1 13.55 17.68 13.05 (B2) Dental glass 2 57.10 57.12 60.03 (B3) Dental glass 1 11.41 11.39 11.94 (C) Initiators (C1) CQ 0.04 0.04 0.05 (C2) DABE 0.07 0.06 0.07 (D) Others (D1) BHT 0.02 0.04 0.05 Total 100.00 100.00 100.00 Viscosity η(20° C.) [Pa .Math. s] 233.9 1522.3 678.8 Viscosity η(50° C.) [Pa .Math. s] 105.8 550.5 310.1 [00028]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ 0.45 0.36 0.46 [00029]$\mathrm{Thermal}\mathrm{effect}\frac{\begin{array}{c}\eta \left(20^{\circ }C.\right)-\\ \eta \left(50^{\circ }C.\right)\end{array}}{\eta \left(20^{\circ }C.\right)}\times 100\%$ 54.8% 63.8% 54.3% Flexural strength [MPa] 118.8 162.9 156.7

TABLE-US-00015 TABLE 15 Comparative Example V4 V5 V6 (A) Monomers (A1) TCDDMA 7.74 3.98 9.96 (A2) BisGMA (A3) UDMA 11.61 BisEMA 10.47 4.49 (B) Fillers (B1) Nano-SiO.sub.2 1 5.75 13.14 13.14 (B2) Dental glass 2 62.25 60.30 60.30 (B3) Dental glass 1 12.44 12.04 12.04 (C) Initiators (C1) CQ 0.06 0.02 0.02 (C2) DABE 0.09 0.03 0.03 (D) Others (D1) BHT 0.06 0.02 0.02 Total 100.00 100.00 100.00 Viscosity η(20° C.) [Pa .Math. s] 206.7 377.0 314.8 Viscosity η(50° C.) [Pa .Math. s] 95.6 242.8 189.1 [00030]$\frac{\eta \left(50^{\circ }C.\right)}{\eta \left(20^{\circ }C.\right)}$ 0.46 0.64 0.60 [00031]$\mathrm{Thermal}\mathrm{effect}\frac{\begin{array}{c}\eta \left(20^{\circ }C.\right)-\\ \eta \left(50^{\circ }C.\right)\end{array}}{\eta \left(20^{\circ }C.\right)}\times 100\%$ 53.7% 35.6% 39.9% Flexural strength [MPa] 159.8 139.4 130.0

[0364] Relevant aspects of the present invention are summarized hereinafter:

[0365] Aspects:

[0366] 1. Dental, light-curable, one-component composite composition, comprising:

[0367] (A) monomers,

[0368] (B) fillers, and

[0369] (C) initiators,

[0370] characterized in that [0371] the viscosity η.sub.20 of the composite composition at 20° C. is greater than 400 Pa*s and [0372] the viscosity η.sub.50 of the composite composition at 50° C. is less than 150 Pa*s and [0373] the quotient η.sub.50/η.sub.20 of the viscosity of the composite composition at 50° C. and the viscosity of the composite composition at 20° C. is less than 0.125.

[0374] 2. Dental, light-curable, one-component composite composition according to Aspect 1, wherein [0375] the viscosity η.sub.20 of the composite composition at 20° C. is greater than 800 Pa*s, preferably greater than 1200 Pa*s, and/or [0376] the viscosity η.sub.50 of the composite composition at 50° C. is less than 120 Pa*s, preferably less than 90 Pa*s, and/or [0377] the quotient η.sub.50/η.sub.20 of the viscosity of the composite composition at 50° C. and the viscosity of the composite composition at 20° C. is less than 0.1.

[0378] 3. Dental, light-curable, one-component composite composition according to any of the preceding aspects, wherein the viscosity η.sub.37 of the composite composition at 37° C. is greater than 400 Pa*s.

[0379] 4. Dental, light-curable, one-component composite composition according to any of the preceding aspects, selected from the group consisting of dental filling material, lining material, luting material and fissure sealant.

[0380] 5. Dental, light-curable, one-component composite composition according to any of the preceding aspects, comprising:

[0381] (A) monomers in an amount of 6% to 35% by weight, based on the total amount of the composite composition, preferably 10% to 35% by weight, more preferably 10% to 25% by weight,

[0382] (B) fillers in an amount of 65% to 93% by weight, based on the total amount of the composite composition, preferably 65% to 89% by weight, more preferably 75% to 89% by weight,

[0383] (C) initiators in an amount of 0.001% to 3% by weight, based on the total amount of the composite composition,

[0384] (D) further additives in an amount of 0.001% to 5% by weight, based on the total amount of the composite composition.

