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

• US 9,598,606 B2
• Filed: 12/22/2015
• Issued: 03/21/2017
• Est. Priority Date: 06/23/2014
• Status: Active Grant

• Current Assignee: Carbon, Inc.
• Original Assignee: Carbon, Inc.
• Inventors: Rolland, Jason P., Chen, Kai, Poelma, Justin, Goodrich, James, Pinschmidt, Robert, DeSimone, Joseph M., Robeson, Lloyd M.
• Primary Examiner(s): Tentoni, Leo B
• Application Number:
  US14/977,876
• Publication Number:
  US 20160137838A1
• Time in Patent Office: 455 Days
• Field of Search: 264/255, 264/308, 264/401, 264/482, 264/489, 264/494, 264/496
• US Class Current: 1/1
• CPC Class Codes: B29C 2033/0005 with transparent parts, e.g. permitting visual inspection of the interior of the cavity
• CPC Class Codes: B29C 2035/0827 using UV radiation
• CPC Class Codes: B29C 2035/0855 using microwave
• CPC Class Codes: B29C 35/0805 using electromagnetic radiation
• CPC Class Codes: B29C 64/106 using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
• CPC Class Codes: B29C 64/124 using layers of liquid which are selectively solidified
• CPC Class Codes: B29C 64/129 characterised by the energy source therefor, e.g. by global irradiation combined with a mask
• CPC Class Codes: B29C 64/135 the energy source being concentrated, e.g. scanning lasers or focused light sources
• CPC Class Codes: B29C 64/165 using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
• CPC Class Codes: B29C 64/255 Enclosures for the building material, e.g. powder containers
• CPC Class Codes: B29C 64/286 Optical filters, e.g. masks
• CPC Class Codes: B29C 64/386 Data acquisition or data processing for additive manufacturing
• CPC Class Codes: B29C 64/40 Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
• CPC Class Codes: B29C 71/0009 using liquids, e.g. solvents, swelling agents spectacle cases, e.g. for cleaning contact lenses A45C11/04; disinfecting or sterilising contact lenses A61L12/00, using liquid substances A61L2/20; cleaning involving the use of liquid in general B08B3/00; for hydrating contact lenses B29D11/00067
• CPC Class Codes: B29C 71/02 Thermal after-treatment B29C71/0063 and B29C71/0072 take precedence
• CPC Class Codes: B29D 11/00009 Production of simple or compound lenses
• CPC Class Codes: B29D 11/00663 Production of light guides
• CPC Class Codes: B29K 2075/00 Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2075/02 Polyureas
• CPC Class Codes: B29K 2105/0002 monomers or prepolymers
• CPC Class Codes: B29K 2105/0058 : Liquid or visquous
• CPC Class Codes: B29K 2105/0073 : Solution
• CPC Class Codes: B29K 2105/0091 : IPN, i.e. interpenetrating polymer networks
• CPC Class Codes: B29K 2105/043 : Skinned foam
• CPC Class Codes: B29K 2105/16 : Fillers
• CPC Class Codes: B29K 2105/251 : Particles, powder or granules expandable particles B29K2105/046
• CPC Class Codes: B29K 2509/00 : Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler
• CPC Class Codes: B29K 2995/0026 : Transparent
• CPC Class Codes: B29L 2011/00 : Optical elements, e.g. lenses, prisms
• CPC Class Codes: B29L 2011/0016 : Lenses
• CPC Class Codes: B29L 2011/0075 : Light guides, optical cables
• CPC Class Codes: B29L 2031/001 : Profiled members, e.g. beams, sections
• CPC Class Codes: B29L 2031/10 : Building elements, e.g. bricks, blocks, tiles, panels, posts, beams frameless domes B29L2025/00, doors B29L2031/724
• CPC Class Codes: B33Y 10/00 : Processes of additive manufacturing
• CPC Class Codes: B33Y 30/00 : Apparatus for additive manufacturing; Details thereof or accessories therefor
