A method of forming a three-dimensional object, wherein said three-dimensional object is an insert for use between a helmet and a human body, is described. The method may use a polymerizable liquid, or resin, useful for the production by additive manufacturing of a three-dimensional object, comprising a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from said first component.

A method of forming a three-dimensional object is carried out by: (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween; (b) filling the build region with a polymerizable liquid, the polymerizable liquid including a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from the first component; (c) irradiating the build region with light through the optically transparent member to form a solid polymer scaffold from the first component and also advancing the carrier away from the build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, the three-dimensional object, and containing the second solidifiable component carried in the scaffold in unsolidified and/or uncured form; and (d) concurrently with or subsequent to the irradiating step, solidifying and/or curing the second solidifiable component in the three-dimensional intermediate to form the three-dimensional object.

Heterocyclic-functional resins, such as epoxides, oxetanes, cyclic carbonates, lactides and lactones, are used in radiation-curable formulations along with ethylenically unsaturated materials such as (meth)acrylates to achieve improved mechanical properties and/or lower shrinkage in the cured compositions prepared therefrom as compared to formulations containing the ethylenically unsaturated materials but no heterocyclic-functional resin. Polymerizable, ethylenically unsaturated metal complexes, such as Zn and Ca carboxylates prepared using unsaturated carboxylic acids or anhydrides, may be employed to effect thermal cure of the heterocyclic-functional resin component of such formulations, which are particularly useful in the production of 3D-printed articles and the like.

Heterocyclic-functional resins, such as epoxides, oxetanes, cyclic carbonates, lactides and lactones, are used in radiation-curable formulations along with ethylenically unsaturated materials such as (meth)acrylates to achieve improved mechanical properties and/or lower shrinkage in the cured compositions prepared therefrom as compared to formulations containing the ethylenically unsaturated materials but no heterocyclic-functional resin. Polymerizable, ethylenically unsaturated metal complexes, such as Zn and Ca carboxylates prepared using unsaturated carboxylic acids or anhydrides, may be employed to effect thermal cure of the heterocyclic-functional resin component of such formulations, which are particularly useful in the production of 3D-printed articles and the like.

A method of forming a three-dimensional object, wherein said three-dimensional object is an insert for use between a helmet and a human body, is described. The method may use a polymerizable liquid, or resin, useful for the production by additive manufacturing of a three-dimensional object, comprising a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from said first component.

A method of forming a three-dimensional object (e.g. comprised of polyurethane, polyurea, or copolymer thereof) is carried out by: (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween; (b) filling the build region with a polymerizable liquid, the polymerizable liquid comprising a mixture of: (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from the first component; (c) irradiating the build region with light through the optically transparent member to form a solid blocked polymer scaffold and advancing the carrier away from the build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, the three-dimensional object, with the intermediate containing the second solidifiable component; and then (d) contacting the three-dimensional intermediate to water to form the three-dimensional object.

A method of forming a three-dimensional object is carried out by: (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween; (b) filling the build region with a polymerizable liquid, the polymerizable liquid including a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from the first component; (c) irradiating the build region with light through the optically transparent member to form a solid polymer scaffold from the first component and also advancing the carrier away from the build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, the three-dimensional object, and containing the second solidifiable component carried in the scaffold in unsolidified and/or uncured form; and (d) concurrently with or subsequent to the irradiating step, solidifying and/or curing the second solidifiable component in the three-dimensional intermediate to form the three-dimensional object.

A method of forming a three-dimensional object is carried out by: (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween; (b) filling the build region with a polymerizable liquid, the polymerizable liquid including a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from the first component; (c) irradiating the build region with light through the optically transparent member to form a solid polymer scaffold from the first component and also advancing the carrier away from the build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, the three-dimensional object, and containing the second solidifiable component carried in the scaffold in unsolidified and/or uncured form; and (d) concurrently with or subsequent to the irradiating step, solidifying and/or curing the second solidifiable component in the three-dimensional intermediate to form the three-dimensional object.

A method of forming a three-dimensional object, wherein said three-dimensional object is an insert for use between a helmet and a human body, is described. The method may use a polymerizable liquid, or resin, useful for the production by additive manufacturing of a three-dimensional object, comprising a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from said first component.

A method of forming a three-dimensional object (e.g. comprised of polyurethane, polyurea, or copolymer thereof) is carried out by: (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween; (b) filling the build region with a polymerizable liquid, the polymerizable liquid comprising a mixture of: (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from the first component; (c) irradiating the build region with light through the optically transparent member to form a solid blocked polymer scaffold and advancing the carrier away from the build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, the three-dimensional object, with the intermediate containing the second solidifiable component; and then (d) contacting the three-dimensional intermediate to water to form the three-dimensional object.