[0385] 6. Dental, light-curable, one-component composite composition according to any of the preceding aspects, wherein constituent (A) comprises a mixture of at least

[0386] (A-i) one first monomer substance and

[0387] (A-ii) one second monomer substance, wherein [0388] the viscosity η.sub.20 of the second monomer substance (A-ii) at 20° C. is greater than 100 Pa*s, [0389] the viscosity η.sub.20 of the first monomer substance (A-i) at 20° C. is greater than 100 mPa*s, [0390] the viscosity of the second monomer substance (A-ii) at 20° C. is greater than that of the first monomer substance (A-i) and [0391] the mass ratio of the first monomer substance (A-i) to the second monomer substance (A-ii) is in the range from 2:1 to 1:10,

[0392] wherein the second monomer substance (A-ii) preferably contains at least 40% by weight of 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (bis-GMA) and/or light-curable derivatives of diisocyanatodiphenylmethane (MDI) and/or light-curable derivatives of tetramethyl-m-xylylene diisocyanate (TMXDI), where the percentage by weight is based on the total mass of the monomers (A).

[0393] 7. Dental, light-curable, one-component composite composition, preferably according to any of the preceding aspects, wherein the monomers (A) consist of

[0394] (A1) 10% to 60% by weight, preferably 20% to 50% by weight, more preferably 25% to 40% by weight, of light-curable bi- or tricyclic compounds Q(Y.sub.xZ.sub.e).sub.b wherein

[0395] Q denotes a saturated or olefinically unsaturated bi- or tricyclic structural element, each index b is a natural number selected from the group of the natural numbers 1, 2, and 3, each Z denotes a light-curable group,

[0396] each index e is a natural number selected from the group of the natural numbers 1, 2 and 3, each Y in the structure Q(Y.sub.xZ.sub.e).sub.b with x=1 denotes a structural element which connects the structural element Q to e structural elements Z and which denotes a straight or branched alkylene group, wherein the alkylene group may be interrupted by oxygen atoms, and each index x is 0 or 1,

[0397] (A2) 40% to 90% by weight, preferably 50% to 80% by weight, more preferably 60% to 75% by weight, of 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (bis-GMA) and/or light-curable derivatives of diisocyanatodiphenylmethane (MDI) and/or light-curable derivatives of tetramethyl-m-xylylene diisocyanate (TMXDI),

[0398] (A3) 0% to 15% by weight, preferably 0% to 10% by weight, more preferably 0% to 5% by weight, most preferably 0% by weight, of further free-radically polymerizable monomers that cannot be assigned to (A1) or (A2), wherein the percentages by weight (A1), (A2) and (A3) are based on the total mass of the monomers (A).

