Methods of producing polyurethane three-dimensional objects from materials having multiple mechanisms of hardening

A method of forming a three-dimensional object comprised of polyurethane, polyurea, or copolymer thereof, said method 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;
• (c) irradiating said build region with light through said optically transparent member to form a solid blocked polymer scaffold and 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, with said intermediate containing said chain extender;
• and then
• (d) heating or microwave irradiating said three-dimensional intermediate sufficiently to form from said three-dimensional intermediate said three-dimensional object comprised of polyurethane, polyurea, or copolymer thereof;
• wherein:
• said polymerizable liquid comprising a mixture of (i) a blocked or reactive blocked prepolymer, (ii) a chain extender, (iii) a photoinitiator, (iv) optionally a polyol and/or a polyamine, and (v) optionally a reactive diluent, (vi) optionally a pigment or dye, (vii) optionally a filler;
• and wherein
• said reactive blocked prepolymer is blocked by reaction of a polyisocyanate oligomer with an amine (meth)acrylate, alcohol (meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent.

A method of forming a three-dimensional object comprised of polyurethane, polyurea, or copolymer thereof, said method 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;
• (c) irradiating said build region with light through said optically transparent member to form a solid blocked polymer scaffold and 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, with said intermediate containing said chain extender;
• and then
• (d) heating or microwave irradiating said three-dimensional intermediate sufficiently to form from said three-dimensional intermediate said three-dimensional object comprised of polyurethane, polyurea, or copolymer thereof;
• wherein:
• said polymerizable liquid comprising a mixture of (i) a blocked or reactive blocked diisocyanate, (ii) a polyol and/or polyamine, (iii) a chain extender, (iv) a photoinitiator, (v) optionally a reactive diluent (vi) optionally a pigment or dye, and (vii) optionally a filler;
• and wherein
• said blocked or reactive blocked diisocyanate is blocked by reaction of a polyisocyanate with an alcohol (meth)acrylate, amine (meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent.

A method of forming a three-dimensional object comprised of polyurethane, polyurea, or copolymer thereof, said method 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 at least one of:
• (i) a blocked or reactive blocked prepolymer, (ii) a blocked or reactive blocked diisocyanate, or (iii) a blocked or reactive blocked diisocyanate chain extender;
• (c) irradiating said build region with light through said optically transparent member to form a solid blocked polymer scaffold and 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, with said intermediate containing said chain extender;
• and then
• (d) heating or microwave irradiating said three-dimensional intermediate sufficiently to form from said three-dimensional intermediate said three-dimensional object comprised of polyurethane, polyurea, or copolymer thereof;
• wherein said polymerizable liquid further comprises a mixture of (i) a polyol and/or polyamine, (ii) a blocked or reactive blocked diisocyanate chain extender, (iii) optionally one or more additional chain extenders, (iv) a photoinitiator, (v) optionally a reactive diluent (vi) optionally a pigment or dye, and (vii) optionally a filler.