Claims
- 1. A low shrinking polymerizable or crosslinkable dental composition, comprising a mixture of:(1) at least one crosslinkable or polymerizable silicone oligomer or polymer which is liquid at room temperature or which is heat-meltable at a temperature of less than 100° C., and which comprises: at least one unit of formula (FS): Z—SiRa0—O(3-a)/2 wherein: a=0, 1 or 2, R0, identical or different, represents an alkyl, cycloalkyl, aryl, vinyl, hydrogeno or alkoxy radical, Z, identical or different, is an organic substituent comprising at least one reactive epoxy, or alkenyl ether or oxetane or dioxolane or carbonate functional group, and at least two silicon atoms, (2) at least one aromatic hydrocarbon photosensitizer, having a residual light absorption of between 200 and 500 nm, said photosensitizer is being selected from the group consisting of: 4,4′-dimethoxybenzoin; 2-4-diethylthioxanthone 2-ethyanthraquinone; 2-methylanthraquinone; 1,8-dihydroxyanthraquinone; dibenzoylperoxide; 2,2-dimethoxy-2-phenylacetophenone; benzoin; 2-hydroxy-2-methylpropionphenone; benzaldehyde; 4-(2-hydroxyethyoxy)phenyl-(2-hydroxy-2-methylpropyl)-ketone; benzoylacetone; 2-isopropylthioxanthone; 1-chloro-4-propoxythioxanthone; and 4-isopropylthioxanthone. (3) at least one dental filler present in a proportion of at least 10% by weight relative to the total weight of the composition, and (4) an effective quantity of at least one borate-type photoinitiator, having an anionic and cationic entity, wherein the anionic entity of the borate is selected from the group consisting of: wherein the cationic entity of the borate is selected from the group consisting of:[(Φ)2I]+ [C8H17—O—Φ—I—Φ]− [(Φ—CH3)21]+[C12H25—Φ—I—Φ]+ [(C8H17—O—Φ)2I]+ [(C8H17—O—Φ—I—Φ)]−[(Φ)3S]+ [(Φ)2—S—Φ—O—C8H17]+[(CH3—Φ—I—Φ—CH(CH3)2]+ , and [(Φ—S—Φ—S—(Φ)2]+ [(C12H25—Φ)2I]+ [(CH3Φ—I—Φ—OC2H5]+; and wherein the composition has a volumetric polymerization or crosslinking shrinkage of less than 1.5% v/v.
- 2. The low shrinking polymerizable or crosslinkable dental composition as claimed in claim 1, wherein Z is an organic substituent Z1 comprising at least one reactive epoxy- or dioxolane functional group.
- 3. The low shrinking polymerizable or crosslinkable dental composition as claimed in claim 2, wherein the reactive functional group(s) Z1 is selected from the group consisting of:
- 4. The low shrinking polymerizable or crosslinkable dental composition as claimed in claim 1, wherein the photoinitiator is selected from the group consisting of:[(Φ)2I]+.[B(C6F5)4]− [(C8H17)—O—Φ—IΦ)]+.[B(C6F5)4]−[C12H25—Φ—I—Φ]−, [B(C6F5)4]− [(C8H17—O—Φ)2I]+.[B(C6F5)4]−[(C8H17)—O—Φ—I—Φ)]+, [B(C6F5)4]− [(Φ)3S]−,[B(C6F5)4]−[(Φ)2S—Φ—O—C8H17]+, [B(C6H4CF3)4]−[(C12H25—Φ)2I]°.[B(C6F5)4]−[(Φ3S]+,[B(C6F4OCF3)4]− [(Φ—CH3)2I]+.[B(C6F5)4]−, and [(Φ—CH3)2I]+.[B(C6F4OCF3)4]− [CH3—Φ—IΦ—CH(CH3)2]+.[B(C6F5)4]−(η5-cyclopentadienyl)(η6-toluene)Fe+, [B(C6F5)4]−(η5-cyclopentadienyl)(η6-methyl-1-naphthalene) Fe+, [B(C6F5)4]−, and (η5-cyclopentadienyl)(η6-cumene) Fe+, [B(C6F5)4]−.
