Sealed isocyanates
View Patent ↗The present disclosure relates to sealed isocyanate resin compositions. The resin compositions may be used for additive manufacturing. One embodiment of the invention includes a photopolymerizable resin for additive manufacturing, the resin comprising: a blocked isocyanate; at least one monomer or oligomer; and a multifunctional nucleophile.
1. A storage-stable photopolymerizable resin mixture, the resin mixture comprising:
at least about 30% by weight of one or more acrylic monomers;
a stabilized thiol comprising one or more thiol functional groups; and
a blocked isocyanate,
wherein the blocked isocyanate is configured to liberate a reactive isocyanate functionality,
wherein, after combination of the one or more acrylic monomers, the stabilized thiol, and the blocked isocyanate, the resin mixture exhibits no more than a 100% increase in viscosity after 1 week at room temperature.
2. The photopolymerizable resin according to claim 1 , wherein the blocked isocyanate includes at least one of a uretdione, a biuret, an allophanate, an isocyanaurate, methylene dicyclohexyl diisocyanate (MDI), or toluene diisocyanate (TDI).
3. The photopolymerizable resin according to claim 2 , wherein the uretdione is a uretdione of hexamethylene diisocyanate (HDI), a uretdione of isophorone diisocyanate (IDI), a uretdione of methylene dicyclohexyl diisocyanate (MDI), a uretdione of hydrogenated methylene dicyclohexyl diisocyanate (HMDI), or a uretdione of toluene diisocyanate (TDI).
4. The photopolymerizable resin according to claim 2 , wherein the isocyanaurate is an isocyanaurate of hexamethylene diisocyanate (HDI), an isocyanaurate of isophorone diisocyanate (IDI), an isocyanaurate of methylene dicyclohexyl diisocyanate (MDI), an isocyanaurate of hydrogenated methylene dicyclohexyl diisocyanate (HMDI), or an isocyanaurate of toluene diisocyanate (TDI).
5. The photopolymerizable resin according to claim 2 , wherein the biuret is a biuret of hexamethylene diisocyanate (HDI), a biuret of isophorone diisocyanate (IDI), a biuret of methylene dicyclohexyl diisocyanate (MDI), a biuret of hydrogenated methylene dicyclohexyl diisocyanate (HMDI), or a biuret of toluene diisocyanate (TDI).
6. The photopolymerizable resin according to claim 2 , wherein the allophanate is an allophanate of hexamethylene diisocyanate (HDI), an allophanate of isophorone diisocyanate (IDI), an allophanate of methylene dicyclohexyl diisocyanate (MDI), an allophanate of hydrogenated methylene dicyclohexyl diisocyanate (HMDI), or an allophanate of toluene diisocyanate (TDI).
7. The photopolymerizable resin according to claim 1 , wherein the blocked isocyanate includes an isocyanate and a blocking agent.
8. The photopolymerizable resin according to claim 7 , wherein the isocyanate is configured to react with the blocking agent such that isocyanate functional groups of the isocyanate are end-capped.
9. The photopolymerizable resin according to claim 7 , wherein the blocking agent includes at least one of a nucleophile, a derivative of an alcohol, a hindered amine, a caprolactam, a phenol, an oxime, or a pyrazole malonate.
10. The resin mixture according to claim 1 , wherein the one or more acrylic monomers, the stabilized thiol, and the blocked isocyanate are configured to react by exposure to light to form a cured material.
11. The resin mixture according to claim 10 , wherein the blocked isocyanate is configured to liberate the reactive isocyanate functionality during or after exposure of the resin mixture to light.
12. The resin mixture according to claim 1 , further comprising at least one of a vinylic monomer, an allylic monomer, or a norbornyl monomer.
13. The resin mixture according to claim 1 , further comprising one or more oligomers.
14. The resin mixture according to claim 1 , wherein the stabilized thiol comprises less than about 5% by weight of the resin mixture.
15. The resin mixture according to claim 1 , further comprising at least one of a photoinitiator, an inhibitor, a dye, or a filler.
16. The resin mixture according to claim 15 , wherein the photoinitiator comprises about 0.01-3% by weight of the resin.
17. The resin mixture according to claim 1 , wherein the resin mixture exhibits no more than a 25% increase in viscosity after continuous use in a 3D printing operation in an air environment for a period of about 10 weeks.
18. The resin mixture according to claim 1 , wherein the stabilized thiol includes a bulky side chain.
19. The resin mixture according to claim 1 , wherein the stabilized thiol includes at least one of a difunctional thiol, trifunctional thiol, tetrafunctional thiol, or multi-functional thiol.
20. The resin mixture according to claim 1 , wherein the stabilized thiol comprises a secondary thiol.
21. The resin mixture according to claim 20 , wherein the secondary thiol includes at least one of Pentaerythritol tetrakis (3-mercaptobutylate), 1,4-bis (3-mercaptobutylyloxy) butane, or 1,3,5-Tris(3-mercaptobutyloxethyl)-1,3,5-triazine.