WO2002085974A1 - Light-polymerizable dental composition containing an inhibitor - Google Patents

Light-polymerizable dental composition containing an inhibitor Download PDF

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Publication number
WO2002085974A1
WO2002085974A1 PCT/US2002/011978 US0211978W WO02085974A1 WO 2002085974 A1 WO2002085974 A1 WO 2002085974A1 US 0211978 W US0211978 W US 0211978W WO 02085974 A1 WO02085974 A1 WO 02085974A1
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groups
dental composition
substituted
acrylates
meth
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PCT/US2002/011978
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French (fr)
Inventor
Joachim E. Klee
Uwe Walz
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Dentsply International Inc.
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Priority to EP02739151A priority Critical patent/EP1381646A1/en
Priority to CA002425953A priority patent/CA2425953A1/en
Priority to JP2002583500A priority patent/JP2004537512A/en
Publication of WO2002085974A1 publication Critical patent/WO2002085974A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A61K6/893—Polyurethanes

Definitions

  • the present invention relates to a light-polymerizable dental composition comprising a specific inhibitor. Moreover, the present invention also relates to the use of specific fullerene compounds in a dental composition.
  • Light-polymerizable dental compositions comprise a polymerizable monomer, a light-sensitive polymerization initiator, and optionally further components such as an organic or inorganic filler or an organic or inorganic pigment. It is known to use a stabilizer for preventing a composition containing polymerizable acrylates and/or methacrylates from spontaneous polymerization. 2,6-Di-tert-butyl-4-cresol (BHT), hydroquinone or hydroquinonemonomethylether (HQME) are known as free radical savengers for dental compositions.
  • BHT 2,6-Di-tert-butyl-4-cresol
  • HQME hydroquinone or hydroquinonemonomethylether
  • Light curing polymerisable dental compositions are usually applied in the presence of substantial irradiation of the environment particularily radiation generated by operating lamps.
  • international standards require that a dental dental composite remains stable under an illumination of 10.000 lux for 60 seconds (ISO 4049).
  • Dental pit and fissure sealants are required to remain stable under an illumination of 8000 lux for 25 seconds (ISO 6874) and light activated water- based cements are required to remain stable under an illumination of 8000 lux for 30 seconds (ISO 99917-2).
  • TEMPO 2,2,6,6-tetramethylpiperidinyl-1 -oxide
  • galvinoxyl radicals, hydroxy-TEMPO and 2,2-diphenyl-1-picrylhydrazyl radicals as anaerobic polymerization inhibitors (US 5,468,789).
  • TEMPO as polymerization inhibitor in polymerizable dental compositions and its influence on the depth of curing is known for light curing restorative materials from W.D. Cook, P.M. Standish, Austr. Dent. J., 28 (1983) 307.
  • US 5,847,025 discloses the use of TEMPO and other stable radiclas such as 2,2-Diphenyl- -picrylhydrazyl radicals, galvinoxyl radicals and triphenylmethyl radicals for reducing the light sensitivity of a dental light-curing composite material.
  • the dental composition of the present invention comprises an inhibitor which is a substituted fullerene compound.
  • the inhibitor may contain one or more substituted fullerene compounds.
  • the substituted fullerene compoundd is preferably soluble in the composition, in particular in the polymerisable monomer.
  • the inhibitor is selected from the group of substituted C 60 , C 70 , C 72 , C 76 , C 78 , or C 84 fullerenes.
  • a substituted fullerene compound according to the invention is derived from an unsubstituted fullerene compound by addition or insertion of substituents to the fullerene cage.
  • the substituents added or inserted to the fulleren cage may be further modified in order to provide the desired substituted fullerene compound used in the dental compositions of the invention.
  • the substituents are preferably able to render the fullerene compound soluble in the composition, in particular in the polymerisable monomer.
  • the substituents preferably contribute to the electronic properties of the inhibitor as a radical scavenger.
  • the substituents preferably are able to modify the fullerene cage such that any chromophores absorbing in the range of visible light are destroyed.
  • substituents may be present on the fullerene cage whereby it is preferred that at least two substituents are present. In case at least two substituents are present on the fullerene cage , the substituents may be the same or different.
  • the substituents of the substituted fullerenes are preferably selected from the group of substituted or unsubstituted C ⁇ o-alkyl groups, C ⁇ -alkoxy groups, C 1 . 2 o-alkyl-C 1 . 20 -alkoxy groups, C,. 20 -alkylthio groups, C ⁇ o-alkylthio-C ⁇ o-alkyl groups, C ⁇ oalkylamino groups, C ⁇ o - groups or groups.
