Dental compositions containing upconversion phosphors and methods of use
A luminescent coating is disclosed that is used to dimensionally control the curing of a photocurable agent placed in close contact with the coating. The coating is applied at the interface of structures, such as brackets and prosthetics, or may be applied directly on a curable material for use in 3D printing, at the location where bonding material is needed to be cured. The luminescent coating irradiates from its structure the curing radiations necessary to photopolymerize the resin in response to a first radiation irradiated on its structure of a different wavelength.
1. A luminescent coating composition comprising:
a binder; and
upconversion phosphors;
wherein the upconversion phosphors emit radiation at a predetermined wavelength in a range of about 360 nm to 520 nm when the upconversion phosphors are irradiated with radiation having a wavelength of at least 780 nm; and
wherein the binder comprises a (meth)acrylate resin binder selected from the group consisting of 2,2-bis[4-(2-hydroxy-3-methacryloyl oxypropoxy)phenyl] propane (Bis-GMA), 1,6-bis(2-methacryloxyethoxycarbonylamino)-2,4,4-trim ethyl hexane (UDMA), 2,2-bis[4-(methacryloyloxy-ethoxy)phenyl] propane (or ethoxylated bisphenol A-dimethacrylate) (EBPADMA), isopropyl methacrylate, triethyleneglycol dimethacrylate (TEGDMA), diethyleneglycol dimethacrylate, tetraethyleneglycol dimethacrylate, 3-(acryloyloxy)-2-hydroxypropyl methacrylate, 1,3-propanediol dimethacrylate, 1,6-hexanediol dimethacrylate (HDDMA), pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and combinations thereof.
2. The luminescent coating composition of claim 1 comprising at least 50% by weight upconversion phosphors.
3. The luminescent coating composition of claim 1 , wherein the luminescent coating composition is substantially free of photoinitiator.
4. The luminescent coating composition of claim 1 , wherein the upconversion phosphors comprise an inorganic host lattice doped with a rare earth ion.
5. The luminescent coating composition of claim 4 , wherein the inorganic host is selected from the group consisting of lanthanide fluorides, oxysulfides, oxyfluorides, halides, and oxide hosts.
6. The luminescent coating composition of claim 5 , wherein the inorganic host is selected from the group consisting of NaYF 4 , NaYbF 4 , Na 5 Y 9 F 32 , Na 5 Yb 9 F 32 , lutetium oxide, and yttrium oxide.
7. The luminescent coating composition of claim 5 , wherein the inorganic host is doped or co-doped with one or more trivalent rare earth ions.
8. The luminescent coating composition of 7 , wherein the trivalent rare earth ions are selected from the group consisting of ytterbium (Yb 3+ ), lutetium (Lu 3+ ), thulium (Tm 3+ ), terbium (Tb 3+ ), erbium (Er 3+ ), praseodymium (Pr 3+ ), and combinations thereof.
9. The luminescent coating composition of claim 1 , wherein the upconversion phosphors emit radiation having a wavelength of 495 nm or less.
10. A method of attaching a dental article to the surface of a tooth comprising:
providing the dental article to be attached to the surface of the tooth;
applying a luminescent coating to a surface of the dental article configured to face toward the surface of the tooth, the luminescent coating having a luminescent coating composition comprising:
a binder; and
upconversion phosphors;
wherein the upconversion phosphors emit radiation at an activation wavelength in a range of about 360 nm to 520 nm when the upconversion phosphors are irradiated with radiation having a wavelength of at least 780 nm; and
wherein the binder comprises a (meth)acrylate resin binder selected from the group consisting of 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl] propane (Bis-GMA), 1,6-bis(2-methacryloxyethoxycarbonylamino)-2,4,4-trimethylhexane (UDMA), 2,2-bis[4-(methacryloyloxy-ethoxy)phenyl] propane (or ethoxylated bisphenol A-dimethacrylate) (EBPADMA), isopropyl methacrylate, triethyleneglycol dimethacrylate (TEGDMA), diethyleneglycol dimethacrylate, tetraethyleneglycol dimethacrylate, 3-(acryloyloxy)-2-hydroxypropyl methacrylate, 1,3-propanediol dimethacrylate, 1,6-hexanediol dimethacrylate (HDDMA), pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and combinations thereof;
applying to the surface of the tooth a dental cement composition comprising a polymerizable resin and a photoinitiator, the dental cement composition being substantially free of upconversion phosphors;
placing the dental article on the surface of the tooth such that the luminescent coating comprising upconversion phosphors is adjacent the dental cement composition;
irradiating the luminescent coating comprising upconversion phosphors with a radiation source that emits radiation at a predetermined fixed wavelength in a range of the electromagnetic spectrum that causes the upconversion phosphors to emit radiation at the activation wavelength of the photoinitiator such that the dental cement composition cures in a region adjacent the luminescent coating; and
removing remaining uncured dental cement composition outside the dental article from the tooth.
11. The method of claim 10 , wherein the dental article is an orthodontic bracket.
12. The method of claim 11 , wherein the surface of the tooth is a labial surface of the tooth.
13. The method of claim 10 , wherein the dental article is a dental prosthetic.
14. The method of claim 13 , wherein the dental prosthetic is a crown.
15. The method of claim 10 , wherein the luminescent coating composition comprising upconversion phosphors is at least 50% by weight upconversion phosphors.
16. The method of claim 10 , wherein the resin binder of the coating composition is the same as the polymerizable resin of the dental cement.
17. The method of claim 10 , wherein the step of applying the luminescent coating to the surface of the dental article comprises coating an outer periphery of the surface of the dental article.
18. The method of claim 10 , wherein the step of applying the luminescent coating to the surface of the dental article comprises leaving an outer edge of the surface of the dental article uncoated.
19. The method of claim 10 , wherein the step of irradiation comprises irradiating the upconversion phosphors with near-infrared radiation having a wavelength in the range of about 780 nm to about 1064 nm.
20. The method of claim 10 , wherein the dental article is metallic and wherein, after the step of removing remaining uncured dental cement composition outside the dental article from the tooth, irradiating the dental article with a blue light to cure any remaining uncured dental cement composition intermediate the labial surface of the tooth and the surface of the dental article.