[0399] 8. Dental, light-curable, one-component composite composition according to Aspect 7, wherein Q is selected from the group of structural elements consisting of bicyclo[1.1.1]pentane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[2.2.1]heptene, bicyclo[3.1.1]heptane, bicyclo[2.2.2]octane, bicyclo[4.1.1]octane, bicyclo[3.2.1]octane, bicyclo[4.2.1]nonane, bicyclo[3.3.1]nonane, bicyclo[5.1.1]nonane, bicyclo[3.2.2]nonane, bicyclo[6.1.1]decane, bicyclo[5.2.1]decane, bicyclo[4.2.2]decane, bicyclo[3.3.2]decane, bicyclo[7.1.1]undecane, bicyclo[6.2.1]undecane, bicyclo[5.2.2]undecane, bicyclo[4.3.2]undecane, bicyclo[3.3.3]undecane, bicyclo[8.1.1]dodecane, bicyclo[7.2.1]dodecane, bicyclo[6.2.2]dodecane, bicyclo[5.3.2]dodecane, bicyclo[4.3.3]dodecane, bicyclo[4.4.2]dodecane, bicyclo[5.4.1]dodecane, bicyclic tridecanes, bicyclic tetradecanes, bicyclic pentadecanes, tricyclo[3.2.1.0.sup.2,6]octane, tricyclo[4.2.1.0.sup.2,6]nonane, tricyclo[5.2.1.0.sup.2,6]decane, tricyclo[6.2.1.0.sup.2,6]undecane, tricyclo[7.2.1.0.sup.2,6]dodecane, tricyclo[4.2.1.1.sup.2,5]decane, tricyclo[4.3.1.1.sup.2,5]decane, tricyclo[4.4.1.1.sup.2,5]decane, tricyclo[2.2.1.0.sup.2,6]heptane, tricyclo[2.2.2.0.sup.2,6]octane, tricyclo[3.2.2.0.sup.2,6]nonane, tricyclo[3.3.1.1.sup.3,7]decane, tricyclo[3.2.1.1.sup.3,7]nonane, tricyclo[4.2.2.2.sup.2,5]dodecane, tricyclo[4.3.2.2.sup.2,5]tridecane, tricyclo[4.4.2.2.sup.2,5]tetradecane, tricyclo[4.2.1.0.sup.3,7]nonane, tricyclo[4.4.1.1.sup.1,5]dodecane, tricyclo[6.2.1.0.sup.2,7]undecane, tricyclo[5.2.2.0.sup.2,6]undecane, tricyclo[6.2.2.0.sup.2,7]dodecane, tricyclo[4.3.2.0.sup.2,5]undecane, tricyclo[4.2.2.0.sup.2,5]decane and tricyclo[5.5.1.0.sup.3,11]tridecane, wherein

[0400] Q is preferably selected from the group of structural elements consisting of bicyclo[2.2.1]heptane, bicyclo[2.2.1]hept-2-ene, tricyclo[3.3.1.1.sup.3,7]decane and tricyclo[5.2.1.0.sup.2,6]decane and wherein Q is more preferably tricyclo[5.2.1.0.sup.2,6]decane.

[0401] 9. Dental, light-curable, one-component composite composition according to any of Aspects 7 and 8, wherein the light-curable group Z denotes a structural element selected from the group consisting of —O—(C═O)—CH═CH.sub.2, —O—(C═O)—C(CH.sub.3)═CH.sub.2, —(C═O)—CH═CH.sub.2, —(C═O)—C(CH.sub.3)═CH.sub.2, —CH═CH.sub.2, —C(CH.sub.3)═CH.sub.2, —CH.sub.2—CH═CH.sub.2, —CH.sub.2—C(CH.sub.3)═CH.sub.2 and —O—CH═CH.sub.2, preferably selected from the group consisting of —O—(C═O)—CH═CH.sub.2 and —O—(C═O)—C(CH.sub.3)═CH.sub.2.

[0402] 10. Dental, light-curable, one-component composite composition according to any of Aspects 7 to 9, wherein

[0403] component (A1) comprises or consists of bis(methacryloyloxymethyl)tricyclo[5.2.1 0.sup.2,6]decane and/or alkoxylated bis(methacryloyloxymethyl)tricyclo[5.2.1.0.sup.2,6]decane, preferably comprises or consists of bis(methacryloyloxymethyl)tricyclo[5.2.1.0.sup.2,6]decane, and/or component (A2) comprises or consists of bis-GMA.

[0404] 11. Dental, light-curable, one-component composite composition according to any of Aspects 7 to 10, wherein (A3) comprises one or more di(meth)acrylate monomers selected from the group consisting of ethylene glycol di(meth)acrylate, alkoxylated ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, hexane-1,6-diol di(meth)acrylate, triethylene glycol di(meth)acrylate, dodecane-1,12-diol di(meth)acrylate, decane-1,10-diol di(meth)acrylate, bisphenol A di(meth)acrylate, alkoxylated bisphenol A di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di-(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 7,7,9-trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate, butanediol di(meth)acrylate, propanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, alkoxylated neopentyl glycol di(meth)acrylate, 2-hydroxypropyl 1,3-di(meth)acrylate, 3-hydroxypropyl 1,2-di(meth)acrylate, pentaerythritol di(meth)acrylate, alkoxylated pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, alkoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, alkoxylated dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, alkoxylated dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, alkoxylated dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, alkoxylated dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkoxylated dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, alkoxylated trimethylolpropane tri(meth)acrylate and cyclohexanedimethanol di(meth)acrylate.

