Kit and method for indirect chairside production of composite inlays

Abstract

The present invention relates to a kit for indirect production of composite inlays, comprising a polymerizable material for production of a dental model, a polymerizable material for production of an inlay, a polymerizable material for luting of a crosslinked and non-sand-blasted, non-silanized, non-etched, non-primed and non-roughened composite inlay, the surfaces of which have been fully polymerized, in the cavity. Also disclosed is a polymerizable material for increasing the bond strength between the polymerizable material for luting of a crosslinked non-sand-blasted, non-silanized, non-etched, non-primed and non-roughened composite inlay, the surfaces of which have been fully polymerized, in the cavity, and the hard substance of the tooth, and an acid solution for surface etching of the hard substance of the tooth. The invention further relates to methods for producing a composite inlay.

Claims

1. A kit for restoration of a tooth cavity, comprising A. a polymerizable material for production of a dental model, comprising either A.a. addition-crosslinking silicones or A.b. cationically curable polyethers, B. a polymerizable material for production of a composite inlay, comprising B.a. a total amount of fillers in the range from more than 75 to 95% by weight, based on the total mass of the polymerizable material for production of a composite inlay B, B.b. a total amount of polymerizable monomers or monomer mixtures in the range from 3 to less than 25% by weight, based on the total mass of the polymerizable material for production of a composite inlay B, wherein the total amount of polymerizable monomers is selected from the group consisting of carbosilanes, monomers which cure via ring-opening metathesis polymerization, and dental (meth)acrylate monomers, and B.c. one or more photoinitiator(s) and/or initiator(s) for chemical curing, and C. a polymerizable material for luting of a composite inlay in the cavity, comprising C.a. a total amount of fillers of more than 40 to 80% by weight based on the total mass of the polymerizable material for luting of a composite inlay in the cavity C, C.b. 16.8 to less than 60% by weight of a total amount of one, two or more polymerizable monomers, based on the total mass of the polymerizable material for luting of a composite inlay in the cavity C, the one, two or more polymerizable monomers being selected from the group consisting of carbosilanes, monomers which cure via ring-opening metathesis polymerization, and dental (meth)acrylate monomers, C.c. 0.1 to 10% by weight of one or more photoinitiator(s) and/or initiator(s) for chemical curing, based on the total mass of the polymerizable material for luting of a composite inlay in the cavity C, C.e. polymerization inhibitors, and C.f. less than 3% by weight of additives, based on the total mass of the polymerizable material, for luting of a composite inlay in the cavity C, wherein the composite inlay which has not been sand-blasted, nor silanized, nor etched, nor primed, nor roughened, before being bonded into the tooth cavity and is obtainable by curing the polymerizable material for production of a composite inlay B. has fully polymerized surfaces, and the deformation under pressure of the polymerizable material for production of a dental model A., measured to ISO 4823, is not more than 3.5%, and the polymerizable material for production of a dental model A has a Shore D hardness, determined to DIN 53505, of between 25 and 85, and the polymerization shrinkage of the polymerizable material for production of a composite inlay B., measured by the bonded-disc method, is not more than 2.0%, and wherein the adhesive force between the composite inlay and the luting cement, measured by the VOCO test method, is at least 8 MPa.

2. The kit for restoration of a tooth cavity according to claim 1, wherein A.a. comprises A.a.1. 10-40% by weight of polysiloxanes comprising polyatomic crosslinkable groups, A.a.2. 2-10% by weight of organo-hydropolysiloxanes, A.a.3. 0.01-1% by weight of catalyst, and A.a.4. 50-90% by weight of fillers, wherein the percentages by weight are based on the total mass of the addition-crosslinking silicones, or A.b. comprises A.b.1. 30-90% by weight of aziridine group-bearing copolymers, A.b.2. 1-10% by weight of starter substances suitable for bringing about the curing of the aziridine group-bearing copolymers, A.b.3. 3-45% by weight of fillers, A.b.4. 2-85% by weight of additives, wherein the percentages by weight are based on the total mass of the cationically curable polyethers, and B.a. comprises B.a.1. a total amount in the range from 2 to 30% by weight of organically surface-modified nanoparticles having a mean primary particle size less than 200 nm and B.a.2. a total amount in the range from 45 to less than 85% by weight of microparticles having a mean particle size in the range from 0.4 μm to 10 μm, wherein the percentages by weight for components B.a.1 and B.a.2 are based on the total mass of the polymerizable material for production of a composite inlay B, and C.a. comprises C.a.1. one or more fractions of microparticles having a mean particle size of 0.4 μm to 10 μm, C.a.2. nanoscale, solid particles having a primary particle size of not more than 200 nm.

