Dual cure article of manufacture with portions of differing solubility

A method of forming a three-dimensional object intermediate comprising an acidic region, comprising the steps of:

• (a) providing a carrier and a build plate, said build plate comprising a build surface with said build surface and said carrier defining a build region therebetween;
• (b) filling said build region with a polymerizable liquid composition useful for additive manufacturing, comprising:
• (i) a free radical photoinitiator;
• (ii) monomers and/or prepolymers that are polymerizable by exposure to actinic radiation or light, optionally wherein some or all of said monomers and/or prepolymers comprise one or more acid-labile groups;
• (iii) a chain extender, optionally wherein said chain extender comprises one or more acid-labile groups;
• and
• (iv) a photoacid generator,
• wherein at least one of said monomers and/or prepolymers, or said chain extender, comprises one or more acid-labile groups, and
• wherein said free radical photoinitiator and said photoacid generator are, or are selected to be, activated by light at different ranges of wavelengths or intensities, said polymerizable liquid composition contacting said build surface;
• (c) polymerizing said polymerizable liquid composition to form a crosslinked polymer, wherein said polymerizing is carried out by irradiating said build region through said build plate with a light at a first wavelength or intensity to activate the free radical photoinitiator and crosslink the monomers and/or prepolymers, thereby forming a crosslinked polymer in said build region;
• (d) activating the photoacid generator by further irradiating a portion of the build region intended to be acidic through said build plate with light at a second wavelength or intensity, whereby the photoacid generator produces acid in said crosslinked polymer to thereby form said acidic region;
• and
• (e) advancing said carrier with said crosslinked polymer adhered thereto away from said build surface on said build plate to create a subsequent build region between said crosslinked polymer and said build surface;
• to thereby form said three-dimensional object intermediate comprising an acidic region.

A method of forming a three-dimensional object intermediate comprising an acidic region, comprising the steps of:

• (a) providing a carrier and a build plate, said build plate comprising a semipermeable member, said semipermeable member comprising a build surface with said build surface and said carrier defining a build region therebetween, and with said build surface in fluid communication by way of the semipermeable member with a source of polymerization inhibitor;
• (b) filling said build region with a polymerizable liquid composition useful for additive manufacturing, comprising:
• (i) a free radical photoinitiator;
• (ii) monomers and/or prepolymers that are polymerizable by exposure to actinic radiation or light, optionally wherein some or all of said monomers and/or prepolymers comprise one or more acid-labile groups;
• (iii) a chain extender, optionally wherein said chain extender comprises one or more acid-labile groups;
• and
• (iv) a photoacid generator,
• wherein at least one of said monomers and/or prepolymers, or said chain extender, comprises one or more acid-labile groups, and
• wherein said free radical photoinitiator and said photoacid generator are, or are selected to be, activated by light at different ranges of wavelengths or intensities, said polymerizable liquid composition contacting said build surface;
• (c) polymerizing said polymerizable liquid composition to form a crosslinked polymer, wherein said polymerizing is carried out by irradiating said build region through said build plate with light at a first wavelength or intensity to activate the free radical photoinitiator and crosslink the monomers and/or prepolymers in said build region, while forming or maintaining a liquid film release layer comprised of said polymerizable liquid composition formed between said crosslinked polymer and said build surface, wherein polymerization of the liquid film release layer is inhibited by said polymerization inhibitor;
• (d) activating the photoacid generator by further irradiating a portion of the build region intended to be acidic through said build plate with light at a second wavelength or intensity, whereby the photoacid generator produces acid in said crosslinked polymer to thereby form said acidic region, while forming or maintaining the liquid film release layer comprised of said polymerizable liquid composition formed between said crosslinked polymer and said build surface, wherein polymerization of the liquid film release layer is inhibited by said polymerization inhibitor;
• and
• (e) advancing said carrier with said crosslinked polymer adhered thereto away from said build surface on said build plate to create a subsequent build region between said crosslinked polymer and said build surface;
• to thereby form a three-dimensional object intermediate comprising an acidic region.