[0405] 12. Dental, light-curable, one-component composite composition according to any of Aspects 1-6, wherein the monomers (A) consist of

[0406] (A4) 10% to 60% by weight, preferably 20% to 50% by weight, more preferably 25% to 40% by weight, of one or more compounds selected from the group consisting of [0407] light-curable bi- or tricyclic compounds Q(Y.sub.xZ.sub.e).sub.b wherein [0408] Q denotes a saturated or olefinically unsaturated bi- or tricyclic structural element, each index b is a natural number selected from the group of the natural numbers 1, 2, and 3, [0409] each Z denotes a light-curable group, [0410] each index e is a natural number selected from the group of the natural numbers 1, 2 and 3, [0411] each Y in the structure Q(Y.sub.xZ.sub.e).sub.b with x=1 denotes a structural element which connects the structural element Q to e structural elements Z and which denotes a straight or branched alkylene group, wherein the alkylene group may be interrupted by oxygen atoms, and [0412] each index x is 0 or 1, [0413] 7,7,9-trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate (UDMA), [0414] alkoxylated bisphenol A di(meth)acrylates having 2 to 6 alkoxy units, [0415] poly(meth)acrylates containing hydroxyl groups, selected from the group consisting of dipentaerythritol di(meth)acrylate, alkoxylated dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, alkoxylated dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, alkoxylated dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, alkoxylated dipentaerythritol penta(meth)acrylate, pentaerythritol di(meth)acrylate, alkoxylated pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, alkoxylated pentaerythritol tri(meth)acrylate, and [0416] light-curable, chain-like and/or cyclic and/or cage-type polysiloxanes,

[0417] (A2) 40% to 90% by weight, preferably 50% to 80% by weight, more preferably 60% to 75% by weight, of 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (bis-GMA) and/or light-curable derivatives of diisocyanatodiphenylmethane (MDI) and/or light-curable derivatives of tetramethyl-m-xylylene diisocyanate (TMXDI),

[0418] (A5) 0% to 15% by weight, preferably 0% to 10% by weight, more preferably 0% to 5% by weight, most preferably 0% by weight, of further free-radically polymerizable monomers that cannot be assigned to (A4) or (A2),

[0419] wherein the percentages by weight of (A4), (A2) and (A5) are based on the total mass of the monomers (A).

[0420] 13. Dental, light-curable, one-component composite composition according to any of Aspects 1-6, wherein the monomers (A) consist of

[0421] (A4) 10% to 60% by weight, preferably 20% to 50% by weight, more preferably 25% to 40% by weight, of one or more compounds selected from the group consisting of [0422] light-curable bi- or tricyclic compounds Q(Y.sub.xZ.sub.e).sub.b wherein [0423] Q denotes a saturated or olefinically unsaturated bi- or tricyclic structural element, [0424] each index b is a natural number selected from the group of the natural numbers 1, 2, and 3, [0425] each Z denotes a light-curable group, [0426] each index e is a natural number selected from the group of the natural numbers 1, 2 and 3, [0427] each Y in the structure Q(Y.sub.xZ.sub.e).sub.b with x=1 denotes a structural element which connects the structural element Q to e structural elements Z and which denotes a straight or branched alkylene group, wherein the alkylene group may be interrupted by oxygen atoms, and [0428] each index x is 0 or 1, [0429] 7,7,9-trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate (UDMA), [0430] 7,9,9-trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate [0431] 7,9-dimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate [0432] 3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate [0433] 1,5,5-trimethyl-1-[(2-methacryloyloxyethyl)carbamoylmethyl]-3-(2-methacryloyloxyethyl)carbamoylcyclohexane [0434] 7,7,9,9-tetramethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate [0435] 2,7,7,9,15-pentamethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate [0436] 2,7,9,9,15-pentamethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate [0437] 2,7,9,15-tetramethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate [0438] 2,15-dimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate [0439] 1,5,5-trimethyl-1-[(1-methacryloyloxypropan-2-yl)carbamoylmethyl]-3-(1-methacryloyloxypropan-2-yl)carbamoylcyclohexane [0440] 2,7,7,9,9,15-hexamethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate, [0441] alkoxylated bisphenol A di(meth)acrylates having 2 to 6 alkoxy units, [0442] poly(meth)acrylates containing hydroxyl groups, selected from the group consisting of dipentaerythritol di(meth)acrylate, alkoxylated dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, alkoxylated dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, alkoxylated dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, alkoxylated dipentaerythritol penta(meth)acrylate, pentaerythritol di(meth)acrylate, alkoxylated pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, alkoxylated pentaerythritol tri(meth)acrylate, and [0443] light-curable, chain-like and/or cyclic and/or cage-type polysiloxanes,