3. The kit for restoration of a tooth cavity according to claim 2, wherein, from the polymerizable material for production of a dental model A., component A.a.1 comprises a mixture of two linear vinylmethylsiloxanes, wherein the dynamic viscosity, measured to DIN 53018 at 25° C., of one linear vinylmethylsiloxane having terminal vinyl groups is in the range from 200 mPas up to and including 2500 mPas (low-viscosity vinylmethylsiloxane), and that of the second linear vinylmethylsiloxane likewise having terminal vinyl groups is within the range from greater than 2500 mPas up to and including 65000 mPas (high-viscosity vinylmethylsiloxane), and wherein the weight ratio of the low-viscosity to the high-viscosity vinylmethylsiloxane is 6:1 to 1:4, wherein component A.a.2 has two to three Si—H bonds per molecule, wherein component A.a.3 is a platinum catalyst, wherein component A.a.4 is selected from the group consisting of cristobalite, silicates, montmorillonites, bentonites, metal oxide powders, titanium dioxide, gypsum, inorganic salts, glass, crystalline and amorphous silica, quartz, diatomaceous earth, and nanoscale particles in the form of non-aggregated and non-agglomerated particles, wherein the fillers are in surface-treated form, wherein the addition-crosslinking silicone A.a is a two-component system composed of base paste and catalyst paste, wherein base paste and catalyst paste are present in a volume ratio of 10:1 to 1:10 and wherein A.a has a processing time at 23° C. of more than 30 seconds, and a setting time at 30° C. of less than 7 minutes.

4. The kit for restoration of a tooth cavity according to claim 2, wherein the polymerizable material for production of a composite inlay B comprises component B.a.1 to an extent of more than 8% by weight to 30% by weight of organically surface-modified nanoparticles having a mean primary particle size less than 100 nm, and component B.a.2 to an extent of more than 65 to less than 85% by weight of microparticles having a mean particle size of 0.4 μm to 10 μm, wherein the percentages by weight are based on the total mass of the polymerizable material for production of a composite inlay B.

5. The kit for restoration of a tooth cavity according to claim 4, wherein the microparticles of component B.a.2 have a multimodal particle size distribution.

6. The kit for restoration of a tooth cavity according to claim 2, wherein A.a further comprises: A.a.5 additives, wherein component A.a.5 comprises one or more inhibitor(s) in amounts of 0.001-0.15% by weight, based on the total mass of component A.a, one or more stabilizer(s) in amounts of 0.1 to 5% by weight, based on the total mass of component A.a, and one or more rheology modifiers in amounts of 1 to 10% by weight, based on the total mass of component A.a.

7. The kit for restoration of a tooth cavity according to claim 1, wherein the dental (meth)acrylates of the polymerizable material for production of a composite inlay B are selected from the groups of B.b.1 comprising one, two or more monomers selected from the group consisting of 2,2-bis[4-(2-hydroxy-3-(meth)acryloyloxypropoxy)phenyl)propane (bis-GMA), bisphenol A glycidyl (meth)acrylate, bisphenol B glycidyl (meth)acrylate, bisphenol C glycidyl (meth)acrylate, bisphenol F glycidyl (meth)acrylate, alkoxylated bisphenol A glycidyl (meth)acrylate, alkoxylated bisphenol A di(meth)acrylate, 7,7,9-trimethyl-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate (UDMA), compounds which are free-radically polymerizable via (meth)acrylate groups and comprise a polyalicyclic structural element, and ormocers and B.b.2 comprising one, two or more further free-radically polymerizable monomer(s) selected from the group consisting of (meth)acrylates which are not part of the list described for B.b.1, and wherein the ratio of the mass of components B.b.1 to the mass of components B.b.2 is in the range from 10:1 to 1:10.

8. The kit for restoration of a tooth cavity according to claim 7, wherein the one, two or more further free-radically polymerizable monomers selected from the group consisting of (meth)acrylates of components B.b.2 are selected from the group consisting of ethylene glycol di(meth)acrylate (EGDMA), 1,6-hexanediol di(meth)-acrylate (HEDMA), triethylene glycol di(meth)acrylate (TEDMA), 1,12-dodecanediol di(meth)acrylate (DODMA), decanediol di(meth)-acrylate, polyethylene glycol di(meth)acrylate (PEGDMA), butanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-hydroxypropyl 1,3-di(meth)acrylate, 3-hydroxypropyl 1,2-di(meth)-acrylate, pentaerythrityl di(meth)acrylate, glyceryl di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1,2-dihydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)-acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxypropyl 1,3-di(meth)acrylate and 3-hydroxypropyl 1,2-di(meth)acrylate, 2-(meth)-acryloyloxyethyl dihydrogenphosphate, bis[2-(meth)acryloyloxyethyl] hydrogenphosphate, 2-(meth)acryloyloxyethylphenyl hydrogenphosphate, 6-(meth)acryloyloxyhexyl dihydrogenphosphate, 10-(meth)acryloyloxydecyl dihydrogenphosphate (MDP), 1,3-di(meth)acryloyloxypropane 2-dihydrogenphosphate, 1,3-di(meth)acryloyloxypropane 2-phenyl hydrogenphosphate and bis[5-(2-(meth)acryloyloxyethoxycarbonyl)heptyl] hydrogenphosphate, 4-(meth)acryloyloxyethyltrimellitic acid (4-MET), 4-(meth)acryloyloxyethyltrimellitic anhydride (4-META), 4-(meth)acryloyloxydecyltrimellitic acid, 4-(meth)acryloyloxydecyltrimellitic anhydride, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, 1,4-di(meth)acryloyloxypyromellitic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxyethylphthalic acid and 2-(meth)acryloyloxyethylhexahydrophthalic acid, and polymerizable phosphoric esters bearing a polyalicyclic structural element.

