Resin materials for making three-dimensional objects and methods of using the same

1 . A polymerizable liquid used for producing three-dimensional objects by methods of additive manufacturing, said polymerizable liquid comprising:

a blocked or reactively blocked polyurethane prepolymer;

a blocked or reactively blocked curing agent, wherein the blocked or reactively blocked curing agent is a diol compound with two hydroxyl groups protected, a diamine compound with two amino groups protected, or a diimine compound with two imino groups protected, and under a reactive condition, protecting groups in the blocked or reactively blocked curing agent are cleaved to make the two blocked amino groups, the blocked two imine groups, or the two blocked hydroxyl groups exposed to form the two amino groups, the two imine groups, or the two hydroxyl groups for curing; and

a photoinitiator.

2 . The polymerizable liquid of claim 1 , wherein the blocked or reactively blocked curing agent comprises a photopolymerizable group.

3 . The polymerizable liquid of claim 1 , wherein said blocked or reactively blocked curing agent has a structure of Formula (A1), Formula (A2), or Formula (A3):

wherein each of R 1 , R 2 , and R 3 includes a linear or branched C1-C36 alkyl, a linear or branched C1-C36 alkylene, an alkenyl, an alkenylene, an aryl, an arylene, a heteroaryl, a heteroarylene, a cycloalkyl, or cycloalkenyl; and

each of Y 1 and Y 2 includes a protecting group that protects amino groups, imine groups, or hydroxyl groups.

4 . The polymerizable liquid of claim 3 , wherein said blocked or reactively blocked curing agent comprises an imine group, said imine group is a substituent derived from a reaction of an aldehyde or ketone with an amine.

5 . The polymerizable liquid of claim 3 , wherein said blocked or reactively blocked curing agent comprises a carbamate group, said carbamate group is a substituent derived from a reaction of a carboxylic acid or carboxylic ester with an amine.

6 . The polymerizable liquid of claim 3 , wherein each of at least one of said Y 1 or said Y 2 further comprises a photopolymerizable group.

7 . The polymerizable liquid of claim 6 , wherein said photopolymerizable group comprises an acrylate group or a methacrylate group.

8 . The polymerizable liquid of claim 1 , wherein said blocked or reactively blocked curing agent has a structure of Formula (A4), Formula (A5), or Formula (A6):

wherein each of R 4 , R 5 , and R 6 includes an amino-dialkyl, a C3-C36 aryl, an arylene, a cycloalkyl, or a cycloalkenyl;

each of Y 1 and Y 2 includes a protecting group that protects amino groups, imine groups, or hydroxyl groups; and

X comprises a photopolymerizable group.

9 . The polymerizable liquid of claim 8 , wherein said blocked or reactively blocked curing agent comprises an imine group, said imine group is a substituent derived from a reaction of an aldehyde or ketone with an amine.

10 . The polymerizable liquid of claim 8 , wherein said blocked or reactively blocked curing agent comprises a carbamate group, said carbamate group is a substituent derived from a reaction of a carboxylic acid or carboxylic ester with an amine.

11 . The polymerizable liquid of claim 8 , wherein said X comprises an acrylate group or a methacrylate group.

12 . The polymerizable liquid of claim 1 , said polymerizable liquid further comprising:

a reactive diluent.

13 . The polymerizable liquid of claim 1 , said polymerizable liquid further comprising:

a blocked or reactively blocked diisocyanate.

14 . The polymerizable liquid of claim 1 , wherein the blocked or reactively blocked curing agent includes at least one photopolymerizable group, and one of the at least one photopolymerizable group is located in a position of the blocked or reactively blocked curing agent, excluding the protecting groups.

15 . The polymerizable liquid of claim 1 , wherein the two amino groups, the two imine groups, and the two hydroxyl groups are terminally positioned in the diol compound, the diamine compound, and the diimine compound, respectively.

16 . A method for forming a three-dimensional object, comprising:

providing a printing region defined by a forming platform and a resin reservoir having a forming surface;

filling said printing region with a polymerizable liquid, said polymerizable liquid including a blocked or reactively blocked polyurethane prepolymer, a blocked or reactively blocked curing agent, and a photoinitiator, wherein the blocked or reactively blocked curing agent is a diol compound with two hydroxyl groups protected, a diamine compound with two amino groups protected, or a diimine compound with two imino groups protected, and under a reactive condition, protecting groups in the blocked or reactively blocked curing agent are cleaved to make the two blocked amino groups, the two blocked imine groups, or the two blocked hydroxyl groups exposed to form the two amino groups, the two imine groups, or the two hydroxyl groups for curing;

exposing said printing region filled with the polymerizable liquid to energy to form a solid printing intermediate having substantially a same shape as said three-dimensional object; and

providing energy to said solid printing intermediate to form said three-dimensional object.

17 . The method of claim 16 , wherein said blocked or reactively blocked curing agent is contained in said solid printing intermediate in a cured form.

18 . The method of claim 16 , wherein said three-dimensional object comprises a copolymer of polyurethane and polyacrylate.

19 . The method of claim 16 , wherein said three-dimensional object comprises a polymer blend, an interpenetrating polymer network, a semi-interpenetrating polymer network, or a sequential interpenetrating polymer network of polyurethane and polyacrylate.