초록 ▼

The present invention relates to novel free-radically curable dental compositions, comprising chain-like and/or cyclic and/or cage-type polysiloxanes substituted by free-radically polymerizable groups and having at least 3 silicon atoms and/or mixed forms thereof, disiloxanes substituted by free-rad

The present invention relates to novel free-radically curable dental compositions, comprising chain-like and/or cyclic and/or cage-type polysiloxanes substituted by free-radically polymerizable groups and having at least 3 silicon atoms and/or mixed forms thereof, disiloxanes substituted by free-radically polymerizable groups, optionally one, two, three or more free-radically curable dental monomers having no silicon atom, fillers, initiators and/or catalysts for free-radical polymerization, and also further customary additives, to the cured dental products formed from the dental compositions of the invention, and to the respective use thereof as dental material, especially as flowable filling composites (called “flow materials”), core buildup materials and luting cements. The invention further relates to a method for producing the dental compositions and to a process for producing a respective dental product. Additionally claimed are inventive kits containing the novel free-radically curable dental compositions.

대표청구항 ▼

1. A free radically curable dental composition comprising a) chain-like polysiloxanes, cyclic polysiloxanes, cage type polysiloxanes, mixed forms thereof, or combinations thereof, wherein the polysiloxanes are substituted by free radically polymerizable groups and have at least 3 silicon atoms,b) di