9. The kit for restoration of a tooth cavity according to claim 1, wherein the deformation under pressure of the polymerizable material for production of a dental model A, measured to ISO 4823, is not more than 1.5%, and the polymerization shrinkage of the polymerizable material for production of a composite inlay B, measured by the bonded-disc method, is not more than 1.8%.

10. The kit for restoration of a tooth cavity according to claim 1, further comprising: D. a polymerizable material for establishment of a bond between the hard substance of the tooth and luting cement, comprising D.a. one or more adhesion monomer(s) containing a phosphoric acid radical, a diphosphoric acid radical, a phosphonic acid radical, a thiophosphoric acid radical or a sulfonic acid radical, D.b. monomers copolymerizable with component D.a. other than component D.a., D.c. one or more fillers, D.d. one or more photoinitiator(s) and/or initiator(s) for chemical curing, and D.e. polymerization inhibitors.

11. The kit for restoration of a tooth cavity according to claim 1, further comprising E. an acid solution for etching the hard substance of the tooth.

12. The kit for restoration of a tooth cavity according to claim 1, wherein the polymerizable material for luting of a composite inlay in the cavity C. further comprises: C.d. one or more adhesion monomer(s) other than component C.b. for luting of the composite inlay in the cavity, wherein the component C.d. adhesion monomer(s) comprises a phosphoric acid radical, a diphosphoric acid radical, a phosphonic acid radical, a thiophosphoric acid radical or a sulfonic acid radical in a proportion of less than 35% by weight, based on the total mass of the polymerizable material for luting of a composite inlay in the cavity C.

13. A method for production of a composite inlay, the method comprising the following steps: casting an impression of a tooth cavity with a first polymerizable material for production of a dental model A, polymerizing the first polymerizable material to produce the dental model A, applying a second polymerizable material for production of a composite inlay B, to the dental model, formed by the first polymerized material, forming the second polymerizable material, into the form of an inlay which fills the tooth cavity of which an impression has been taken, polymerizing the second polymerizable material to produce the composite inlay B, withdrawing the polymerized composite inlay B produced from the dental model A, removing the inhibited or incompletely polymerized second polymerizable material from the composite inlay B by wiping-off and application of alcohol or alcoholic or aqueous disinfection solutions; wherein the first polymerizable material for production of a dental model A comprises either: A.a.) addition-crosslinking silicones, or A.b.) cationically curable polyethers; and wherein the deformation under pressure of said first polymerizable material, measured to ISO 4823, is not more than 3.5%, and wherein the first polymerizable material has a Shore D hardness, determined to DIN 53505, of between 25 and 85; wherein the second polymerizable material for production of a composite inlay B comprises: B.a.) a total amount of fillers in the range from more than 75 to 95% by weight, based on the total mass of the second polymerizable material, B.b.) a total amount of polymerizable monomers or monomer mixtures in the range from 3 to less than 25% by weight, based on the total mass of the second polymerizable material, wherein the total amount of polymerizable monomers is selected from the group consisting of carbosilanes, monomers which cure via ring-opening metathesis polymerization, and dental (meth)acrylate monomers, and B.c.) one or more photoinitiator(s) and/or initiator(s) for chemical curing; wherein the polymerization shrinkage of the second polymerizable material as measured by the bonded-disc method is not more than 2.0%, and wherein the composite inlay B has fully polymerized surfaces and has not been sand-blasted, nor silanized, nor etched, nor primed, nor roughened.