[0444] (A2) 40% to 90% by weight, preferably 50% to 80% by weight, more preferably 60% to 75% by weight, of 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (bis-GMA) and/or light-curable derivatives of diisocyanatodiphenylmethane (MDI) and/or light-curable derivatives of tetramethyl-m-xylylene diisocyanate (TMXDI),

[0445] (A5) 0% to 15% by weight, preferably 0% to 10% by weight, more preferably 0% to 5% by weight, most preferably 0% by weight, of further free-radically polymerizable monomers that cannot be assigned to (A4) or (A2),

[0446] wherein the percentages by weight of (A4), (A2) and (A5) are based on the total mass of the monomers (A).

[0447] 14. Dental, light-curable, one-component composite composition according to any of Aspects 1 to 5, wherein component (A) comprises more than 60% by weight of light-curable, chain-like and/or cyclic and/or cage-type polysiloxanes.

[0448] 15. Dental, light-curable, one-component composite composition according to any of the preceding aspects, wherein the fillers (B) consist of and/or are producible by mixing

[0449] (B1) 2% to 25% by weight, preferably 3% to 20% by weight, of inorganic filler having a D.sub.50 of 1 nm to 200 nm, and further filler constituents, preferably

[0450] (B2) 40% to 90% by weight, preferably 50% to 80% by weight, of inorganic filler having a D.sub.50 of greater than 1 μm to 10 μm,

[0451] (B3) 8% to 50% by weight, preferably 15% to 40% by weight, of inorganic filler in a size having a D.sub.50 of 0.4 μm to 1.0 μm and

[0452] (B4) 0% to 25% by weight, preferably 0% to 15% by weight, of further fillers that cannot be assigned to (B1), (B2) or (B3),

[0453] wherein the percentages by weight of (B1), (B2), (B3) and (B4) are based on the total mass of the fillers (B).

[0454] 16. Dental, light-curable, one-component composite composition according to Aspect 15, wherein

[0455] the particles of the inorganic filler (B1) are not aggregated and not agglomerated and/or the inorganic filler (B1) is in a size having a D.sub.50 below 100 nm, preferably below 70 nm, and/or

[0456] the inorganic filler (B2) is in a size having a D.sub.50 of 1.2 μm to 5.0 μm, preferably of 1.5 μm to 4.0 μm, and/or

[0457] the inorganic filler (B3) is in a size having a D.sub.50 of 0.5 μm to 0.9 μm and preferably of 0.6 μm to 0.8 μm.

[0458] 17. Dental, light-curable, one-component composite composition according to any of Aspects 15 or 16, wherein (B1) contains [0459] oxides or mixed oxides selected from the group consisting of the elements silicon, titanium, yttrium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, ytterbium, lanthanum, cerium, aluminium and mixtures thereof, preferably silica, and/or [0460] sulfides, selenides and tellurides of metals, mixed metals and mixtures thereof and/or [0461] salts of the rare earths, of scandium and of yttrium, preferably ytterbium fluoride, and/or [0462] salts of barium and of strontium, preferably barium sulfate and/or strontium fluoride, and/or [0463] mixed fluorides between ytterbium fluoride and strontium fluoride, preferably strontium fluoride-doped ytterbium fluoride and/or ytterbium fluoride-doped strontium fluoride.

[0464] 18. Dental, light-curable, one-component composite composition according to any of Aspects 15 to 17, wherein constituents (B2) and (B3) comprise: [0465] materials based on oxides or mixed oxides of SiO.sub.2, ZrO.sub.2, TiO.sub.2 and/or [0466] quartz glass ceramic or glass powder, barium silicate glasses, barium fluorosilicate glasses, strontium silicate glasses, strontium borosilicates, Li/Al silicate glasses, barium glasses, calcium silicates, sodium aluminium silicates, fluoroaluminium silicate glasses, oxides of aluminium or silicon, zeolites, apatite, zirconium silicates and/or [0467] metal salts, preferably barium sulfate or calcium fluoride, and/or [0468] ytterbium fluoride.