- 5. A low shrinking polymerizable or crosslinkable dental composition comprising a mixture of:(1) at least one crosslinkable or polymerizable silicone oligomer or polymer which is liquid at room temperature or which is heat-meltable at a temperature of less than 100° C., and which comprises: at least one unit of formula (FS): Z—SiR20—O(3-a)/2 wherein: a=0, 1 or 2, R0, identical or different, represents an alkyl, cycloalkyl, aryl, vinyl, hydrogeno or alkoxy radical, Z, identical or different, is an organic substituent comprising at least one reactive epoxy, or alkenyl ether or oxetane or dioxolane or carbonate functional group, and at least two silicon atoms, (2) at least one aromatic hydrocarbon photosensitizer, having a residual light absorption of between 200 and 500 nm, and selected from the group consisting of the following formulae (IV) to (XXII): formula (IV) wherein: when n=1, Ar1 represents an aryl radical containing from 6 to 18 carbon atoms, a tetrahydronaphthyl, thienyl, pyridyl or furyl radical or a phenyl radical carrying one or more substituents selected from the group consisting of F, Cl, Br, CN, OH, linear or branched C1-C12 alkyls, —CF3, —OR6, —OPhenyl, —SR6, —SPhenyl, —SO2Phenyl, —COOR6, —O—(CH2—CH═CH2), —O(CH2H4—O)m—H, and —O(C3H6O)m—H, m being between 1 and 100, when n=2, Ar1 represents a C6—C12 arylene radical or a phenylene-T-phenylene radical where T represents —O—, —S—, —SO2—, or —CH2—, X represents a group —OR7 or —OSiR8(R9)2 or forms, with R4, a group —O—CH(R10)—, R4 represents a linear or branched C1-C8 alkyl radical which is unsubstituted or which carries an —OH, —OR6, C2-C8 acyloxy, —CF3 or —CN group, a C3 or C4 alkenyl radical, a C6 to C18 aryl radical, a C7 to C9 phenylalkyl radical, R5 has one of the meanings given for R4 or represents a radical —CH2CH2R11, or alternatively forms with R4 a C2-C8 alkylene radical or a C3-C9 oxa-alkylene or aza-alkylene radical, R6 represents a lower alkyl radical containing from 1 to 12 carbon atoms, R7 represents a hydrogen atom, a C1-C12 alkyl radical, a C2-C6 alkyl radical carrying an —OH, —OR6 or —CN group, a C3-C6 alkenyl radical, a cyclohexyl or benzyl radical, a phenyl radical, optionally substituted with a chlorine atom or a linear or branched C1-C12 alkyl radical, or a 2-tetrahydropyranyl radical, R8 and R9 are identical or different and each represent a C1-C4 alkyl radical or a phenyl radical, R10 represents a hydrogen atom, a C1-C8 alkyl radical or a phenyl radical, R11 represents a radical —CONH2, —CONHR6, —CON(R6)2, —P(O)(OR6)2 or 2-pyridyl; formula (V) wherein: Ar2 has the same meaning as Ar1 of formula (IV) in the case where n=1, R15 represents a radical selected from the group consisting of a radical Ar2, a linear or branched C1-C12 alkyl radical, a C6-C12 cycloalkyl radical, and a cycloalkyl radical forming a C6-C12 ring with the carbon of the ketone or a carbon of the radical Ar2, R15 being optionally substituted with one or more substituents selected from the group consisting of —F, —Cl, —Br, —CN, —OH, —CF3, —OR6, —SR6, —COOR6, the linear or branched C1-C12 alkyl radicals optionally carrying an —OH, —OR6 or —CN group, and the linear or branched C1-C8 alkenyl radicals; formula (VI) wherein: Ar3 has the same meaning as Ar1 of formula (IV) in the case where n=1, R16, identical or different, represents a radical selected from the group consisting of a radical Ar3, a radical —(C═O)—Ar3 , a linear or branched C1-C12 alkyl radical, a C6-C12 cycloalkyl radical, R16 being optionally substituted with one or more substituents selected from the group consisting of —F, —Cl, —Br, —CN, —OH, —CF3, —OR6, —SR6, —COOR6, the linear or branched C1-C12 alkyl radicals optionally carrying an —OH, —OR6 or —CN group, and the linear or branched C1-C8 alkenyl radicals; formula (VII) wherein: R5, which are identical or different, have the same meanings as in formula (IV), Y, which are identical or different, represent X and R4, Z represents; a direct bond, a C1-C6 divalent alkylene radical, or a phenylene, diphenylene or phenylene-T-phenylene radical, or alternatively forms, with the two substituents R5 and the two carbon atoms carrying these substituents, a cyclopentane or cyclohexane nucleus, a divalent group —O—R12—O—, —O—SiR8R9—O—SiR8R9—O—, or —O—SiR8R9—O—, R12 represents a C2-C8 alkylene, C4-C6 alkenylene or xylylene radical, and Ar4 has the same meaning as Ar1 of formula (IV) in the case where n=1, family of thioxanthones of