14. The method for production of a composite inlay according to claim 13, wherein the first polymerizable material comprises either A.a. addition-crosslinking silicones comprising A.a.1. 10-40% by weight of polysiloxanes comprising polyatomic crosslinkable groups, A.a.2. 2-10% by weight of organo-hydropolysiloxanes, A.a.3. 0.01-1% by weight of catalyst, and A.a.4. 50-90% by weight of fillers wherein the percentages by weight are based on the total mass of the addition-crosslinking silicones, or A.b. cationically curable polyethers comprising A.b.1. 30-90% by weight of aziridine group-bearing copolymers, A.b.2. 1-10% by weight of starter substances suitable for bringing about the curing of the aziridine group-bearing copolymers, A.b.3. 3-45% by weight of fillers, and A.b.4. 2-85% by weight of additives, wherein the percentages by weight are based on the total mass of the cationically curable polyethers, and wherein component A.a.4 is selected from the group consisting of cristobalite, silicates, montmorillonites, bentonites, metal oxide powders, titanium dioxide, gypsum, inorganic salts, glass, crystalline and amorphous silica, quartz, diatomaceous earth, and nanoscale particles in the form of non-aggregated and non-agglomerated particles, wherein the addition-crosslinking silicone A.a is a two-component system composed of base paste and catalyst paste, wherein base paste and catalyst paste are present in a volume ratio of 10:1 to 1:10 and wherein A.a has a processing time at 23° C. of more than 30 seconds, and a setting time at 30° C. of less than 7 minutes, and wherein the deformation under pressure of the addition-crosslinked silicone A.a measured to ISO 4823 is not more than 3.5% and the Shore D hardness, determined to DIN 53505, is in the range between 25 and 85, and wherein the second polymerizable material comprises B.a. a total amount of fillers in the range from more than 75 to 95% by weight, based on the total mass of the second polymerizable material, wherein the total amount of fillers is a mixture of fillers comprising B.a.1. a total amount in the range from 2 to 30% by weight of organically surface-modified nanoparticles having a mean primary particle size less than 200 nm and B.a.2. a total amount in the range from 45 to less than 85% by weight of microparticles having a mean particle size in the range from 0.4 μm to 10 μm, wherein the percentages by weight for components B.a.1 and B.a.2 are based on the total mass of the second polymerizable material, and wherein the microparticles of component B.a.2 are selected from the group consisting of materials based on silicon dioxide, zirconium dioxide and/or titanium dioxide, and also mixed oxides, fumed silicas or precipitated silicas, quartz glass ceramics or dental glass powders, barium glasses or strontium glasses, fluoride ion-releasing glasses, oxides of aluminum or silicon, zeolites, apatites, zirconium silicates, sparingly soluble metal salts and X-ray-opaque fillers, and wherein the organically surface-modified nanoparticles of component B.a.1 are oxides or mixed oxides selected from the group consisting of oxides and mixed oxides of the elements silicon, titanium, yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, ytterbium, lanthanum, cerium, aluminum and mixtures thereof, wherein the surface-modified nanoparticles are silanized, and B.b. a total amount of polymerizable monomers or monomer mixtures in the range from 3 to 25% by weight is present, based on the total mass of the second polymerizable material, wherein the total amount of polymerizable monomer is selected from the group consisting of carbosilanes, monomers which cure via ring-opening metathesis polymerization, and dental (meth)acrylate monomers, wherein the dental (meth)acrylate monomers in the second polymerizable material are selected from the group consisting of B.b.1 comprising one, two or more monomers selected from the group consisting of 2,2-bis[4-(2-hydroxy-3-(meth)acryloyloxypropoxy)phenyl)propane (bis-GMA), bisphenol A glycidyl (meth)acrylate, bisphenol B glycidyl (meth)acrylate, bisphenol C glycidyl (meth)acrylate, bisphenol F glycidyl (meth)acrylate, ethoxylated bisphenol A glycidyl (meth)acrylate, alkoxylated bisphenol A di(meth)acrylate, 7,7,9-trimethyl-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydi(meth)acrylate (UDMA), compounds which are free-radically polymerizable via (meth)acrylate groups and comprise a polyalicyclic structural element, and ormocers and B.b.2 comprising one, two or more further free-radically polymerizable monomer(s) selected from the group consisting of (meth)acrylates which are not part of the list described for B.b.1, and wherein B.b.2 is selected from the group consisting of ethylene glycol di(meth)acrylate (EGDMA), 1,6-hexanediol di(meth)acrylate (HEDMA), triethylene glycol di(meth)acrylate (TEDMA), 1,12-dodecanediol di(meth)acrylate (DODMA), polyethylene glycol di(meth)acrylate (PEGDMA), butanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-hydroxypropyl 1,3-di(meth)acrylate, 3-hydroxypropyl 1,2-di(meth)acrylate, pentaerythrityl di(meth)acrylate, glyceryl di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)-acrylate, 3-hydroxypropyl (meth)acrylate, 1,2-dihydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-di-hydroxypropyl (meth)acrylate, 2-hydroxy-propyl 1,3-di(meth)acrylate and 3-hydroxypropyl 1,2-di(meth)acrylate, 2-(meth)acryloyloxyethyl dihydrogenphosphate, bis[2-(meth)acryloyloxyethyl] hydrogenphosphate, 2-(meth)acryloyloxy-ethylphenyl hydrogenphosphate, 6-(meth)-acryloyloxyhexyl dihydrogenphosphate, 10-(meth)acryloyloxydecyl dihydrogenphosphate (MDP), 1,3-di(meth)acryloyloxypropane 2-dihydrogenphosphate, 1,3-di(meth)acryloyloxypropane 2-phenyl hydrogenphosphate and bis[5-(2-(meth)acryloyloxyethoxycarbonyl)heptyl] hydrogenphosphate, 4-(meth)acryloyloxy-ethyltrimellitic acid (4-MET), 4-(meth)acryloyloxyethyltrimellitic anhydride (4-META), 4-(meth)acryloyloxy-decyltrimellitic acid, 4-(meth)acryloyl-oxydecyltrimellitic anhydride, 11-(meth)acryloyloxy-1,1-undecanedi-carboxylic acid, 1,4-di(meth)acryloyl-oxypyromellitic acid, 2-(meth)acryloyl-oxyethylmaleic acid, 2-(meth)acryloyloxy-ethylphthalic acid and 2-(meth)acryloyl-oxyethylhexahydrophthalic acid, and polymerizable phosphoric esters bearing a polyalicyclic structural element, and wherein the ratio of the mass of component B.b.1 to the mass of component B.b.2 is in the range from 10:1 to 1:10, and B.c. one or more photoinitiators and/or initiators for chemical curing, wherein the photoinitiators are selected from the group consisting of alpha-diketones, benzoin alkyl ethers, thioxanthones, benzophenones, acylphosphine oxides, acetophenones, ketals, titanocenes, sensitizing dyes and borate salts, and the initiators of chemical curing are selected from the group consisting of peroxides, barbituric acids, barbituric acid derivatives, salts of barbituric acid, salts of a barbituric acid derivative, malonyl-sulfamides and sulfur compounds in the +2 or +4 oxidation state, and wherein the photoinitiators are used individually or in mixtures, and the photoinitiators used individually or in mixtures are used in combination with accelerators, wherein the accelerators provided are amines, aldehydes, sulfur compounds, barbituric acids and tin compounds, and wherein the chemical catalysts are used in combination with redox partners, B.d. selected from the group consisting of inhibitors, fluoride-releasing substances, UV absorbers, dyes and flavorings, wherein the inhibitors are selected from the group consisting of hydroquinone monomethyl ether, phenols, phenothiazine, derivatives of phenothiazine, 2,3,6,6-tetramethylpiperidinyl-1-oxyl radicals, triphenylmethyl radicals, galvinoxyl radicals, 2,2-diphenyl-1-picrylhydrazyl radicals, tert-butylhydroxyanisole and 2,6-di-tert-butyl-4-methylphenol, and wherein the inhibited or incompletely polymerized second polymerizable material is removed from the composite inlay B by wiping-off and application of alcohols, and/or by application of aqueous/alcoholic solutions.