  • substituents of the fullerene cage may be selected form the group of substituents given as substituents for the fullerene cage. Moreover, such substituents may be selected from the group consisting of hydroxyl groups, amino groups, thiol groups. In a specific embodiment, one or more substituents of the fullerene cage are substitued with a polymerizable group.
  • the polymerizable group may be selected from acryloyl, C 1 . 20 -alkylacryloyl, or C 1 . 20 -alkenyl groups.
  • the substituted fullerenes are added to the dental composition in an amount ranging from 0.001 to 3.0% by weight, preferably in an amount of from 0.01 to 1.0% by weight and most preferably in an amount of from 0.01 to 0.2% by weight.
  • the dental composition of the present invention comprises a light-polymerizable monomer component.
  • the light-polymerizable monomer component contains one or more monomer compounds. In case the monomer component contains two or more monomer compounds, the monomer compounds may differ with regard to the molecular weight and/or the number of polymerizable moieties.
  • a macromonomer and a reactive diluent are used in the polymerizable monomer component.
  • the monomer compound to be used in the monomer component of the dental composition of the present invention preferably has at least one polymerizable group and is a mono- or polyfunctional (meth)acrylate or a macromonomer.
  • Preferable monomers are 2,2-Bis-[p-(2-hydroxy-3-methacryloyloxypropoxy)-phenyl]-propane, 7, 7,9-trimethyl-4, 13-dioxo-3, 14-dioxa-5, 12-diazahexadecan-1 , 16-diol methacrylate, dipentaerthrytrolpentamethacrylate monophosphate, ⁇ , ⁇ -methacryloyl terminated epoxide-amine macromonomers, ⁇ , ⁇ -methacryloyl terminated epoxidecarboxylic acid macromonomers, ⁇ , ⁇ -methacryloyl terminated epoxide-phenol macromonomers.
  • U the macromonomers disclosed in U.
  • Reactive diluents are mono(meth) acrylates and polyfunctional (meth) acrylates, such as polyalkylenoxide di-(meth)acrylates or poly(meth)acrylates, urethane di(meth) acrylates or poly(meth)acrylates, vinyl-, vinylen- or vinyliden-, acrylate- or methacrylate substituted spiroorthoesters, spiroorthocarbonates or bicycloorthoesters.
  • mono(meth) acrylates and polyfunctional (meth) acrylates such as polyalkylenoxide di-(meth)acrylates or poly(meth)acrylates, urethane di(meth) acrylates or poly(meth)acrylates, vinyl-, vinylen- or vinyliden-, acrylate- or methacrylate substituted spiroorthoesters, spiroorthocarbonates or bicycloorthoesters.
  • Preferred reactive diluents are diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, 3,(4),8,(9)dimethacryloyloxymethyltricyclodecane, dioxolan bismethacrylate, glycerol trimethacrylate, and furfuryl methacrylate.
  • the polymerizable monomer component may be present in the dental composition of the present invention in an amount of from 1 to 99 percent by weight, preferably in an amount of from 10 to 60 percent by weight.
  • the dental composition of the present invention comprises a light-sensitive polymerization initiator.
  • Suitable initiators are benzophenone, benzoin or derivatives therof.
  • Preferred initiators are ⁇ -diketones such as 9,10-phenanthrene quinone, diacetyl, furyl, anisyl, 4,4'-dichlorobenzil and 4,4'-dialkoxybenzil. Particularily preferred is camphorquinone.
  • the initiators may be used in combination with an amine as activator. Examples for such activators are N.N-dimethyl-p-toluidine, N,N- dihydroxyethyl-p-toluidine, and N-(2-cyanoethyl)-N-methylaniline.
  • the initiator may be present in the dental composition of the present invention in an amount of 0.001 to 2 percent by weight, preferably in an amount of from 0.5 to 1 percent by weight.
  • the dental composition of the present invention optionally comprises a filler.
  • the filler may be an inorganic fillers such as La 2 O 3 , ZrO 2 , BiPO 4 , CaWO 4 , BaWO 4 , SrF 2 , Bi 2 O 3 , glasses.
  • the filler may also be or an organic fillers, such as a polymer granulate.
  • the filler may be a combination of organic and inorganic fillers.
  • the filler may be present in the dental composition of the present invention in an amount of 20 to 85 percent by weight.
  • the filler is present in an amount of from 50 to 85 percent by weight, and in case of a sealer the filler is preferably present in an amount of from 20 to 50 percent by weight.
  • the dental composition of the present invention optionally comprises a pigment.
  • pigments which may be incorporated into a composition of the present invention are titanium oxides and iron oxides.
  • the dental composition of the present invention optionally comprises a solvent. Suitable solvents for use in a dental composition according to the invention are acetone, methylethyl ketone, and ethanol.
  • a preferred dental composition according to the invention is a composite comprising from
  • a preferred dental composition according to the invention is a sealer comprising from
  • an inhibitor optionally 20 to 50 percent by weight of a filler and/or pigment, and optionally 0 to 10 percent by weight of a solvent.
  • the dental composition according to the present invention may be prepared by mixing the components of the composition.