1. A free radically curable dental composition comprising a) chain-like polysiloxanes, cyclic polysiloxanes, cage type polysiloxanes, mixed forms thereof, or combinations thereof, wherein the polysiloxanes are substituted by free radically polymerizable groups and have at least 3 silicon atoms,b) disiloxanes substituted by free radically polymerizable groups and having the following structure: R1aR2(3-a)Si—O—SiR2(3-b)R1b whereinR2 is selected from the group consisting of alkyl, alkenyl, aryl, alkylaryl, and arylalkyl, wherein different R2 may be the same or different,R1 is YZ,Z is a free radically polymerizable group selected from the structural elements —O—(C═O)—CH═CH2, —O—(C═O)—C(CH3)═CH2, —(C═O)—CH═CH2, —(C═O)—C(CH3)═CH2, —CH═CH2, —C(CH3)═CH2, —NH—(C═O)—CH═CH2 and —NH—(C═O)—C(CH3)═CH2,wherein different Z may be the same or different,a is 1 or 2,b is 1 or 2,Y is a connecting element which links the silicon atom to the free radically polymerizable group and consists of an alkylene group,wherein the alkylene group is an unsubstituted, linear, straight chain or branched hydrocarbyl chain orwherein the alkylene group is an unsubstituted hydrocarbyl group interrupted by a urethane group, urea group, ester group, thiourethane group or amide group orwherein the alkylene group is a hydrocarbyl group substituted by a hydroxyl group or this hydroxyl group has been esterified or etherified orwherein the alkylene group is a hydrocarbyl group interrupted by an oxygen atom, a nitrogen atom, a sulfur atom, ester groups, thioester groups, or combinations thereof and is substituted by a hydroxyl group or this hydroxyl group has been esterified or etherified, andwherein different Y may be the same or different, andwherein Y contains 20 or fewer carbon atoms, andwherein YZ is chosen such that Z always has a maximum number of atoms,c) optionally one, two, three or more free radically curable monomers having no silicon atom,d) 85 percent by weight or less of one or more fillers based on the total weight of the free radically curable dental composition,e) initiators, catalysts, or combinations thereof for the free radical polymerization andf) further additives for use in dental materials. 2. The dental free radically curable composition as claimed in claim 1, wherein the polysiloxanes a) are obtained by hydrolysis or partial hydrolysis and subsequent condensation or co-condensation of one, two, three or more compounds R1aR2bSiXc wherein X is halogen or alkoxy,R2 is selected from the group consisting of alkyl, alkenyl, aryl, alkylaryl, and arylalkyl, wherein different R2 may be the same or different,R1 is YZ,Z is a free radically polymerizable group selected from the structural elements —O—(C═O)—CH═CH2, —O—(C═O)—C(CH3)═CH2, —(C═O)—CH═CH2, —(C═O)—C(CH3)═CH2, —CH═CH2, —C(CH3)═CH2, —NH—(C═O)—CH═CH2 and —NH—(C═O)—C(CH3)═CH2,wherein different Z may be the same or different,a is 1 or 2,b is 0 or 1,c is 2 or 3,a+b+c=4,Y is a connecting element which links the silicon atom to the free radically polymerizable group and consists of an alkylene group,wherein the alkylene group is an unsubstituted, linear, straight chain or branched hydrocarbyl chain orwherein the alkylene group is an unsubstituted hydrocarbyl group interrupted by a urethane group, urea group, ester group, thiourethane group or amide group orwherein the alkylene group is a hydrocarbyl group substituted by a hydroxyl group or this hydroxyl group has been esterified or etherified orwherein the alkylene group is a hydrocarbyl group interrupted by an oxygen atom, a nitrogen atom, a sulfur atom, ester groups, thioester groups, or combinations thereof and is substituted by a hydroxyl group or this hydroxyl group has been esterified or etherified, andwherein different Y may be the same or different, andwherein Y contains 20 or fewer carbon atoms, andwherein YZ is chosen such that Z always has a maximum number of atoms. 3. The free radically curable dental composition as claimed in claim 1, wherein the composition contains: constituent a) in an amount of 10%-35% by weight,constituent b) in an amount of 2%-25% by weight,constituent c) in an amount of 0%-20% by weight,constituent d) in an amount of 50%-85% by weight,constituent e) in an amount of 0.001%-5% by weight andconstituent f) in an amount of 0.001%-20% by weight,and wherein the respective percentages by weight are based on the total mass of the composition. 4. The free radically curable dental composition as claimed in claim 1, wherein the composition contains, as constituent b), 1,3 bis(3methacryloyloxypropyl)tetramethyldisiloxane. 5. The free radically curable dental composition as claimed in claim 1, wherein the composition does not contain any constituent c). 6. The free radically curable dental composition as claimed in claim 1, containing a mixture of fillers d) comprising: d1) organically surface modified inorganic nanoparticles having an average particle size of less than 200 nm,d2) inorganic microparticles having an average particle size in the range from 0.4 μm to 10 μm andd3) optionally further fillers which do not correspond to d1) and d2). 7. The free radically curable dental composition as claimed in claim 6, wherein component d1) is at least partly in nonagglomerated or nonaggregated form. 8. The free-radically curable dental composition as claimed in claim 6, wherein component d2) contains two or more micro fractions, wherein a first micro fraction or each of a plurality of first micro fractions has an average particle size in the range from 1 to 10 μm, and wherein a second microparticle fraction or each of a plurality of second microparticle fractions has an average particle size in the range from greater than 0.4 μm to less than 1 μm. 9. The free-radically curable dental composition as claimed in claim 8, wherein the ratio of the total mass of the first microparticle fraction(s) to the total mass of the second microparticle fraction(s) is in the range from 1:1 to 12:1. 10. The free-radically curable dental composition as claimed in claim 8, wherein the ratio of the average particle size of the first or a first microparticle fraction to the average particle size of the second or a second microparticle fraction of component d2) is in the range from 1.5:1 to 10:1. 11. The free-radically curable dental composition as claimed in claim 6, wherein at least some of the microparticles of component d2) are selected from the group consisting of organically surface modified particles, dental glass particles, and combinations thereof, wherein at least some of the microparticles of component d2) are organically surface modified dental glass particles. 12. The free-radically curable dental composition as claimed in claim 6, wherein the composition contains: component d1) in an amount of 1%-20% by weight,component d2) in an amount of 30%-84% by weight,component d3) in an amount of 0%-30% by weight,and wherein the percentages by weight are based on the total mass of the free radically curable dental composition. 13. The free-radically curable dental composition as claimed in claim 1, wherein constituent d) contains x ray opaque fractions. 14. The free-radically curable dental composition as claimed in claim 13, wherein the x ray opaque fractions are nanoscale YbF3, BaSO4, or combinations thereof. 15. The free-radically curable dental composition as claimed in claim 1, wherein the free radically polymerizable groups are acrylate or methacrylate groups. 16. A process for producing a cured dental composition, the method comprising: providing a free-radically curable dental composition as claimed in claim 1, andpolymerizing the free-radically curable dental composition. 17. A method for producing a free-radically curable composition as claimed in claim 1 comprising mixing constituents a) to f). 18. A cured free-radically curable dental composition produced by the method of claim 16, wherein the cured dental composition has a shrinkage of less than 3.5% by volume. 19. A kit comprising at least one component selected from the group consisting of a dental syringe, a dental compule, a double-chamber cartridge, and combinations thereof, wherein the kit further comprises (i) one or more free-radically curable dental compositions as claimed in claim 1,(ii) one or more base pastes and one or more catalyst pastes, wherein a free-radically curable dental material as claimed in claim 1 is obtained by mixing a base paste and a corresponding catalyst paste,or combinations of (i) and (ii). 20. The free radically curable dental composition as claimed in claim 1, wherein the composition contains: constituent a) in an amount of 15%-25% by weight,constituent b) in an amount of 5%-15% by weight,constituent c) in an amount of 0%-10% by weight,constituent d) in an amount of 60%-78% by weight,constituent e) in an amount of 0.1%-2% by weight andconstituent f) fi in an amount of 0.001%-10% by weight,and wherein the respective percentages by weight are based on the total mass of the composition.