15. The method for production of a composite inlay according to claim 14, wherein component A.a.1 comprises a mixture of two linear vinylmethylsiloxanes, wherein the dynamic viscosity, measured to DIN 53018 at 25° C., of one linear vinylmethylsiloxane having terminal vinyl groups is in the range from 200 mPas up to and including 2500 mPas (low-viscosity vinylmethylsiloxane), and that of the second linear vinylmethylsiloxane likewise having terminal vinyl groups is within the range from greater than 2500 mPas up to and including 65000 mPas (high-viscosity vinylmethylsiloxane), and wherein the weight ratio of the low-viscosity to the high-viscosity vinylmethylsiloxane is 6:1 to 1:4.

16. The method for production of a composite inlay according to claim 14, wherein A.a further comprises: A.a.5 additives, wherein component A.a.5 comprises one or more inhibitor(s) in amounts of 0.001-0.15% by weight, based on the total mass of component A.a, one or more stabilizer(s) in amounts of 0.1 to 5% by weight, based on the total mass of component A.a, and one or more rheology modifiers in amounts of 1 to 10% by weight, based on the total mass of component A.a.

17. The method for production of a composite inlay according to claim 14, wherein component A.a.2 has two to three Si—H bonds per molecule, and component A.a.3 is a platinum catalyst.

18. The method for production of a composite inlay according to claim 14, wherein component B.a. further comprises: B.a.3. fillers other than B.a.1 and B.a.2, wherein the fillers of component B.a.3 are selected from the group consisting of fibers, finely divided chip 30 polymers, and bead polymers.

19. The method for production of a composite inlay according to claim 14, wherein the chemical catalysts are used in combination with accelerators; wherein the photoinitiators are used together with the catalysts of chemical curing; wherein the photoinitiator consists of a combination of camphorquinone/amine or of one or more phosphine oxides or of the combination of camphorquinone/amine/phosphine oxides, and the chemical catalyst consists of a combination of peroxide/amine or of the barbituric acid/barbituric acid derivative/salt of barbituric acid/salt of a barbituric acid derivative system and one or more heavy metal salt(s) and/or heavy metal complexes, wherein the heavy metal salt of the barbituric acid/barbituric acid derivative/salt of barbituric acid/salt of a barbituric acid derivative system is selected from the group consisting of iron salt, copper salt or cobalt salt and copper acetylacetonate or the bis(1-phenylpentane-1,3-dionato)copper(II) complex, wherein the barbituric acid/barbituric acid derivative/salt of barbituric acid/salt of a barbituric acid derivative system additionally comprises ionically bonded halogens or pseudohalogens, and wherein a peroxy compound as an oxidizing agent is added to the barbituric acid/barbituric acid derivative/salt of barbituric acid/salt of a barbituric acid derivative system.

20. The method for production of a composite inlay according to claim 13, further comprising repeating the application, forming and polymerizing of the second polymerizable material, when the inlay is to be built up layer by layer.

Description

EXAMPLES

(1) The invention is illustrated in detail by examples hereinafter, but these do not constitute a restriction of the subject matter of the invention.

(2) As examples, a polymerizable material for production of a dental model (example 1a), a polymerizable material for production of an inlay (example 2a), and a non-self-adhesive (example 3) and a self-adhesive (example 4) polymerizable material for luting of the composite inlay were produced as constituents of an inventive kit for indirect chairside production of composite inlays. For comparison, a polymerizable material for production of a dental model (example 1b) and a polymerizable material for production of an inlay (example 2b) were produced, these being unsuitable as constituents of an inventive kit for indirect chairside production of composite inlays.