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nanotechnology (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dental Preparations (AREA)

Abstract

Light-polymerizable dental composition comprising (i) a polymerizable monomer component, (ii) a light-sensitive polymerization initiator, (iii) an inhibitor, (iv) optionally a filler and/or pigment, and (v) optionally a solvent, characterized in that the inhibitor is a substituted fullerene compound present in an amount suitable for improving light stability of the dental composition.

Description

Light-polymerizable dental composition containing an inhibitor
The present invention relates to a light-polymerizable dental composition comprising a specific inhibitor. Moreover, the present invention also relates to the use of specific fullerene compounds in a dental composition.
Light-polymerizable dental compositions comprise a polymerizable monomer, a light- sensitive polymerization initiator, and optionally further components such as an organic or inorganic filler or an organic or inorganic pigment. It is known to use a stabilizer for preventing a composition containing polymerizable acrylates and/or methacrylates from spontaneous polymerization. 2,6-Di-tert-butyl-4-cresol (BHT), hydroquinone or hydroquinonemonomethylether (HQME) are known as free radical savengers for dental compositions.
Light curing polymerisable dental compositions are usually applied in the presence of substantial irradiation of the environment particularily radiation generated by operating lamps. In order to insure suffciently long working times, international standards require that a dental dental composite remains stable under an illumination of 10.000 lux for 60 seconds (ISO 4049). Dental pit and fissure sealants are required to remain stable under an illumination of 8000 lux for 25 seconds (ISO 6874) and light activated water- based cements are required to remain stable under an illumination of 8000 lux for 30 seconds (ISO 99917-2).
From SU 3,34845 it is known that 2,2,6,6-tetramethylpiperidinyl-1 -oxide (TEMPO) may be used to inhibit the polymerisation of acrylate. Moreover, it is known to use galvinoxyl radicals, hydroxy-TEMPO and 2,2-diphenyl-1-picrylhydrazyl radicals as anaerobic polymerization inhibitors (US 5,468,789).
The effect of TEMPO as polymerization inhibitor in polymerizable dental compositions and its influence on the depth of curing is known for light curing restorative materials from W.D. Cook, P.M. Standish, Austr. Dent. J., 28 (1983) 307. Moreover, US 5,847,025 discloses the use of TEMPO and other stable radiclas such as 2,2-Diphenyl- -picrylhydrazyl radicals, galvinoxyl radicals and triphenylmethyl radicals for reducing the light sensitivity of a dental light-curing composite material.
Although many attempts have been made to lengthen the working times under the conditions of a dental practice by choosing a combination of an initiator and an inhibitor, only minor reductions of light sensitivity are obtained without increasing the working times.
Therefore, it is the problem of the present invention to provide a dental composition, which has a sufficiently long working time while still providing an acceptable light sensitivity of the composition and whereby the mechanical properties and the color shading of the dental material are not deteriorated.
This problem is solved according to claim 1 with a light-polymerizable dental composition comprising
(i) a polymerizable monomer component,
(ii) a light-sensitive polymerization initiator,
(iii) an inhibitor,
(iv) optionally a filler and/or pigment, and
(v) optionally a solvent whereby the inhibitor is a substituted fullerene compound present in an amount suitable for improving light stability of the dental composition.
It was found that when a substituted fullerene such as 1 ,2-(dimethoxymethano)- fullerene is added to a dental composition, surprisingly the stability of the composition under an irradiation with 10,000 lux is about 90 seconds. This is more than twice as much as the stability observed with a comparable composition that only comprises BHT as stabilizer which shows a stability under an irradiation with 10,000 lux of only 40 seconds . At the same time, the mechanical properties and the storage stability of the dental composition remain excellent in the presence of the inhibitor of the present invention.