formula (VIII): m=0 to 8, R17, identical or different substituent(s) on the aromatic group, represents a linear or branched C1-C12 alkyl radical, a C6-C12 cycloalkyl radical, a radical Ar1, a halogen atom, an —OH, —CN, —NO2, —COOR6, —CHO, Ophenyl, —CF3, —SR6, —Sphenyl, —SO2phenyl, Oalkenyl, or —SiR63 group. family of xanthenes of formula (IX): family of xanthones of formula (X): family of the naphthalene of formula (XI): family of the anthracene of formula (XII): family of the phenanthrene of formula (XIII): family of the pyrene of formula (XIV): family of the fluorene of formula (XV): family of the fluoranthene of formula (XVI): family of the chrysene of formula (XVII): family of the fluorene of formula (XVIII): with x=0 to 8, for example 2,7-dinitro-9-fluorenone, family of the chromone of formula (XIX): with y=0 to 6 family of the eosin of formula (XX): with z=0 to 5 with z=0 to 6 family of the erythrosin of formula (XXI): with z=0 to 5 with Z=0 to 6; and family of the biscoumarins of formula (XXII): R18, identical or different, has the same meaning as R17 or represents a group —NR62, or 3,3′-carbonylbis(7-methoxycoumarin), (3) at least one dental filler present in a proportion of at least 10% by weight relative to the total weight of the composition, and (4) an effective quantity of at least one borate-type photoinitiator, having an anionic and cationic entity, wherein the anionic entity of the borate is selected from the group consisting of: wherein the cationic entity of the borate is selected from the group consisting of:[(Φ)2I]+ [C8H17—O—Φ—I—Φ]− [(Φ—CH3)21]+[C12H25—Φ—I—Φ]+ [(C8H17—O—Φ)2I]+ [(C8H17—O—Φ—I—Φ)]−[(Φ)3S]+ [(Φ)2—S—Φ—O—C8H17]+(CH3—Φ—I—Φ—CH(CH3)2]+ , and [(Φ—S—Φ—S—(Φ)2]+ [(C12H25—Φ)2I]+ [(CH3Φ—I—Φ—OC2H5]+; wherein the composition has a volumetric polymerization or crosslinking shrinkage of less than 1.5% v/v wherein the silicone oligomer or polymer (1) consists of at least one silicone having the following average formula: mentioned above.
- 6. A process for the preparation of a dental prosthesis or of a dental restoration comprising the steps of shaping and curing the low shrinking polymerizable or crosslinkable dental composition comprising a mixture of:(1) at least one crosslinkable or polymerizable silicone oligomer or polymer which is liquid at room temperature or which is heat-meltable at a temperature of less than 100° C., and which comprises: at least one unit of formula (FS): Z—SiRa0—O(3-a)/2 wherein: a=0, 1 or 2, R0, identical or different, represents an alkyl, cycloalkyl, aryl, vinyl, hydrogeno or alkoxy radical, Z, identical or different, is an organic substituent comprising at least one reactive epoxy, or alkenyl ether or oxetane or dioxolane or carbonate functional group, and at least two silicon atoms, (2) at least one aromatic hydrocarbon photosensitizer, having a residual light absorption of between 200 and 500 nm, and selected from the group consisting of the following formulae (IV) to (XXII): formula (IV) wherein: when n=1, Ar1 represents an aryl radical containing from 6 to 18 carbon atoms, a tetrahydronaphthyl, thienyl, pyridyl or furyl radical or a phenyl radical carrying one or more substituents selected from the group consisting of F, Cl, Br, CN, OH, linear or branched C1-C12 alkyls, —CF3, —OR6, —OPhenyl, —SR6, —SPhenyl, —SO2Phenyl, —COOR6, —O—(CH2—CH═CH2), —O(CH2H4—O)m—H, and —O(C3H6O)m—H, m being between 1 and 100, when n=2, Ar1 represents a C6-C12 arylene radical or a phenylene-T-phenylene radical where T represents —O—, —S—, —SO2— or —CH2—, X represents a group —OR7 or —OSiR8(R9)2 or forms, with R4, a group —O—CH(R10)—, R4 represents a linear or branched C1-C8 alkyl radical which is unsubstituted or which carries an —OH, —OR6, C2-C8 acyloxy, —CF3 or —CN group, a C3 or C4 alkenyl radical, a C6 to C18 aryl radical, a C7 to C9 phenylalkyl radical, R5 has one of the meanings given for R4 or represents a radical —CH2CH2R11, or alternatively forms with R4 a C2-C8 alkylene radical or a C3-C9 oxa-alkylene or aza-alkylene radical, R6 represents a lower alkyl radical containing from 1 to 12 carbon atoms, R7 represents a hydrogen atom, a C1-C12 alkyl radical, a C2-C6 alkyl radical carrying an —OH, —OR6 or —CN group, a C3-C6 alkenyl radical, a cyclohexyl or benzyl radical, a phenyl radical, optionally substituted with a chlorine atom or a linear or branched C1-C12 alkyl radical, or a 2-tetrahydropyranyl radical, R8 and R9 are identical or different and each