Photopolymers and use in dental restorative materials
View Patent ↗Photopolymerizable polymer composites based on dimethacrylate systems have been increasingly utilized as dental restorative materials. One of the biggest drawbacks of current dental resin systems is the volume shrinkage and shrinkage induced stresses that arise during the polymerization. Other major problems include incomplete double bond conversion and insufficient wear resistance. This invention involves the development of an entirely novel approach to the photopolymerization process that utilizes thiol-ene systems as low shrinkage and ultra-low shrinkage stress dental restorative materials. Compared with the traditional dimethacrylate dental resins, these novel photopolymerizations have demonstrated a dramatically decreased volume shrinkage, extremely rapid polymerization, abilities to photopolymerize ultrathick materials and achieve much higher conversion, lack of oxygen inhibition and ultra-low shrinkage stress due to low volume shrinkage and drastically delayed gel point conversion. These polymers have thus shown outstanding suitability as dental restorative materials.
1. A photopolymerizable dental restorative material consisting essentially of: particles of filler; first monomers having thiol functional groups; second monomers having vinyl functional groups; an initiator selected from camphorquinone or 2,2-dimethoxy-2-phenylacetophenone; and an optional amine accelerator; wherein at least about 10% of the functional groups in the dental restorative material are thiol functional groups; and wherein the material does not contain an additional initiator; and wherein, upon exposure to light, the material cures without oxygen inhibition; and wherein after polymerization the material exhibits a flexural strength of greater than 100 Mega Pascals.
2. The photopolymerizable dental restorative material of claim 1 , wherein at least about 15% to about 60% of the functional groups in the dental restorative material are thiol functional groups.
3. The photopolymerizable dental restorative material of claim 1 , wherein at least about 45% to about 55% of the functional groups in the dental restorative material are thiol functional groups.
4. The photopolymerizable dental restorative material of claim 1 that when polymerized exhibits a volume shrinkage of less than 10%.
5. The photopolymerizable dental restorative material of claim 1 that when polymerized creates a polymer having an average weight loss, when dried, of 0.4 to 0.6% relative to an original mass before extraction.
6. The photopolymerizable dental restorative material of claim 1 that when polymerized creates a polymer having a shrinkage stress of less that 3.0 MPa.
7. The photopolymerizable dental restorative material of claim 1 that when polymerized creates a polymer having a shrinkage stress of less that 1.5 MPa.
8. The photopolymerizable dental restorative material of claim 1 that when polymerized creates a polymer having a shrinkage stress of less that 0.5 MPa.
9. The photopolymerizable dental restorative material of claim 1 , which is curable with visible light, wherein the initiator is camphorquinone.
10. The photopolymerizable dental restorative material of claim 9 , containing an amine accelerator.
11. The photopolymerizable dental restorative material of claim 10 , wherein the amine accelerator is ethyl 4-(dimethylamino)benzoate.
12. The photopolymerizable dental restorative material of claim 1 , which is curable with ultraviolet-light, wherein the initiator is 2,2-dimethoxy-2-phenylacetophenone.