[0469] 19. Dental, light-curable, one-component composite composition according to any of Aspects 15 to 18,

[0470] wherein the ratio of the total mass of (B2) to (B3) is in the range from 1:1 to 12:1, preferably in the range from 1.5:1 to 8:1 and/or

[0471] wherein the ratio of the average particle size of (B2) to the average particle size of (B3) is in the range from 1.5:1 to 10:1, preferably in the range from 2:1 to 5:1.

[0472] 20. Dental, light-curable, one-component composite composition according to any of Aspects 15 to 19, wherein (B4) comprises [0473] reinforcing filler materials, preferably glass fibres or polyamide or carbon fibres and/or [0474] further inorganic fillers and/or [0475] splinter or bead polymers, preferably bead polymers of homo- or copolymers of organically curable monomers.

[0476] 21. Dental, light-curable, one-component composite composition according to any of Aspects 15 to 20,

[0477] wherein components (B1) and/or (B2) and/or (B3) and/or (B4) have been organically surface-modified, preferably silanized.

[0478] 22. Dental, light-curable, one-component composite composition according to any of Aspects 15 to 21, wherein components (B1) and/or (B2) and/or (B3) and/or (B4) have been surface-modified by compounds of the general formula X-Sp-V

[0479] wherein “X” and “V” denote functional groups connected to one another by a linker “Sp” and wherein [0480] the functional group “X” is selected such that it can enter into a corresponding bond to the surface of the filler particle with complex formation, and is preferably a group of the silane, phosphate, phosphonate, carboxylate, dithiophosphate, dithiophosphonate, amine or amide type, and [0481] the linker “Sp” has linear or branched alkyl chains, aromatic systems or combinations of these groups, each of which may be interrupted by heteroatoms such as 0, N, or P or by a urethane group and [0482] the functional group “V” has light-curable groups, preferably (meth)acrylate groups.

[0483] 23. Dental, light-curable, one-component composite composition according to any of Aspects 15 to 22, wherein components (B1) and/or (B2) and/or (B3) and/or (B4) have been silanized with a compound of the formula (1) or (2)

##STR00008##

[0484] wherein R.sup.1 denotes a C1- to C4-alkyl group, and

[0485] R.sup.2 denotes a C1- to C8-alkyl group, and

[0486] R.sup.3 denotes a hydrogen atom or a methyl group, and

[0487] a=1, 2 or 3, and

[0488] b=3-a, and

[0489] n=1 to 8, and

[0490] m=1 to 8.

[0491] 24. Cured composite composition, obtained by light curing of a dental, light-curable, one-component composite composition according to any of the preceding aspects.

[0492] 25. Dental, light-curable, one-component composite composition according to any of Aspects 1 to 23, for use in a method of dental treatment, preferably for use in a method of dental treatment having the following steps: [0493] heating the composite composition to a temperature of 40° C. or more, preferably a temperature in the range from 40° C. to 80° C., preferably in an oven and/or by irradiation, preferably with IR rays, [0494] contacting the composite composition that has been heated to a temperature of 40° C. or more, preferably a temperature in the range from 40° C. to 80° C., with a patient's tooth to be treated, preferably as dental filling material, lining material, luting material and fissure sealant.

[0495] 26. Use of a composite composition according to any of Aspects 1 to 23 for production of a dental product, wherein the production is not effected on the human or animal body.

[0496] 27. Device for applying a composite composition, comprising a cavity filled at least partly with an amount of a composite composition according to any of Aspects 1 to 23 and

[0497] an application tip connected to the cavity and having an exit opening for the composite composition.

[0498] 28. Device according to Aspect 27, wherein the exit opening has a cross-sectional exit area in the range from 0.2 to 3.0 mm.sup.2, preferably a cross-sectional exit area of not more than 2.0 mm.sup.2, more preferably a cross-sectional exit area of not more than 1.5 mm.sup.2.

[0499] 29. Device according to any of Aspects 27 or 28, wherein

[0500] the application tip is a cannula preferably consisting of metal or plastic and/or

[0501] the device is selected from the group consisting of compules and syringes.

