Dual cure additive manufacturing of rigid intermediates that generate semi-rigid, flexible, or elastic final products

Patent metadata

Field	Value
Publication number	US-2018361660-A1
Application number	US-201616060568-A
Country	US
Kind code	A1
Filing date	Dec 19, 2016
Priority date	Dec 22, 2015
Publication date	Dec 20, 2018
Grant date	—

Abstract

Provided herein is a method of forming a three-dimensional object, comprising: (a) providing a carrier and a fill level having a build region therebetween; (b) filling said build region with a polymerizable liquid comprising a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable 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; and (d) solidifying and/or curing said second solidifiable component in said three-dimensional intermediate. The solidifying and/or curing step (d) may increase the elasticity and/or decrease the rigidity of said intermediate in forming said three-dimensional object.

First claim

1 . 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 (through said optically transparent member when present), 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; (d) optionally, but in some embodiments preferably, 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; with said solidifying and/or curing step (e) increasing the elasticity and/or decreasing the rigidity of said intermediate in forming said three-dimensional object.

2 . The method of claim 1 , wherein said solidifying and/or curing step (e) decreases the Young's modulus of said intermediate by at least percent, in forming said three-dimensional object.

3 . The method of claim 1 , wherein the three-dimensional object has a Young's modulus of from 2, percent, to 80 percent, of the Young's Modulus of the three-dimensional intermediate.

4 . The method of claim 1 , wherein the three-dimensional intermediate has a Young's Modulus of from 30 Megapascals to 200 Megapascals, and the three-dimensional object has a Young's modulus of from 0.1 Megapascals to 20 Megapascals.

5 . The method of claim 1 , wherein said second component comprises a polymerizable liquid solubilized in or suspended in said first component.

6 .- 7 . (canceled)

8 . The method of claim 1 , wherein said three-dimensional object comprises a polymer blend, interpenetrating polymer network, semi-interpenetrating polymer network, or sequential interpenetrating polymer network formed from said first component and said second component.

9 .- 10 . (canceled)

11 . The method of claim 1 , wherein said solidifying and/or curing step (e) is carried out subsequent to said irradiating step (c) and is carried out by:
(i) heating said second solidifiable component; (ii) irradiating said second solidifiable component with light at a wavelength different from that of the light in said irradiating step (c); (iii) contacting said second polymerizable component to water; and/or (iv) contacting said second polymerizable component to a catalyst.

12 . The method of claim 1 , wherein: said second component comprises the precursors to a polyurethane, polyurea, or copolymer thereof, a silicone resin, an epoxy resin, a cyanate ester resin, or a natural rubber; and said solidifying step is carried out by heating.

13 . (canceled)

14 . The method of claim 1 , wherein:
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 component.

15 .- 26 . (canceled)

27 . A method of forming a three-dimensional object comprised of polyurethane, polyurea, or copolymer thereof, said method 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 at least one of: (i) a blocked or reactive blocked prepolymer, (ii) a blocked or reactive blocked diisocyanate or branched isocyanate, or (iii) a blocked or reactive blocked diisocyanate or branched isocyanate chain extender; (c) irradiating said build region with light (through said optically transparent member when present) 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; (d) optionally, but in some embodiments preferably, washing said three-dimensional intermediate; and then (e) heating and/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; optionally, but in some embodiments preferably, with said heating and/or microwave irradiating step (e) increasing the elasticity and/or decreasing the rigidity of said intermediate in forming said three-dimensional object.

28 . The method of claim 27 , wherein said heating and/or microwave irradiating step (e) decreases the Young's modulus of said intermediate by at least 20 percent, in forming said three-dimensional object.

29 . The method of claim 27 , wherein the three-dimensional object has a Young's modulus of from 2 percent, to 80 percent, of the Young's Modulus of the three-dimensional intermediate.

30 . The method of claim 27 , wherein the three-dimensional intermediate has a Young's Modulus of from 30 Megapascals to 200 Megapascals, and the three-dimensional object has a Young's modulus of from 0.1 Megapascals to 20 Megapascals.

31 .- 33 . (canceled)

34 . The method of claim 27 , 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, (v) optionally a reactive diluent, (vi) optionally a pigment or dye, and (vii) optionally a filler.

35 . The method of claim 34 , wherein said blocked or reactive blocked prepolymer comprises a compound of the formula A-X-A or X(-A) n where n is at least 2.1, (on average), where X is a hydrocarbyl group and each A is an independently selected substituent of Formula (X):

where R is a hydrocarbyl group, R′ is O or NH, and Z is a blocking group, said blocking group optionally having a reactive terminal group.

36 .- 40 . (canceled)

41 . The method of claim 27 , said polymerizable liquid comprising a mixture of (i) a blocked or reactive blocked diisocyanate or branched isocyanate, (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.

42 . The method of claim 41 , wherein said blocked or reactive blocked diisocyanate or branched isocyanate comprises a compound of the formula A′-X′-A′ or X′(-A′) n , where n is at least 2.1 (on average), X′ is hydrocarbyl group and each A′ is an independently selected substituent of Formula (X′):

where Z is a blocking group, said blocking group optionally having a re

Assignees

• Carbon Inc

Inventors

• Chen Kai
• Robeson Lloyd M
• Rolland Jason P

Classifications

• B33Y50/02

  for controlling or regulating additive manufacturing processes · CPC title

• B29K2075/02

  Polyureas · CPC title

• B29C64/393

  for controlling or regulating additive manufacturing processes · CPC title

• B29C64/245

  Platforms or substrates (support structures intended to be sacrificed after manufacture B29C64/40) · CPC title

• B33Y10/00

  Processes of additive manufacturing · CPC title