The dental composition of the present invention comprises an inhibitor which is a substituted fullerene compound. The inhibitor may contain one or more substituted fullerene compounds. The substituted fullerene compoundd is preferably soluble in the composition, in particular in the polymerisable monomer. Preferably, the inhibitor is selected from the group of substituted C60, C70, C72, C76, C78, or C84 fullerenes. A substituted fullerene compound according to the invention is derived from an unsubstituted fullerene compound by addition or insertion of substituents to the fullerene cage. The substituents added or inserted to the fulleren cage may be further modified in order to provide the desired substituted fullerene compound used in the dental compositions of the invention. The substituents are preferably able to render the fullerene compound soluble in the composition, in particular in the polymerisable monomer. Moreover, the substituents preferably contribute to the electronic properties of the inhibitor as a radical scavenger. Finally, the substituents preferably are able to modify the fullerene cage such that any chromophores absorbing in the range of visible light are destroyed.
One or more substituents may be present on the fullerene cage whereby it is preferred that at least two substituents are present. In case at least two substituents are present on the fullerene cage , the substituents may be the same or different. The substituents of the substituted fullerenes are preferably selected from the group of substituted or unsubstituted C^o-alkyl groups, C^-alkoxy groups, C1.2o-alkyl-C1.20-alkoxy groups, C,. 20-alkylthio groups, C^o-alkylthio-C^o-alkyl groups, C^oalkylamino groups, C^o-
Figure imgf000004_0001
groups or
Figure imgf000004_0002
groups. In case the substituents of the fullerene cage are substituted, such substituents may be selected form the group of substituents given as substituents for the fullerene cage. Moreover, such substituents may be selected from the group consisting of hydroxyl groups, amino groups, thiol groups. In a specific embodiment, one or more substituents of the fullerene cage are substitued with a polymerizable group. The polymerizable group may be selected from acryloyl, C1.20-alkylacryloyl, or C1.20-alkenyl groups.
The substituted fullerenes are added to the dental composition in an amount ranging from 0.001 to 3.0% by weight, preferably in an amount of from 0.01 to 1.0% by weight and most preferably in an amount of from 0.01 to 0.2% by weight.
The dental composition of the present invention comprises a light-polymerizable monomer component. The light-polymerizable monomer component contains one or more monomer compounds. In case the monomer component contains two or more monomer compounds, the monomer compounds may differ with regard to the molecular weight and/or the number of polymerizable moieties. In a preferred embodiment, a macromonomer and a reactive diluent are used in the polymerizable monomer component.
The monomer compound to be used in the monomer component of the dental composition of the present invention preferably has at least one polymerizable group and is a mono- or polyfunctional (meth)acrylate or a macromonomer. Preferable monomers are 2,2-Bis-[p-(2-hydroxy-3-methacryloyloxypropoxy)-phenyl]-propane, 7, 7,9-trimethyl-4, 13-dioxo-3, 14-dioxa-5, 12-diazahexadecan-1 , 16-diol methacrylate, dipentaerthrytrolpentamethacrylate monophosphate, α,ω-methacryloyl terminated epoxide-amine macromonomers, α,ω-methacryloyl terminated epoxidecarboxylic acid macromonomers, α,ω-methacryloyl terminated epoxide-phenol macromonomers. Specifically, reference is made to the macromonomers disclosed in U.S. Patent application serial number 08/359,217 filed December 19, 1994.
Reactive diluents are mono(meth) acrylates and polyfunctional (meth) acrylates, such as polyalkylenoxide di-(meth)acrylates or poly(meth)acrylates, urethane di(meth) acrylates or poly(meth)acrylates, vinyl-, vinylen- or vinyliden-, acrylate- or methacrylate substituted spiroorthoesters, spiroorthocarbonates or bicycloorthoesters. Preferred reactive diluents are diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, 3,(4),8,(9)dimethacryloyloxymethyltricyclodecane, dioxolan bismethacrylate, glycerol trimethacrylate, and furfuryl methacrylate.
The polymerizable monomer component may be present in the dental composition of the present invention in an amount of from 1 to 99 percent by weight, preferably in an amount of from 10 to 60 percent by weight.
The dental composition of the present invention comprises a light-sensitive polymerization initiator. Suitable initiators are benzophenone, benzoin or derivatives therof. Preferred initiators are α-diketones such as 9,10-phenanthrene quinone, diacetyl, furyl, anisyl, 4,4'-dichlorobenzil and 4,4'-dialkoxybenzil. Particularily preferred is camphorquinone. The initiators may be used in combination with an amine as activator. Examples for such activators are N.N-dimethyl-p-toluidine, N,N- dihydroxyethyl-p-toluidine, and N-(2-cyanoethyl)-N-methylaniline.
