US 11,654,620 B2
Serially curable resins useful in additive manufacturing
Marie K. Herring, Palo Alto, CA (US); and Matthew S. Menyo, San Francisco, CA (US)
Assigned to Carbon, Inc., Redwood City, CA (US)
Filed by Carbon, Inc., Redwood City, CA (US)
Filed on Sep. 2, 2021, as Appl. No. 17/464,964.
Application 17/464,964 is a continuation of application No. 16/018,260, filed on Jun. 26, 2018, granted, now 11,135,765.
Claims priority of provisional application 62/544,052, filed on Aug. 11, 2017.
Prior Publication US 2021/0394435 A1, Dec. 23, 2021
Int. Cl. B29C 64/129 (2017.01); B33Y 10/00 (2015.01); B33Y 70/00 (2020.01); B33Y 70/10 (2020.01); B29C 64/295 (2017.01); B29C 35/08 (2006.01); B29K 105/00 (2006.01); B29K 105/16 (2006.01); B29K 75/00 (2006.01)
CPC B29C 64/129 (2017.08) [B33Y 10/00 (2014.12); B33Y 70/00 (2014.12); B33Y 70/10 (2020.01); B29C 64/295 (2017.08); B29C 2035/0855 (2013.01); B29K 2075/00 (2013.01); B29K 2105/0002 (2013.01); B29K 2105/16 (2013.01)] 18 Claims
 
1. A method of forming a three-dimensional object, comprising:
(a) providing a carrier and an optically transparent member having a build surface, said carrier and said build surface defining a build region therebetween;
(b) filling said build region with a polymerizable liquid, said polymerizable liquid comprising a reactive blocked monomer and/or prepolymer, said reactive blocked monomer and/or prepolymer comprising a self-polymerizing monomer and/or prepolymer blocked with a light-polymerizable blocking group;
(c) irradiating said build region with light through said optically transparent member to form a solid polymer scaffold from said reactive blocked monomer and/or prepolymer and also advancing said carrier away from said build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, said three-dimensional object; and then
(d) heating, microwave irradiating, or both heating and microwave irradiating, said three-dimensional intermediate sufficiently to degrade said scaffold and regenerate said monomer and/or prepolymer in de-blocked form, which monomer and/or prepolymer in turn self-polymerize, to form said three-dimensional object,
wherein said reactive blocked monomer and/or prepolymer comprises a reactive blocked polyisocyanate, and said monomer and/or prepolymer in de-blocked form self-polymerizes by trimerization of said polyisocyanate, and
wherein said polymerizable liquid further comprises an isocyanate trimerization catalyst.