(3) Unless stated otherwise, all figures are based on weight. The following abbreviations customary in the field are used:

(4) BHT: 2,6-di-tert-butyl-4-methylphenol

(5) Bis-GMA: 2,2-bis[4-(2-hydroxy-3-methacryloyloxy-propoxy)phenyl)propane

(6) DABE: ethyl p-N,N-dimethylaminobenzoate

(7) TEDMA: triethylene glycol dimethacrylate

(8) UDMA: 7,7,9-trimethyl-4,13-dioxo-5,12-diazahexadecane 1,16-dioxydimethacrylate

Example 1: Polymerizable Material for Production of a Dental Model

(9) TABLE-US-00001 Base paste 1a 1b A.a.5 Additive: Ethynylcyclohexanol 0.175 0.04 A.a.2 Si—H-functionalized polydimethylsiloxane (Si—H 14.52 10.98 content: 7.8 mmol/g) A.a.2 Si—H-functionalized polydimethylsiloxane (Si—H 4.57 content: 3.0 mmol/g) A.a.1 Vinyl-functionalized polydimethylsiloxane 5.83 5.05 (Vinyl content: 1.40 mmol/g; viscosity: 3000- 5000 mPas) A.a.1 Vinyl-functionalized polydimethylsiloxane 1.71 0.00 (Vinyl content: 0.05 mmol/g; viscosity: 10 000 mPas) A.a.1 Vinyl-functionalized polydimethylsiloxane 0.00 10.04 (Vinyl content: 0.2 mmol/g; viscosity: 9000 mPas) A.a.1 Vinyl-functionalized polydimethylsiloxane 14.27 31.92 (Vinyl content: 0.3 mmol/g; viscosity: 200 mPas) A.a.4 Fumed silanized silica (primary particle size = 2.73 9.94 6 nm) A.a.4 Silanized cristobalite flour (d.sub.50 =30 μm) 58.20 27.46 A.a.5 Additive: Color paste 0.99 0.00 Catalyst paste 1a 1b A.a.3 Platinum concentrate (Karstedt catalyst in 0.46 0.26 polydimethylsiloxane (Pt content 2%)) A.a.1 Vinyl-functionalized polydimethylsiloxane 6.15 4.56 (Vinyl content: 1.40 mmol/g; viscosity: 3000- 5000 mPas) A.a.1 Vinyl-functionalized polydimethylsiloxane 1.81 0.00 (Vinyl content: 0.05 mmol/g; viscosity: 10 000 mPas) A.a.1 Vinyl-functionalized polydimethylsiloxane 0 9.12 (Vinyl content: 0.03 mmol/g; viscosity: 65 000 mPas) A.a.1 Vinyl-functionalized polydimethylsiloxane 29.14 38.19 (Vinyl content: 0.3 mmol/g; viscosity: 200 mPas) A.a.1 Vinyl-functionalized polydimethylsiloxane 0 10 (Vinyl content: 0.2 mmol/g; viscosity: 9000 mPas) A.a.4 Fumed silanized silica (primary particle size = 2.71 10.21 6 nm) A.a.4 Silanized cristobalite flour (d.sub.50 = 30 μm) 58.74 27.66 A.a.5 Additive: Color paste 0.99 0

(10) The respective constituents of the base and catalyst pastes were homogenized by intimate mixing with a double planetary mixer and then degassed under reduced pressure. The material was then dispensed free of air bubbles into 2K cartridges (50 ml, 1:1, from Mixpac). For the measurements, the cartridge was inserted into a suitable dispenser and a mixing cannula (MB 3.2 16 S) was used for automatic mixing of the material in the correct mixing ratio of 1:1 when it was pressed out.

(11) The processing time was measured at 23° C. (50% rel. air humidity) by discharging a strip of the model silicone of length 15 cm onto a mixing block. Subsequently, a spatula was used every 5 seconds to check whether the viscosity of the material had altered. The time until significant change in the viscosity was noted as the processing time.

(12) The setting time was determined in an oscillating measurement with a Rheometer Physica MCR 301 (Anton Paar GmbH, Graz, Austria). For this purpose, the polymerizable material for production of a dental model to be examined was applied directly from the cartridge to the measurement plate of a plate/plate system (D=25 mm, gap=1 mm), and the rise in viscosity caused by setting was recorded at 30° C. and at a frequency of f=4 Hz and a deformation of γ=1%. The setting time has been attained when the magnitude of the complex viscosity (lη*l) viscosity reaches a plateau value. The setting times (from commencement of mixing) of the polymerizable materials of examples 1a and 1b were 5 min.

(13) The measurement of deformation under pressure was performed to ISO 4823 (elastomeric impression materials). The specimen was demolded 2:30 min after commencement of mixing; the measurement was started after 3 min.

(14) For the material from example 1a, a processing time of 60 seconds and a deformation under pressure of 0.68% were determined, and for the material from example 1b likewise a processing time of 60 seconds and a deformation under pressure of 6.17%.