• CPC Class Codes: B33Y 50/02 : for controlling or regulating additive manufacturing processes
• CPC Class Codes: B33Y 70/00 : Materials specially adapted for additive manufacturing
• CPC Class Codes: B33Y 80/00 : Products made by additive manufacturing
• CPC Class Codes: C08F 220/1808 : C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
• CPC Class Codes: C08F 220/1811 : C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
• CPC Class Codes: C08F 220/34 : Esters containing nitrogen , e.g. N,N-dimethylaminoethyl (meth)acrylate
• CPC Class Codes: C08F 222/102 : of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• CPC Class Codes: C08F 222/1063 : of alcohol terminated polyethers
• CPC Class Codes: C08F 283/006 : on to polymers provided for in C08G18/00 C08F283/004 takes precedence
• CPC Class Codes: C08F 290/067 : Polyurethanes; Polyureas
• CPC Class Codes: C08G 18/10 : Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/244 : tin salts of carboxylic acids
• CPC Class Codes: C08G 18/40 : High-molecular-weight compounds C08G18/2805 takes precedence
• CPC Class Codes: C08G 18/42 : Polycondensates having carboxylic or carbonic ester groups in the main chain
• CPC Class Codes: C08G 18/48 : Polyethers
• CPC Class Codes: C08G 18/4825 : Polyethers containing two hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: C08G 18/4854 : Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• CPC Class Codes: C08G 18/672 : Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08G 18/69 : Polymers of conjugated dienes hydrogenated polymers of conjugated dienes C08G18/6208
• CPC Class Codes: C08G 18/73 : acyclic
• CPC Class Codes: C08G 18/755 : and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• CPC Class Codes: C08G 18/758 : containing two or more cycloaliphatic rings
• CPC Class Codes: C08G 18/7671 : containing only one alkylene bisphenyl group
• CPC Class Codes: C08G 18/81 : Unsaturated isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/8175 : with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08J 2375/14 : Polyurethanes having carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08J 5/00 : Manufacture of articles or shaped materials containing macromolecular substances manufacture of semi-permeable membranes B01D67/00 - B01D71/00
• CPC Class Codes: C08K 3/01 : characterized by their specific function
• CPC Class Codes: C08K 3/013 : Fillers, pigments or reinforcing additives
• CPC Class Codes: C08K 5/0008 : Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• CPC Class Codes: C08K 5/0041 : Optical brightening agents, organic pigments
• CPC Class Codes: C08L 75/04 : Polyurethanes
• CPC Class Codes: C08L 75/14 : Polyurethanes having carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09D 135/02 : Homopolymers or copolymers of esters C09D135/06, C09D135/08 take precedence
• CPC Class Codes: C09D 175/04 : Polyurethanes
• CPC Class Codes: C09D 175/08 : from polyethers
• CPC Class Codes: G03F 7/00 : Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor using photoresist structures for special production processes, see the relevant places, e.g. B44C, H01L, e.g. H01L21/00, H05K
• CPC Class Codes: G03F 7/0037 : Production of three-dimensional images
• CPC Class Codes: G03F 7/027 : Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence
• CPC Class Codes: G03F 7/038 : Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021
• CPC Class Codes: G03F 7/0757 : Macromolecular compounds containing Si-O, Si-C or Si-N bonds G03F7/0752 takes precedence
• CPC Class Codes: G03F 7/38 : Treatment before imagewise removal, e.g. prebaking G03F7/265 takes precedence