The initiator may be present in the dental composition of the present invention in an amount of 0.001 to 2 percent by weight, preferably in an amount of from 0.5 to 1 percent by weight.
The dental composition of the present invention optionally comprises a filler. The filler may be an inorganic fillers such as La2O3, ZrO2, BiPO4, CaWO4, BaWO4, SrF2, Bi2O3, glasses. The filler may also be or an organic fillers, such as a polymer granulate. Moreover, the filler may be a combination of organic and inorganic fillers. The filler may be present in the dental composition of the present invention in an amount of 20 to 85 percent by weight. Preferably in case of a composite the filler is present in an amount of from 50 to 85 percent by weight, and in case of a sealer the filler is preferably present in an amount of from 20 to 50 percent by weight.
The dental composition of the present invention optionally comprises a pigment. Examples of pigments which may be incorporated into a composition of the present invention are titanium oxides and iron oxides. The dental composition of the present invention optionally comprises a solvent. Suitable solvents for use in a dental composition according to the invention are acetone, methylethyl ketone, and ethanol.
A preferred dental composition according to the invention is a composite comprising from
15 to 50 percent by weight of a polymerizable monomer component,
0.1 to 3.0 percent by weight of a light-sensitive polymerization initiator,
0.01 to 1 percent by weight of an inhibitor, and
50 to 85 percent by weight of a filler and/or pigment.
A preferred dental composition according to the invention is a sealer comprising from
50 to 80 percent by weight of a polymerizable monomer component,
0.1 to 3.0 percent by weight of a light-sensitive polymerization initiator,
0.01 to 1.0 percent by weight of an inhibitor, optionally 20 to 50 percent by weight of a filler and/or pigment, and optionally 0 to 10 percent by weight of a solvent.
The dental composition according to the present invention may be prepared by mixing the components of the composition.
The invention will now be further illustrated by the following example and comparative example.
Example 1
19,814 g Urethane dimethacrylate, 1.239 g trimethylolpropane trimethacrylate, 3.715 g diethyleneglycol dimethacrylate, 0.075 g camphorquinone, 0.087 g dimethylaminoethylbenzoicacid ethylester, 0.025 g (0.113 mmol) BHT and 0.025 g (0.031 mmol) 1 ,2-(dimethoxymethano)-fullerene (Fluka) were homogeneously mixed. To this resin mixture, 75.020 g of a strontium alumofluorosilicate glass was added and homogeneously mixed to provide a dental composition. The properties of the dental composition were measured and the properties are summarized in Table 1. The light sensitivity to ambient light was also measured. The results are shown in Figure 1.
Example 2
19.854 g Urethane dimethacrylate, 1.241 g trimethylolpropane trimethacrylate, 3.723 g diethyleneglycol d imethacrylate, 0.075 g camphorquinone, 0.087 g d imethylaminoethylbenzoicacid ethylester and 0.020 g (0.025 mmol) 1 ,2-(Dimethoxymethano)-fullerene (Fluka) were mixed homogeneously. To this resin mixture 75.000 g of a strontiumalumofluoro silicate glass was added and mixed homogeneously. The sensitivity to ambient light of this composite is 110 seconds.
Comparative Example 1
19.056 g Urethane dimethacrylate, 1.191 g trimethylolpropane trimethacrylate, 3.573 g diethyleneglycol dimethacrlyate, 0,072 g camphorquinone, 0.084 g dimethylaminoethylbenzoicacid ethylester and 0.024 g BHT were homegeneously mixed. To the resin mixture, 76.000 g of a strontium alumofluorosilicate glass were added and homogeneously mixed. The properties of the dental composition were measured and the properties are summarized in Table 1. The light sensitivity to ambient light was also measured. The results are shown in Figure 1.
Comparative Example 2
19.711 g Urethane dimethacrylate, 1.232 g trimethylolpropane trimethacrylate, 3.696 g diethyleneglycol dimethacrylate, 0.074 g camphorq uinone, 0.087 g dimethylaminoethyl benzoic acid ethylester, 0,025 g (0.113 mmol) BHT and 0.025 g (0.035 mmol) buckminster ullerene C60 (Fluka) were homogeneously mixed. To this resin mixture 75.150 g of a strontium alumofluorosilicate glass was added and homogeneously mixed . It was found that the stability of the composition was about the same as the stability of the composition of comparative example 1. Table 1 Properties of dental composites of example 1 and of comparative example 1
Figure imgf000009_0001
Figure imgf000009_0002
2 4 S 8 10
Time fwl
■m- 1,2-(Dimet βxymot ano)-Λιllapen, BHT
Figure 1 Sensitivity to ambient light of composites comprising BHT or 1 ,2- (Dimethoxymethano)-fullerene and BHT vs. storage time at 23°C (w=weeks)

