Curable composition for use in a high temperature lithography-based photopolymerization process and method of producing crosslinked polymers therefrom
US-2024325117-A1 · Oct 3, 2024 · US
US11045295B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-11045295-B2 |
| Application number | US-201615352274-A |
| Country | US |
| Kind code | B2 |
| Filing date | Nov 15, 2016 |
| Priority date | Dec 31, 2013 |
| Publication date | Jun 29, 2021 |
| Grant date | Jun 29, 2021 |
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A three-dimensional printing system including a feed source of uncured filled resin material, a print head configured to apply discrete layers of a composition including upconversion phosphors, and a radiation source configured to irradiate layers of uncured filled resin material and deposited layers of the composition is provided. A method of three dimensionally printing a dental article is also provided.
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What is claimed is: 1. A method of three dimensionally printing a dental article comprising: providing a first layer of uncured resin material comprising an uncured resin, a photoinitiator, and in the range of about 50% to 90% by weight inert filler particles; depositing, via a print head, a first discrete layer of a composition comprising upconversion phosphors to a predetermined surface region of the first layer of uncured resin material; providing a second layer of the uncured resin material overlying the first layer of uncured resin material and the deposited layer that comprises the upconversion phosphors; depositing, via a print head, a second discrete layer of the composition comprising upconversion phosphors to a predetermined surface region of the second layer of uncured resin material; providing a third layer of the uncured resin material overlying the second layer of uncured resin material and the second deposited layer that comprises the upconversion phosphors; irradiating the layers of uncured resin material and deposited layers comprising upconversion phosphors with a wavelength that causes the upconversion phosphors to luminesce at a wavelength corresponding to an activation wavelength of the photoinitiator in the uncured resin material and thereby curing the resin material in a region adjacent the upconversion phosphors to form a cured resin mass; and separating remaining uncured resin material from the cured resin mass, wherein the layers of the composition comprising upconversion phosphors are deposited to the predetermined surface regions of the uncured resin material in a pattern corresponding to a predetermined form of the dental article. 2. The method of claim 1 , wherein the layers of upconversion phosphors are deposited on surface regions of the uncured resin layers corresponding to the dental article such that the cured resin mass is in the form of the dental article. 3. The method of claim 2 , further comprising conducting secondary shaping operations on the dental article. 4. The method of claim 1 , wherein the layers of upconversion phosphors are deposited on surface regions of the uncured resin layers corresponding to a shell portion surrounding the dental article. 5. The method of claim 4 , wherein the step of separating comprises removing the cured resin mass as the shell portion such that the remaining uncured resin material is in the form of the dental article and thereafter curing the remaining uncured resin material in the form of the dental article. 6. The method of claim 1 , wherein the layers of upconversion phosphors are deposited both on a surface region of the uncured resin layer corresponding to the dental article and a surface region of the uncured resin layer corresponding to a shell portion surrounding the dental article the two surface regions separated by a gap portion of the uncured resin layer surface on which upconversion phosphors are not deposited such the step of irradiating results in a first cured resin mass in the form of the dental article and a second cured resin mass in the form of a shell at least partially surrounding the dental article. 7. The method of claim 6 , wherein the step of separating comprises removing the shell at least partially surrounding the dental article and thereafter removing remaining uncured resin mass from a surface of the dental article. 8. The method of claim 7 further comprising conducting secondary shaping operations on the dental article. 9. The method of claim 1 , wherein the provided layers of uncured resin material have a thickness in the range of about 25 microns to about 250 microns. 10. The method of claim 1 , wherein at least one of the provided layers of uncured resin material has a mechanical stopper to control layer thickness. 11. The method of claim 1 , wherein the provided layers of uncured resin material are provided from a continuous ribbon of material. 12. The method of claim 1 wherein a coating density of the upconversion phosphors of the first deposited layer is different from a coating density of the upconversion phosphors of the second deposited layer. 13. The method of claim 1 , wherein the upconversion phosphors of the composition of the deposited first discrete layer comprise an inorganic host lattice doped with a rare earth ion. 14. The method of claim 13 , wherein the inorganic host is selected from the group consisting of lanthanide fluorides, oxysulfides, fluorides, oxide hosts, a ytterbium fluoride salt, a yttrium fluoride salt, lutetium oxide, and yttrium oxide. 15. The method of claim 13 wherein the inorganic host lattice is doped or co-doped with one or more trivalent rare earth ions. 16. The method of claim 15 , 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+ ), scandium (Sc 3+ ), yttrium (Y 3+ ) and combinations thereof.
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