Example 2: Polymerizable Material for Production of an Inlay

(15) TABLE-US-00002 2a 2b % by % by Constituents wt. wt. B.a.2 First microparticle fraction: silanized dental 49.43 0.0 glass d.sub.50 = 3.5 μm B.a.2 Second microparticle fraction: silanized dental 16.47 68.2 glass d.sub.50 = 1.0 μm B.a.1 Non-agglomerated surface-modified nanoscale 23.0 0.00 SiO.sub.2 particles (d.sub.50 = 50 nm) B.a.1 Fumed silanized silica (primary particle 0.00 5.4 size = 6 nm) B.b.1 Methacrylate 1: bis-GMA 4.3 11.1 B.b.1 Methacrylate 2: UDMA 3.1 11.1 B.b.2 Methacrylate 3: TEDMA 3.1 3.1 B.c Initiators: DABE, camphorquinone 0.65 0.65 B.d Additives: Color pigments, stabilizers ad ad 100 100

(16) Monomers 1, 2 and 3, and initiators and additives, were first homogenized in a plastic vessel by means of a precision glass stirrer. Subsequently, the fillers were added and a homogenous paste was produced by intimate mixing with a double planetary mixer and the mixture was degassed under reduced pressure.

(17) The polymerization volume shrinkage (polymerization shrinkage) was determined by the bonded-disc method (Dental Materials 2004, 20, 88-95). 100 mg of material were exposed for a period of 40 seconds (soft start) (Celalux II, VOCO GmbH Cuxhaven), and the polymerization shrinkage was measured over a period of 1800 seconds.

(18) The flexural strength was determined in accordance with standard ISO 4049 on a material testing machine from Zwick. The measurements reported are each the mean values from five individual measurements.

(19) For the composite from example 2a, a polymerization shrinkage of 1.6% and a flexural strength of 183 MPa were determined. For the composite from example 2b, the values were 2.5% and 154 MPa.

Example 3: Polymerizable Material for Luting of an Inlay

(20) TABLE-US-00003 % by Base paste constituents wt. C.a.1 First microparticle fraction: silanized dental glass 13.8 d.sub.50 = 1.0 μm C.a.1 Second microparticle fraction: silanized dental glass 42.5 d.sub.50 = 3.5 μm C.a.1 Third microparticle fraction: silanized dental glass 14.2 d.sub.50 = 8 μm C.a.2 Fumed silanized silica (primary particle size = 6 nm) 2.8 C.b Methacrylate 1: bis-GMA 13.0 C.b Methacrylate 2: TEDMA 12.9 C.c Initiators: Camphorquinone, DABE, N,N-dihydroxyethyl- 0.797 p-toluidine C.e Polymerization inhibitors: BHT 0.003 % by Catalyst paste constituents wt. C.a.1 First microparticle fraction: silanized dental glass 25.9 d.sub.50 = 0.7 μm C.a.1 Second microparticle fraction: silanized dental glass 42.7 d.sub.50 = 3.0 μm C.a.2 Fumed silanized silica (primary particle size = 6 nm) 2.5 C.b Methacrylate 1: bis-GMA 13.8 C.b Methacrylate 2: TEDMA 13.8 C.c Initiators: Dibenzoyl peroxide 0.18 C.e Polymerization inhibitors: BHT 0.05 C.f Additives: Color pigments ad 100

(21) The monomers, and also initiators and additives, were first homogenized in a plastic vessel by means of a precision glass stirrer. Subsequently, the fillers were added and the mixture was mixed with a double planetary mixer. Subsequently, the paste was homogenized with a three-roll mill and degassed with a double planetary mixer under reduced pressure.

Example 4: Polymerizable Self-Adhesive Material for Luting of an Inlay

(22) TABLE-US-00004 % by Base paste constituents wt. C.a.1 First microparticle fraction: silanized dental glass 4.0 d.sub.50 = 1.5 μm C.a.1 Second microparticle fraction: silanized dental glass 53.8 d.sub.50 = 3.0 μm C.a.2 Fumed silanized silica (primary particle size = 12 nm) 8.0 C.b Methacrylate 1: Ethoxylated bisphenol A dimethacrylate 6.2 C.b Methacrylate 2: UDMA 7.1 C.b Methacrylate 3: Hexanediol dimethacrylate 10.2 C.b Methacrylate 4: TEDMA 6.6 C.c Initiators: Camphorquinone, DABE, N,N- 0.94 dihydroxyethyl-p-toluidine C.e Polymerization inhibitors: BHT 0.09 C.f Additives: Color pigments ad 100 % by Catalyst paste constituents wt. C.a.1 First microparticle fraction: silanized dental glass 5.7 d.sub.50 = 1.5 μm C.a.1 Second microparticle fraction: silanized dental glass 58.1 d.sub.50 = 3.0 μm C.a.2 Fumed silanized silica (primary particle size = 12 nm) 2.2 C.b Methacrylate 1: bis-GMA 3.3 C.b Methacrylate 2: UDMA 11.2 C.b Methacrylate 3: Ethylene glycol dimethacrylate 8.9 C.d Adhesion monomer glyceryl dimethacrylate phosphate 9.5 C.c Initiators: Dibenzoyl peroxide 0.5 C.f Additives: Color pigments ad 100

(23) The monomers, and also initiators and additives, were first homogenized in a plastic vessel by means of a precision glass stirrer. Subsequently, the fillers were added and mixed with a double planetary mixer. Subsequently, the paste was homogenized with a three-roll mill and degassed with a double planetary mixer under reduced pressure.

(24) Measurement Method for Determination of the Adhesion Values

(25) To determine the adhesion properties of the luting cements from examples 3 and 4, the adhesion values were determined analogously to ISO CD 29022 (=VOCO test method) on the composites from examples 2a and 2b.