Claims

Claims
1. Light-polymerizable dental composition comprising (i) a polymerizable monomer component,
(ii) a light-sensitive polymerization initiator,
(iii) an inhibitor,
(iv) optionally a filler and/or pigment, and
(v) optionally a solvent, characterized in that the inhibitor is a substituted fullerene compound present in an amount suitable for improving light stability of the dental composition.
2. The dental composition of claim 1 , wherein the substituted fullerene compound is selected from the group consisting of substituted C60, C70, C72, C76, C78, and C84 fullerene compounds.
3. The dental composition according to claim 1 or 2, which comprises the substituted fullerene compound in a content of 0.001 to 3.0 % by weight.
4. The dental composition of claim 3, which comprises the substituted fullerene compound in a content of 0.01 to 1.0 % by weight.
5. The dental composition of claim 4, which comprises the substituted fullerene compound in a content of 0.01 to 0.2 % by weight.
6. The dental composition of any one of claims 1 to 5 wherein the substituents of the substituted fullerenes are selected from the group of C,.20-alkyl groups, C,. 20-alkoxy groups, C^^-alkyl-C^^-alkoxy groups, C^^-alkylthio groups, C,.20- alkylthio-C1.20-alkyl groups, C^^alkylamino groups, C^o-alkoxy-poly-C^- alkyleneoxy groups or C,_20-aryl groups, whereby these groups may be substituted with one to three substituents selected from the group of hydroxyl groups, amino groups, and thiol groups, C1-20-alkyl groups, C^-alkoxy groups, C^o-alkyl-C^o-alkoxy groups, Cn.20-alkylthio groups, C^o-alkylthio-C^-alkyl groups, C^oalkylamino groups, C^-alkoxy-poly-C^-alkyleneoxy groups, C^- aryl groups, acryloyl, C^^-alkylacryloyl, or C,_20-alkenyl groups.
7. The dental composition of any one of claims 1 to 6 wherein the polymerizable monomer component comprises 2,2-Bis-[p-(2-hydroxy-3- met h aery loy loxyp ropoxy)-p he ny l]-p ropan e , 7, 7,9- trimethyl-4, 13-dioxo-3, 14-dioxa-5, 12-diazahexadecan-1 , 16-diol methacrylate, dipentaerthrytrolpentamethacrylate monophosphate, α,ω-methacryloyl terminated epoxide-amine macromonomers, α,ω-methacryloyl terminated epoxidecarboxylic acid macromonomers, or α,ω-methacryloyl terminated epoxide-phenol macromonomers.
8. The dental composition of any one of claims 1 to 7 wherein the polymerizable monomer component comprises mono(meth) acrylates and polyfunctional (meth) acrylates, such as polyalkylenoxide di-(meth)acrylates or poly(meth)acrylates, urethane di(meth) acrylates or poly(meth)acrylates, vinyl-, vinylen- or vinyliden-, acrylate- or methacrylate substituted spiroorthoesters, spiroorthocarbonates or bicycloorthoesters.
9. The dental composition according to claim 8 wherein the polymerizable monomer component comprises diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, 3,(4),8,(9)dimethacryloyl- oxymethyltricyclodecane, dioxolan bismethacrylate, glycerol trimethacrylate, and furfuryl methacrylate.
10. Use of a substituted fullerene compound in a dental composition for improving light stability and thermal stability of the dental composition.
11. Use according to claim 10 wherein the dental composition is as defined in any one of claims 1 to 9.
PCT/US2002/011978 2001-04-23 2002-04-16 Light-polymerizable dental composition containing an inhibitor WO2002085974A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009135677A1 (en) * 2008-05-08 2009-11-12 Dentsply Detrey Gmbh Radical polymerisation initiators for light-curable dental materials
US20120280174A1 (en) * 2011-05-03 2012-11-08 King Abdulaziz City For Science And Technology Method of inhibiting free radical polymerization of styrene
US8709231B2 (en) 2007-12-21 2014-04-29 Compagnie Gervais Danone Method for enriching water with oxygen by an electrolytic process, oxygen enriched water or beverage and uses thereof
US9795541B2 (en) 2014-11-11 2017-10-24 Voco Gmbh Use of free radically curable compositions in additive manufacturing methods
US9833387B2 (en) 2012-10-05 2017-12-05 Voco Gmbh Kit and method for indirect chairside production of composite inlays
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US11944692B2 (en) 2018-06-19 2024-04-02 Voco Gmbh Thermoactive dental composite composition
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DE102021113969A1 (en) 2021-05-31 2022-12-01 Mühlbauer Technology Gmbh Monomer mixture for the production of a dental material
DE102021134260A1 (en) 2021-12-22 2023-06-22 Voco Gmbh Dental light-curable composition and corresponding restorations, manufacturing processes and uses
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4414773A1 (en) * 1993-04-27 1994-11-24 Basf Ag Processes for stabilising vinylic monomers against uncontrolled polymerisation, and protected surfaces
US6066272A (en) * 1996-10-07 2000-05-23 The Hong Kong University Of Science & Technology Fullerene-containing optical materials with novel light transmission characteristics

