EP1381646A1 - Light-polymerizable dental composition containing an inhibitor - Google Patents
Light-polymerizable dental composition containing an inhibitorInfo
- Publication number
- EP1381646A1 EP1381646A1 EP02739151A EP02739151A EP1381646A1 EP 1381646 A1 EP1381646 A1 EP 1381646A1 EP 02739151 A EP02739151 A EP 02739151A EP 02739151 A EP02739151 A EP 02739151A EP 1381646 A1 EP1381646 A1 EP 1381646A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- groups
- dental composition
- substituted
- acrylates
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 239000003112 inhibitor Substances 0.000 title claims abstract description 19
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 22
- -1 fullerene compound Chemical class 0.000 claims abstract description 21
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000000049 pigment Substances 0.000 claims abstract description 7
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims description 18
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 16
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 9
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 8
- 229920000193 polymethacrylate Polymers 0.000 claims description 4
- IDXHIIQGMDJEAP-UHFFFAOYSA-N 1,3-dioxolane;2-methylprop-2-enoic acid Chemical compound C1COCO1.CC(=C)C(O)=O.CC(=C)C(O)=O IDXHIIQGMDJEAP-UHFFFAOYSA-N 0.000 claims description 2
- NEBBLNDVSSWJLL-UHFFFAOYSA-N 2,3-bis(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(OC(=O)C(C)=C)COC(=O)C(C)=C NEBBLNDVSSWJLL-UHFFFAOYSA-N 0.000 claims description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 2
- VJDSAXFKXAWPIP-UHFFFAOYSA-N 2-hydroxyethyl n-[6-(2-hydroxyethoxycarbonylamino)-2,2,4-trimethylhexyl]carbamate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OCCOC(=O)NCCC(C)CC(C)(C)CNC(=O)OCCO VJDSAXFKXAWPIP-UHFFFAOYSA-N 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- DWXAVNJYFLGAEF-UHFFFAOYSA-N furan-2-ylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CO1 DWXAVNJYFLGAEF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 150000004712 monophosphates Chemical class 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 5
- 206010034960 Photophobia Diseases 0.000 description 5
- 229930006711 bornane-2,3-dione Natural products 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 208000013469 light sensitivity Diseases 0.000 description 5
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- MKVYSRNJLWTVIK-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O MKVYSRNJLWTVIK-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- JZUPRTLCIRGEBK-UHFFFAOYSA-N ethyl 2-[2-(dimethylamino)ethyl]benzoate Chemical compound CCOC(=O)C1=CC=CC=C1CCN(C)C JZUPRTLCIRGEBK-UHFFFAOYSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 3
- 239000012766 organic filler Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 239000011350 dental composite resin Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- XMAWUPHYEABFDR-UHFFFAOYSA-N 1,2-bis(4-chlorophenyl)ethane-1,2-dione Chemical compound C1=CC(Cl)=CC=C1C(=O)C(=O)C1=CC=C(Cl)C=C1 XMAWUPHYEABFDR-UHFFFAOYSA-N 0.000 description 1
- JUVSRZCUMWZBFK-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-4-methylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1 JUVSRZCUMWZBFK-UHFFFAOYSA-N 0.000 description 1
- IXXLKTZOCSRXEM-UHFFFAOYSA-N 3-(n-methylanilino)propanenitrile Chemical compound N#CCCN(C)C1=CC=CC=C1 IXXLKTZOCSRXEM-UHFFFAOYSA-N 0.000 description 1
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 1
- 229910015805 BaWO4 Inorganic materials 0.000 description 1
- 229910004829 CaWO4 Inorganic materials 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical compound CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000068 pit and fissure sealant Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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)
- Materials Engineering (AREA)
- 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-
groups or
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
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
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.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10119831 | 2001-04-23 | ||
| DE10119831A DE10119831A1 (en) | 2001-04-23 | 2001-04-23 | Light-curable dental composition with improved working time contains polymerizable monomers, light-sensitive initiator, fillers and-or pigments and a substituted fullerene compound as light stabilizer |
| PCT/US2002/011978 WO2002085974A1 (en) | 2001-04-23 | 2002-04-16 | Light-polymerizable dental composition containing an inhibitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1381646A1 true EP1381646A1 (en) | 2004-01-21 |
Family
ID=7682388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02739151A Withdrawn EP1381646A1 (en) | 2001-04-23 | 2002-04-16 | Light-polymerizable dental composition containing an inhibitor |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1381646A1 (en) |
| CA (1) | CA2425953A1 (en) |