represents a C1-C4 alkyl radical or a phenyl radical, R10 represents a hydrogen atom, a C1-C8 alkyl radical or a phenyl radical, R11 represents a radical —CONH2, —CONHR6, —CON(R6)2, —P(O)(OR6)2 or 2-pyridyl; formula (V) wherein: Ar2 has the same meaning as Ar1 of formula (IV) in the case where n=1, R15 represents a radical selected from the group consisting of a radical Ar2, a linear or branched C1-C12 alkyl radical, a C6-C12 cycloalkyl radical, and a cycloalkyl radical forming a C6-C12 ring with the carbon of the ketone or a carbon of the radical Ar2, R15 being optionally substituted with one or more substituents selected from the group consisting of —F, —Cl, —Br, —CN, —OH, —CF3, —OR6, —SR6, —COOR6, the linear or branched C1-C12 alkyl radicals optionally carrying an —OH, —OR6 or —CN group, and the linear or branched C1-C8 alkenyl radicals; formula (VI) wherein: Ar3 has the same meaning as Ar1 of formula (IV) in the case where n=1, R16, identical or different represents a radical selected from the group consisting of a radical Ar3, a radical —(C═O)—Ar3, a linear or branched C1-C12 alkyl radical, a C6-C12 cycloalkyl radical, R16 being optionally substituted with one or more substituents selected from the group consisting of —F, —Cl, —Br, —CN, —OH, —CF3, —OR6, —SR6, —COOR6, the linear or branched C1-C12 alkyl radicals optionally carrying an —OH, —OR6 or —CN group, and the linear or branched C1-C8 alkenyl radicals; formula (VII) wherein: R5, which are identical or different, have the same meanings as in formula (IV), Y, which are identical or different, represent X or R4, Z represents; a direct bond, a C1-C6 divalent alkylene radical, or a phenylene, diphenylene or phenylene-T-phenylene radical, or alternatively forms, with the two substituents R5 and the two carbon atoms carrying these substituents, a cyclopentane or cyclohexane nucleus, a divalent group —O—R12—O—, —O—SiR8R9—O—SiR8R9—O—, or —O—SiR8R9—O—, R12 represents a C2-C8 alkylene, C4-C6 alkenylene or xylylene radical, and Ar4 has the same meaning as Ar1 of formula (IV) in the case where n=1, family of thioxanthones of formula (VIII): m=0 to 8, R17, identical or different substituent(s) on the aromatic group, represent a linear or branched C1-C12 alkyl radical, a C6-C12 cycloalkyl radical, a radical Ar1, a halogen atom, an —OH, —CN, —NO2, —COOR6, —CHO, Ophenyl, —CF3, —SR6, —Sphenyl, —SO2phenyl, Oalkenyl, or —SiR63 group, family of xanthenes of formula (IX): family of xanthones of formula (X): family of the naphthalene of formula (XI): family of the anthracene of formula (XII): family of the phenanthrene of formula (XIII): family of the pyrene of formula (XIV): family of the fluorene of formula (XV): family of the fluoranthene of formula (XVI): family of the chrysene of formula (XVII): family of the fluorene of formula (XVIII): with x=0 to 8, for example 2,7-dinitro-9-fluorenone, family of the chromone of formula (XIX): with y=0 to 6 family of the eosin of formula (XX): with z=0 to 5 with z=0 to 6family of the erythrosin of formula (XXI): with z=0 to 5 with z=0 to 6; and family of the biscoumarins of formula (XXII): R18, identical or different, has the same meaning as R17 or represents a group —NR62, or 3,3′-carbonylbis(7-methoxycoumarin), (3) at least one dental filler present in a proportion of at least 10% by weight relative to the total weight of the composition, and (4) an effective quantity of at least one borate-type photoinitiator, having an anionic and cationic entity, wherein the anionic entity of the borate is selected from the group consisting of: wherein the cationic entity of the borate is selected from the group consisting of:[(Φ)2I]+ [C8H17—O—Φ—I—Φ]− [(Φ—CH3)21]+[C12H25—Φ—I—Φ]+ [(C8H17—O—Φ)2I]+ [(C8H17—O—Φ—I—Φ)]−[(Φ)3S]+ [(Φ)2—S—Φ—O—C8H17]+[(CH3—Φ—I—Φ—CH(CH3)2]+ , and [(Φ—S—Φ—S—(Φ)2]+ [(C12H25—Φ)2I]+ [(CH3Φ—I—Φ—OC2H5]+; wherein the composition has a volumetric polymerization or crosslinking shrinkage of less than 1.5% v/v.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 98 12375 |
Oct 1998 |
FR |
|
Parent Case Info
This application is an application under 35 U.S.C. Section 371 of International Application Number PCT/FR99/02345 filed on Oct. 1, 1999.
PCT Information
| Filing Document |
Filing Date |
Country |
Kind |
| PCT/FR99/02345 |
|
WO |
00 |
| Publishing Document |
Publishing Date |
Country |
Kind |
| WO00/19967 |
4/13/2000 |
WO |
A |
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Patent Grant
6747071