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4414773A1 (en) * 1993-04-27 1994-11-24 Basf Ag Processes for stabilising vinylic monomers against uncontrolled polymerisation, and protected surfaces
US6066272A (en) * 1996-10-07 2000-05-23 The Hong Kong University Of Science & Technology Fullerene-containing optical materials with novel light transmission characteristics

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8709231B2 (en) 2007-12-21 2014-04-29 Compagnie Gervais Danone Method for enriching water with oxygen by an electrolytic process, oxygen enriched water or beverage and uses thereof
WO2009135677A1 (en) * 2008-05-08 2009-11-12 Dentsply Detrey Gmbh Radical polymerisation initiators for light-curable dental materials
US20120280174A1 (en) * 2011-05-03 2012-11-08 King Abdulaziz City For Science And Technology Method of inhibiting free radical polymerization of styrene
US8865019B2 (en) * 2011-05-03 2014-10-21 King Fahd University Of Petroleum And Minerals Method of inhibiting free radical polymerization of styrene
US9833387B2 (en) 2012-10-05 2017-12-05 Voco Gmbh Kit and method for indirect chairside production of composite inlays
US9795541B2 (en) 2014-11-11 2017-10-24 Voco Gmbh Use of free radically curable compositions in additive manufacturing methods
US9839585B2 (en) 2014-11-11 2017-12-12 Voco Gmbh Free radically curable dental compositions
US11944692B2 (en) 2018-06-19 2024-04-02 Voco Gmbh Thermoactive dental composite composition
CN110066238A (en) * 2019-05-10 2019-07-30 西南科技大学 Fullerene phenylate class pyrrolidines phenylate analog derivative and its preparation method and application
US11992538B2 (en) 2019-08-19 2024-05-28 Voco Gmbh Polymerizable dental composition based on condensed silanes

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