Polyurethane resins having multiple mechanisms of hardening for use in producing three-dimensional objects

• US 9,453,142 B2
• Filed: 12/22/2015
• Issued: 09/27/2016
• Est. Priority Date: 06/23/2014
• Status: Active Grant

• Current Assignee: Carbon, Inc.
• Original Assignee: Carbon3D, Inc.
• Inventors: Rolland, Jason P., Chen, Kai, Poelma, Justin, Goodrich, James, Pinschmidt, Robert, DeSimone, Joseph M., Robeson, Lloyd M.
• Primary Examiner(s): Choi, Ling
• Assistant Examiner(s): WHITELEY, JESSICA
• Application Number:
  US14/977,974
• Publication Number:
  US 20160137839A1
• Time in Patent Office: 280 Days
• Field of Search: 522/81, 522/71, 522/189, 522/184, 522/1, 520/1
• 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 polymerizable liquid, or resin, useful for the production by additive manufacturing of a three-dimensional object of polyurethane, polyurea, or a copolymer thereof, is described. The resin includes 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.

Claims

1. 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 reactive blocked prepolymer comprising a compound of the formula A-X-A, where X is a hydrocarbyl group and each A is an independently selected substituent of Formula X;

2. The polymerizable liquid of claim 1, wherein said pigment or dye is:

(i) titanium dioxide,

(ii) carbon black, and/or

(iii) an organic ultraviolet light absorber.

3. The liquid of claim 1, wherein said reactive blocked prepolymer comprises a polyisocyanate;

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

4. The liquid of claim 1, wherein said reactive blocked prepolymer comprises a polyisocyanate oligomer produced by the reaction of at least one polyisocyanate with at least one polyol or polyamine.

5. The liquid of claim 1, wherein said reactive blocked prepolymer is blocked by reaction of a polyisocyanate oligomer with an alcohol (meth)acrylate, amine (meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent.

6. The liquid of claim 1, 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.

7. The liquid of claim 1, wherein said chain extender comprises at least one diol, diamine or dithiol chain extender.

8. The liquid of claim 1, wherein said polymerizable liquid comprises:

from 5 to 90 percent by weight of said reactive blocked prepolymer;

optionally, from 1 to 40 percent by weight of said reactive diluent;

from 5 to 30 percent by weight of said chain extender;

from 0.1 to 4 percent by weight of said photoinitiator, and

from 1 to 50 percent filler when present.

25. The liquid of claim 1, said reactive blocked diisocyanate comprising a compound of the formula A′

-X′

-A′

, where X′

is a hydrocarbyl group and each A′

is an independently selected substituent of Formula (X′

);

29. The liquid of claim 1, wherein said reactive blocked prepolymer is blocked by reaction of a polyisocyanate oligomer with an alcohol (meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent.

9. 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 reactive blocked diisocyanate comprising a compound of the formula A′

-X′

-A′

, where X′

is a hydrocarbyl group and each A′

is an independently selected substituent of Formula (X′

);

10. The liquid of claim 9, further comprising:

(h) a reactive blocked diisocyanate prepolymer.

11. The liquid of claim 9, wherein said pigment or dye is present and is a light absorbing pigment or dye in an amount of from 0.001 to 10 percent by weight.

12. The liquid of claim 11, wherein said pigment or dye is:

(i) titanium dioxide,

(ii) carbon black, and/or

(iii) an organic ultraviolet light absorber.

13. The liquid of claim 9, wherein each A′

is an independently selected substituent of Formula XI′

;

14. The liquid of claim 9, wherein said 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.

15. The liquid of claim 9, 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.

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

17. The liquid of claim 9, wherein said polymerizable liquid comprises:

from 5 to 90 percent by weight of said reactive blocked diisocyanate;

from 5 to 90 percent by weight of said polyol or polyamine;

optionally, from 1 to 40 percent by weight of said reactive diluent;

from 5 to 30 percent by weight of said chain extender; and

from 0.1 to 4 percent by weight of said photoinitiator;

from 0.1 to 2 percent pigment when present, and

from 1 to 50 percent filler when present.

26. The liquid of claim 10, said reactive blocked prepolymer comprising a compound of the formula A-X-A, where X is a hydrocarbyl group and each A is an independently selected substituent of Formula X:

30. The liquid of claim 9, wherein said reactive blocked diisocyanate is blocked by reaction of a polyisocyanate with an alcohol (meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent.

18. 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 polyol and/or polyamine,

(b) a reactive blocked diisocyanate chain extender comprising a compound of the formula A″

-X″

-A″

, where X″

is a hydrocarbyl group, and each A″

is an independently selected substituent of Formula (X″

);

19. The liquid of claim 18, comprising:

(h) both a reactive blocked diisocyanate prepolymer and a reactive blocked diisocyanate.

20. The liquid of claim 18, wherein said pigment or dye is present and is a light absorbing pigment or dye in an amount of from 0.001 to 10 percent by weight.

21. The liquid of claim 20, wherein said pigment or dye is:

(i) titanium dioxide,

(ii) carbon black, and/or

(iii) an organic ultraviolet light absorber.

22. The liquid of claim 18, wherein said reactive blocked diisocyanate chain extender comprises a diisocyanate oligomer produced by the reaction of at least one polyisocyanate with at least one chain extender.

23. The liquid of claim 18, wherein said reactive blocked diisocyanate chain extender is blocked by reaction of a diisocyanate oligomer with an alcohol (meth)acrylate, amine (meth)acrylate, maleimide or n-vinylformamide monomer blocking agent.

24. The liquid of claim 18, 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.

27. The liquid of claim 18, said reactive blocked diisocyanate comprising a compound of the formula A′

-X′

-A′

, where X′

is a hydrocarbyl group and each A′

is an independently selected substituent of Formula (X′

);

28. The liquid of claim 19, said reactive blocked diisocyanate comprising a compound of the formula A′

-X′

-A′

, where X′

is a hydrocarbyl group and each A′

is an independently selected substituent of Formula (X′

);