| DE (1) | DE10119831A1 (en) |
| WO (1) | WO2002085974A1 (en) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2925480B1 (en) | 2007-12-21 | 2011-07-01 | Gervais Danone Sa | PROCESS FOR THE ENRICHMENT OF OXYGEN WATER BY ELECTROLYTIC, OXYGEN-ENRICHED WATER OR DRINK AND USES THEREOF |
| CA2723847C (en) * | 2008-05-08 | 2017-12-19 | Dentsply Detrey Gmbh | Radical polymerisation inhibitors for light-curable dental materials |
| DE102010003884A1 (en) | 2010-04-12 | 2011-10-13 | Voco Gmbh | Dual-curing, multi-component dental composition |
| DE102010003881A1 (en) | 2010-04-12 | 2011-10-13 | Voco Gmbh | Dental masking compound |
| DE102010003883A1 (en) | 2010-04-12 | 2011-10-13 | Voco Gmbh | Photopolymerizable dental composition, useful e.g. as dental filling material and crown material, comprises photopolymerizable monomer, photoinitiator, molecular weight regulator, inorganic filler and optionally additional additive |
| EP2436363B1 (en) | 2010-09-30 | 2017-01-18 | VOCO GmbH | Compound comprising a monomer with a polyalicyclic structure element for filling and/or sealing a root canal |
| US9079828B2 (en) | 2010-09-30 | 2015-07-14 | Voco Gmbh | Polymerizable compounds comprising a polyalicylic structure element |
| US9023916B2 (en) | 2010-09-30 | 2015-05-05 | Voco Gmbh | Composite material comprising a monomer with a polyalicyclic structure element |
| EP2436366B1 (en) | 2010-09-30 | 2015-07-29 | VOCO GmbH | Composite material comprising a monomer with a polyalicyclic structure as sealing material |
| EP2436364B1 (en) | 2010-09-30 | 2017-05-31 | VOCO GmbH | Varnish compound comprising a monomer with a polyalicyclic structure element |
| EP2450025B1 (en) | 2010-11-08 | 2012-11-28 | VOCO GmbH | Polymerisable phosphoric acid derivatives comprising a polyalicyclic structure element |
| DE102011003289A1 (en) | 2011-01-27 | 2012-08-02 | Voco Gmbh | Dental provisional superstructures as well as materials for their production and corresponding methods |
| US8865019B2 (en) * | 2011-05-03 | 2014-10-21 | King Fahd University Of Petroleum And Minerals | Method of inhibiting free radical polymerization of styrene |
| EP2578200B1 (en) | 2011-10-04 | 2018-03-28 | VOCO GmbH | Compounds for infiltrating and/or sealing of dental hard substance and method |
| DE102012001979A1 (en) | 2012-02-02 | 2013-08-08 | Voco Gmbh | A curable composition comprising plasticizer having a polyalicyclic structural element for use in the manufacture of dental materials |
| DE102012001978A1 (en) | 2012-02-02 | 2013-08-08 | Voco Gmbh | Dental composite materials containing tricyclic plasticizers |
| DE102012214540A1 (en) | 2012-08-15 | 2014-02-20 | Helmholtz-Zentrum für Infektionsforschung GmbH | Tooth filling materials and coatings for inhibiting the biofilm formation of Streptococcus mutans and their production |
| DE102013008176A1 (en) | 2012-10-05 | 2014-04-10 | Voco Gmbh | Kit and method for the indirect chairside production of composite inlays |
| DE102014210432A1 (en) | 2014-06-03 | 2015-12-03 | Voco Gmbh | Polysiloxane compound and dental materials producible therefrom |
| DE102015220373A1 (en) | 2014-10-23 | 2016-04-28 | Voco Gmbh | Hardenable dental material |
| DE102014116389A1 (en) | 2014-11-11 | 2016-05-12 | Voco Gmbh | Free-radically curable dental compositions |
| DE102014116402A1 (en) | 2014-11-11 | 2016-05-12 | Voco Gmbh | Use of radically curable compositions in additive manufacturing processes |
| DE102018114690A1 (en) | 2018-06-19 | 2019-12-19 | Voco Gmbh | Thermally effective dental composite composition |
| CN110066238B (en) * | 2019-05-10 | 2026-01-30 | 西南科技大学 | Fullerene phenyl ethers, pyrrolidine phenyl ether derivatives, their preparation methods and uses |
| DE102019122174A1 (en) | 2019-08-19 | 2021-02-25 | Voco Gmbh | Dental polymerizable composition based on condensed silanes |
| 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 |
| DE102022116577A1 (en) | 2022-07-04 | 2024-01-04 | Mühlbauer Technology Gmbh | Monomer mixture for producing a dental material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH686438A5 (en) * | 1993-04-27 | 1996-03-29 | Basf Ag | Stabilising vinyl monomers against uncontrolled polymerisation |
| US6066272A (en) * | 1996-10-07 | 2000-05-23 | The Hong Kong University Of Science & Technology | Fullerene-containing optical materials with novel light transmission characteristics |
-
2001
- 2001-04-23 DE DE10119831A patent/DE10119831A1/en not_active Withdrawn
-
2002
- 2002-04-16 EP EP02739151A patent/EP1381646A1/en not_active Withdrawn
- 2002-04-16 CA CA002425953A patent/CA2425953A1/en not_active Abandoned
- 2002-04-16 WO PCT/US2002/011978 patent/WO2002085974A1/en not_active Ceased
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| See references of WO02085974A1 * |
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| DE10119831A1 (en) | 2002-10-24 |
| WO2002085974A1 (en) | 2002-10-31 |
| CA2425953A1 (en) | 2002-10-31 |
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