Abstract

A method of forming a three-dimensional object 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 including 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 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 chain extender; and then (d) heating or microwave irradiating the three-dimensional intermediate sufficiently to form from the three-dimensional intermediate the three-dimensional object of polyurethane, polyurea, or copolymer thereof.

Claims

1. 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;

wherein said irradiating and/or said advancing steps are carried out while also concurrently;

(i) continuously maintaining a dead zone of polymerizable liquid in contact with said build surface, and

(ii) continuously maintaining a gradient of polymerization zone between said dead zone and said solid blocked polymer scaffold and in contact with each thereof, said gradient of polymerization zone comprising said first component in partially cured form; 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.

2. The method of claim 1, wherein said optically transparent member comprises a semipermeable member, and said continuously maintaining a dead zone is carried out by feeding an inhibitor of polymerization through said optically transparent member, thereby creating a gradient of inhibitor in said dead zone and optionally in at least a portion of said gradient of polymerization zone.

3. The method of claim 2, wherein said semipermeable member comprises a fluoropolymer.

4. The method of claim 1, 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.

5. The method of claim 4, wherein said blocked or reactive blocked prepolymer comprises a blocked polyisocyanate;

and/or said reactive blocked prepolymer comprises two or more ethylenically unsaturated end groups.

6. The method of claim 4, wherein said blocked or reactive blocked prepolymer comprises a polyisocyanate oligomer produced by the reaction of at least one polyisocyanate with at least one polyol or polyamine.

8. The method of claim 4, wherein said reactive diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, and combinations of two or more of the foregoing.

9. The method of claim 4, wherein said chain extender comprises at least one diol, diamine or dithiol chain extender.

10. The method of claim 1, 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, and (v) optionally a reactive diluent (vi) optionally a pigment or dye, (vii) optionally a filler.

12. The method of claim 10, wherein said reactive diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, and combinations of two or more of the foregoing.

13. The method of claim 10, wherein said chain extender comprises at least one diol, diamine or dithiol chain extender.

18. The method of claim 1, wherein said three-dimensional object comprises (i) a linear thermoplastic polyurethane, polyurea, or copolymer thereof, (ii) a cross-linked thermoset polyurethane, polyurea, or copolymer thereof, or (iii) combinations thereof, optionally blended with de-blocked blocking group which is copolymerized with said reactive diluents(s).

19. The method of claim 1, wherein:

said three-dimensional object is rigid, is comprised of polyurethane, polyurea, or copolymer thereof, has a Young'"'"'s modulus of 800 to 3500 megapascals, has a tensile strength of 30 to 100 megapascals, and has a percent elongation at break of from 1 to 100;

or

said three-dimensional object is rigid and flexible, is comprised of polyurethane, polyurea, or copolymer thereof, has a Young'"'"'s modulus of 300 to 2500 megapascals, has a tensile strength of from 20 to 70 megapascals, and has a percent elongation at break of from 40 to 600;

or

said three-dimensional object is elastomeric, is comprised of polyurethane, polyurea, or copolymer thereof, has a Young'"'"'s modulus of 0.5 to 40 megapascals, has a tensile strength of from 0.5 to 30 megapascals, and has a percent elongation at break of from 50 to 1000.

20. The method of claim 1, wherein said three-dimensional object further comprises reacted photoinitiator fragments.

21. The method of claim 1, wherein said three-dimensional object further comprises a filler and/or a dye.

22. The method of claim 1, wherein said solidifiable or polymerizable liquid is changed at least once during said method with a subsequent solidifiable or polymerizable liquid;

where said subsequent solidifiable or polymerizable liquid is cross-reactive with each previous solidifiable or polymerizable liquid during said heating or microwave irradiating step (d), to form an object having a plurality of structural segments covalently coupled to one another, each structural segment having different structural properties.

23. The method of claim 1, wherein:

said three-dimensional object is rigid, is comprised of polyurethane, polyurea, or copolymer thereof, has a Young'"'"'s modulus of 800 to 3500 megapascals, has a tensile strength of 30 to 100 megapascals, and has a percent elongation at break of from 1 to 100.

24. The method of claim 1, wherein:

said three-dimensional object is rigid and flexible, is comprised of polyurethane, polyurea, or copolymer thereof, has a Young'"'"'s modulus of 300 to 2500 megapascals, has a tensile strength of from 20 to 70 megapascals, and has a percent elongation at break of from 40 to 300 or 600.

25. The method of claim 1, wherein:

said three-dimensional object is elastomeric, is comprised of polyurethane, polyurea, or copolymer thereof, has a Young'"'"'s modulus of 0.5 to 40 megapascals, has a tensile strength of from 0.5 to 30 megapascals, and has a percent elongation at break of from 50 to 1000.

26. The method of claim 1, wherein said polymerizable liquid further comprises thermoplastic particles.

7. 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.

27. The method of claim 7, wherein said polymerizable liquid further comprises thermoplastic particles.

11. 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.

28. The method of claim 11, wherein said polymerizable liquid further comprises thermoplastic particles.

14. 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.

15. The method of claim 14, wherein said blocked or reactive blocked diisocyanate chain extender comprises a diisocyanate molecule produced by the reaction of at least one polyisocyanate with at least one chain extender.

16. The method of claim 14, wherein said reactive blocked chain extender is blocked by reaction of a diisocyanate molecule with an alcohol (meth)acrylate, amine (meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent.

17. The method of claim 14, wherein said reactive diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, and combinations of two or more of the foregoing.

29. The method of claim 14, wherein said polymerizable liquid further comprises thermoplastic particles.