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

Patent metadata

Field	Value
Publication number	US-9982164-B2
Application number	US-201615240157-A
Country	US
Kind code	B2
Filing date	Aug 18, 2016
Priority date	Jun 23, 2014
Publication date	May 29, 2018
Grant date	May 29, 2018

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.

First claim

We claim:

1. A polymerizable liquid useful for the production of a three-dimensional object comprised of polyurea or a copolymer of polyurethane and polyurea by additive manufacturing, said polymerizable liquid comprising a mixture of:
(a) a reactive blocked prepolymer comprising a compound of formula A-X-A, 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 NH, and Z is a blocking group, said blocking group having a reactive epoxy, alkene, alkyne, or thiol terminal group,
(b) a chain extender,
(c) a photoinitiator,
(d) optionally a polyol and/or a polyamine,
(e) optionally a reactive diluent,
(f) a light absorbing pigment or dye in an amount of from 0.001 to 10 percent by weight, and
(g) optionally a filler, and
(h) a reactive blocked diisocyanate.

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 is present and comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, a polymer containing any one or more of the foregoing, or a combination 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;
from 1 to 40 percent by weight of said reactive diluent when present;
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 by weight of said filler when present.

9. A polymerizable liquid useful for the production of a three-dimensional object comprised of polyurea 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′):

where Z is a blocking group, said blocking group having a reactive epoxy, alkene, alkyne, or thiol terminal group,
(b) a polyamine,
(c) a chain extender,
(d) a photoinitiator, and
(e) optionally a reactive diluent,
(f) optionally a pigment or dye, and
(g) optionally a filler.

10. The liquid of claim 9 , further comprising:
(h) a reactive blocked diisocyante 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 is present and comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, a polymer containing any one or more of the foregoing, or a combination 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 polyamine;
from 1 to 40 percent by weight of said reactive diluent when present;
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 by weight of said pigment or dye when present, and
from 1 to 50 percent by weight of said filler when present.

18. A polymerizable liquid useful for the production of a three-dimensional object comprised of polyurea or a copolymer of polyurethane and polyurea 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″):

where R is a hydrocarbyl group, R′ is NH, and Z is a blocking group, said blocking group having a reactive epoxy, alkene, alkyne, or thiol terminal group,
(c) optionally one or more additional chain extenders,
(d) a photoinitiator,
(e) optionally a reactive diluent,
(f) optionally a pigment or dye,
(g) optionally a filler, and
(h) a reactive blocked diisocyanate prepolymer and/or a reactive blocked diisocyanate.

19. The liquid of claim 18 , comprising:
both the reactive blocked diisocyante prepolymer and the 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 is present and comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, a polymer containing any one or more of the foregoing, or a combination of two or more of the foregoing.

25. The liquid of claim 1 , said reactive blocked diisocyanate comprising a compound of formula A′-X′-A′, where X′ is a hydrocarbyl group and each

Assignees

• Carbon Inc

Inventors

• Rolland Jason P
• Chen Kai
• Poelma Justin
• Goodrich James
• Pinschmidt Robert
• Desimone Joseph M
• Robeson Lloyd M

Classifications

• B29K2105/251

  Particles, powder or granules (expandable particles B29K2105/046) · CPC title

• B29K2105/0091

  IPN, i.e. interpenetrating polymer networks · CPC title

• B29K2105/0073

  Solution · CPC title

• B29C64/286

  Optical filters, e.g. masks · CPC title

• C08G18/244

  tin salts of carboxylic acids · CPC title