(26) For the determination of the bond strength of the luting cements on the composite from example 2a and example 2b, specimens were produced therefrom with a diameter of 15 mm and a height of 4 mm and light-cured for 40 s (Celalux II, VOCO GmbH Cuxhaven). Subsequently, a silicone ring was placed on. The luting cement from example 3 or 4 was introduced into the opening of the silicone ring and light-cured for 40 s (cylindrical test specimen (3 mm (height)×5 mm (diameter) (Celalux, VOCO GmbH Cuxhaven)). The finished samples were stored at 37° C. and 100% relative air humidity in a sample cabinet. After 24 h, the shear bond strength was determined with the aid of a universal testing machine (1 mm/min). After the measurement, the exact dimensions of the test specimen for the calculation of the adhesion (reported in MPa) were determined with a micrometer.

(27) The following adhesion values were determined:

(28) TABLE-US-00005 Bond strength [MPa] Polymerizable material for luting of an 19 inlay from example 3 on composite from example 2a Polymerizable material for luting of an 21 inlay from example 4 on composite from example 2a Polymerizable material for luting of an 3 inlay from example 3 on composite from example 2b Polymerizable material for luting of an 6 inlay from example 4 on composite from example 2b

(29) In further studies, the fitting accuracy of the inlays produced using the components described as constituents of an inventive kit and the comparative examples specified was also examined.

(30) In freshly extracted human molars, three-surface (mesial-occlusal-distal) inlay cavities were first prepared. Impressions were subsequently taken of these with an alginate (Blueprint® Xcreme, from Dentsply DeTrey, Konstanz). The impression obtained was then cast with a polymerizable material for production of a dental model. After the polymerizable material had set, the dental model was removed. Through layer-by-layer introduction of a polymerizable material for production of an inlay and subsequent photopolymerization (20 seconds per layer, Celalux II, VOCO GmbH Cuxhaven) of the respective layer, a composite inlay was obtained. This was wiped twice with isopropanol and dried with oil-free compressed air. Subsequently, it was inserted into the tooth cavity to check for size and then cleaned again with water and isopropanol and dried with oil-free compressed air. If a non-self-adhesive polymerizable material for luting of an inlay has been used, Futurabond DC (batch No. 1151482, VOCO GmbH Cuxhaven) was first introduced into the cavity according to the instructions in the user information as a polymerizable material for increasing the bond strength between polymerizable material for luting of an inlay and the hard substance of the tooth, and photopolymerized. If the polymerizable material for luting of an inlay used subsequently was self-adhesive, this step was not needed. In the next step, a polymerizable material for luting of an inlay was applied to the previously produced and non-pretreated, i.e. non-sand-blasted, non-silanized, non-etched, non-primed and non-roughened, composite inlay, and the composite inlay was inserted directly into the tooth cavity and pressed in gently. Excess polymerizable material for luting of an inlay which escapes at the cavity margins was removed cautiously, and then the curing of the luting cement was awaited. To complete the restoration, it was finally polished with a polisher (Dimanto, Voco GmbH Cuxhaven, 8000 rpm).

(31) The teeth were then subjected to thermal cycling stress (THE1200 Thermocycler, SD Mechatronik, Feldkirchen-Westerham, 3000 cycles, 30 s at 5° C., 12 s dripping time, 30 s at 55° C., 12 s dripping time). After removal from the Thermocycler, the restored teeth were stored in a 2% methylene blue solution at 37° C. for 24 hours and then embedded into an epoxy material (Scandiplex, Scan-DIA Hagen). The embedded teeth were then sawn through from mesial through occlusal to distal (Well 3241, well Diamantdrahtsagen GmbH, Mannheim, A 3.3 diamond saw, diameter 0.30 mm). The two sections of each tooth were examined with a light microscope (Wild M3C, Leica Wetzlar, 40-fold magnification), and firstly the thickness of the cement layer was determined, and secondly the marginal integrity was categorized subjectively on the basis of the depth of any color penetration.

(32) When the polymerizable materials described in examples 1-4 were used, the following results were achieved:

(33) TABLE-US-00006 Layer thickness of the Polymerizable Polymerizable polymerizable material used material used material for for for luting of a production of production of composite a dental a composite inlay from Assessment of marginal model inlay example 4 integrity Example 1a Example 2a 15 μm No color penetration evident Example 1a Example 2b 75 μm Color penetration shows clear marginal gap Example 1b Example 2a Composite inlay was too large to be Example 1b Example 2b bonded into the cavity

(34) The tests described in table 2 were likewise conducted using the material from example 3 rather than the polymerizable material for luting of an inlay from example 4. In this case, as described above, Futurabond DC was additionally used as polymerizable material for increasing the bond strength between the polymerizable material for luting of an inlay and the hard substance of the tooth. The results correspond to the results from table 2. In the case of use of a polymerizable material for production of a dental model with excessively high deformation under pressure (example 1b), the inlays produced were too large to be able to be bonded into the cavity without further processing. A polymerizable material for production of a composite inlay with excessively large polymerization shrinkage (example 2b), in contrast, led to an excessively large bond joint and, as a result of this, to poorer marginal integrity.