[0502] 30. Method of producing a composite composition according to any of Aspects 1 to 23 or for producing a device for application of a composite composition according to any of Aspects 27 to 29, having the following step:

[0503] mixing the constituents [0504] (A) monomers in an amount of 6% to 35% by weight, based on the total amount of the composite composition, preferably 10% to 35% by weight, more preferably 10% to 25% by weight, [0505] (B) fillers in an amount of 65% to 93% by weight, preferably 65% to 89% by weight, more preferably 75% to 89% by weight, based on the total amount of the composite composition, [0506] (C) initiators in an amount of 0.001% to 3% by weight based on the total amount of the composite composition, [0507] (D) further additives in an amount of 0.001% to 5% by weight based on the total amount of the composite composition,

[0508] to give the composite composition,

[0509] wherein the constituents are selected such that the viscosity η.sub.20 of the composite composition at 20° C. is greater than 400 Pa*s and the viscosity η.sub.50 of the composite composition at 50° C. is less than 150 Pa*s and wherein the quotient η.sub.50/η.sub.20 of the viscosity of the composite composition at 50° C. and the viscosity of the composite composition at 20° C. is less than 0.125, preferably less than 0.1.

[0510] 31. Method according to Aspect 30, wherein

[0511] constituent (A) is produced by the following steps: [0512] providing at least [0513] (A-i) one first monomer substance and [0514] (A-ii) one second monomer substance, [0515] wherein [0516] the viscosity η.sub.20 of the second monomer substance (A-ii) at 20° C. is greater than 100 Pa*s, [0517] the viscosity η.sub.20 of the first monomer substance (A-i) at 20° C. is greater than 100 mPa*s, [0518] the viscosity of the second monomer substance (A-ii) at 20° C. is greater than that of the first monomer substance (A-i) and [0519] the mass ratio of the first monomer substance (A-i) to the second monomer substance (A-ii) is in the range from 2:1 to 1:10, [0520] wherein the second monomer substance (A-ii) preferably contains at least 40% by weight of 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (bis-GMA) and/or light-curable derivatives of diisocyanatodiphenylmethane (MDI) and/or light-curable derivatives of tetramethyl-m-xylylene diisocyanate (TMXDI), where the percentage by weight is based on the total mass of the monomers (A), and [0521] mixing the monomer substances (A-i) and (A-ii) provided, prior to the and/or in the course of mixing with constituents (B), (C) and (D), and/or wherein

[0522] constituent (B) is produced by mixing [0523] (B1) 2% to 25% by weight, preferably 3% to 20% by weight, of inorganic filler having a D.sub.50 of 1 nm to 200 nm, and further filler constituents, preferably (B2) 40% to 90% by weight, preferably 50% to 80% by weight, of inorganic filler having a D.sub.50 of greater than 1 μm to 10 μm, [0524] (B3) 8% to 50% by weight, preferably 15% to 40% by weight, of inorganic filler in a size having a D.sub.50 of 0.4 μm to 1.0 μm and [0525] (B4) 0% to 25% by weight, preferably 0% to 15% by weight, of further fillers that cannot be assigned to (B1), (B2) or (B3),

[0526] wherein the percentages by weight of (B1), (B2), (B3) and (B4) are based on the total mass of the fillers (B).

[0527] 32. Method according to either of Aspects 30 and 31, having the following additional step for preparation of the device for application of a composite composition: [0528] introducing the composite composition according to any of Aspects 1 to 23 that has been produced into a cavity of a previously unfilled device for application of a composite composition.

[0529] 33. Method of preparing for a dental treatment of a patient, having the following step: heating a composite composition according to any of Aspects 1 to 23 or a device according to any of Aspects 27 to 29, preferably produced by a method according to Aspect 30 to 32, to a temperature of 40° C. or more, preferably a temperature in the range from 40° C. to 80° C., preferably in an oven and/or by irradiation, preferably with IR rays.

[0530] 34. Use of a dental, light-curable, one-component composite composition according to any of Aspects 1 to 23 in a method of dental treatment, preferably for use in a method of dental treatment having the following steps: [0531] heating the composite composition to a temperature of 40° C. or more, preferably a temperature in the range from 40° C. to 80° C., preferably in an oven and/or by irradiation, preferably with IR rays, [0532] contacting the composite composition that has been heated to a temperature of 40° C. or more, preferably a temperature in the range from 40° C. to 80° C., with a patient's tooth to be treated, preferably as dental filling material, lining material, luting material and fissure sealant.