Accelerants for additive manufacturing with dual cure resins

A method of forming a three-dimensional object, comprising:

• (a) providing a carrier and a fill level, and optionally an optically transparent member having a build surface defining said fill level, said carrier and said fill level having a build region therebetween;
• (b) filling said build region with a polymerizable liquid, said polymerizable liquid comprising a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from said first component;
• (c) irradiating said build region with light to form a solid polymer scaffold from said first component 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 containing said second solidifiable component carried in said scaffold in unsolidified and/or uncured form,
• said polymerizable liquid further comprising a Lewis acid or an oxidizable tin salt in said polymerizable liquid in an amount effective to accelerate the formation of said three-dimensional intermediate during said irradiating;
• (d) optionally washing said three-dimensional intermediate;
• and
• (e) concurrently with or subsequent to said irradiating step, solidifying and/or curing said second solidifiable component in said three-dimensional intermediate to form said three-dimensional object, wherein:
• said solidifying and/or curing step (e) is carried out subsequent to said irradiating step;
• and
• said solidifying and/or curing step (e) is carried out under conditions in which said solid polymer scaffold degrades and forms a constituent necessary for the polymerization of said second solidifiable component.

A method of forming a three-dimensional object, comprising:

• (a) providing a carrier and a fill level, and optionally an optically transparent member having a build surface defining said fill level, said carrier and said fill level having a build region therebetween;
• (b) filling said build region with a polymerizable liquid, said polymerizable liquid comprising a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from said first component;
• (c) irradiating said build region with light to form a solid polymer scaffold from said first component 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 containing said second solidifiable component carried in said scaffold in unsolidified and/or uncured form,
• said polymerizable liquid further comprising a Lewis acid or an oxidizable tin salt in said polymerizable liquid in an amount effective to accelerate the formation of said three-dimensional intermediate during said irradiating;
• (d) optionally washing said three-dimensional intermediate;
• and
• (e) concurrently with or subsequent to said irradiating step, solidifying and/or curing said second solidifiable component in said three-dimensional intermediate to form said three-dimensional object,
• said first component comprising monomers and/or prepolymers that can be polymerized by exposure to actinic radiation or light, and
• said second solidifiable component solidifiable on contacting to heat, water, water vapor, light at a different wavelength than that at which said first component is polymerized, catalysts, evaporation of a solvent from the polymerizable liquid, exposure to microwave irradiation, or combinations thereof.

A three-dimensional object comprised of:

• (a) a light polymerized first component, and
• (b) a second solidified component different from said first component;
• said first component and/or second solidified component further comprising a Lewis acid or an oxidizable tin salt;
• said object optionally comprising a polymer blend formed from said first component and said second solidified component, with said polymer blend comprising an interpenetrating polymer network, a semi-interpenetrating polymer network, or a sequential interpenetrating polymer network;
• and further comprising:
• (c) a third solidified component different from said first component and second solidified component, with said object having at least a first structural segment and a second structural segment covalently coupled to one another,
• said first structural segment comprised of said second solidified component,
• said second structural segment comprised of said third solidified component, and
• both said first and second structural segments comprised of the same or different light polymerized first component.

A polymerizable liquid useful for the production of a three-dimensional object comprised of polyurethane, polyurea, or a copolymer thereof by additive manufacturing, said polymerizable liquid comprising a mixture of:

• (a) a blocked or reactive blocked prepolymer,
• (b) a chain extender,
• (c) a photoinitiator,
• (d) optionally a polyol and/or a polyamine,
• (e) optionally a reactive diluent,
• (f) a light absorbing pigment or dye in an amount of from 0.001 to 10 percent by weight,
• (g) optionally a filler, and
• (h) a Lewis acid or an oxidizable tin salt.