Dual cure resins for additive manufacturing

Patent metadata

Field	Value
Publication number	US-11241822-B2
Application number	US-201917276858-A
Country	US
Kind code	B2
Filing date	Sep 24, 2019
Priority date	Sep 25, 2018
Publication date	Feb 8, 2022
Grant date	Feb 8, 2022

Abstract

Provided herein is a resin product useful for the production of three-dimensional objects by additive manufacturing, and methods using the same. The resin may include a reactive blocked prepolymer comprising a prepolymer blocked with reactive blocking groups; a polyol; a photoinitiator; and at least one organometallic catalyst. A packaged product useful for the production of three-dimensional objects by additive manufacturing, the product comprising a single container having a single chamber and a resin in the chamber with all components mixed together, is also provided.

First claim

We claim:

1. A resin useful for the production of three-dimensional objects by additive manufacturing, comprising:
(a) a reactive blocked prepolymer comprising a prepolymer blocked with reactive blocking groups;
(b) a polyol;
(c) a photoinitiator;
(d) at least one non-tin organometallic catalyst, said at least one non-tin organometallic catalyst comprising a metal carboxylate;
(e) optionally, a reactive diluent;
(f) optionally, a filler; and
(g) optionally, a pigment or dye.

2. The resin of claim 1 , wherein said reactive blocked prepolymer comprises a polyurethane prepolymer, a polyurea prepolymer, a polyurethane-polyurea copolymer, or a combination thereof.

3. The resin of claim 1 , wherein said reactive blocked prepolymer comprises reactive end groups selected from the group consisting of acrylates, methacrylates, alpha-olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers.

4. The resin of claim 1 , wherein said reactive blocking groups comprise an amine (meth)acrylate monomer blocking agent.

5. The resin of claim 1 , wherein said reactive blocked prepolymer comprises a (meth)acrylate-blocked prepolymer.

6. The resin of claim 1 , wherein said reactive blocked prepolymer is blocked with a vinyl amide blocking agent.

7. The resin of claim 1 , wherein said reactive blocked prepolymer comprises a vinyl amide blocked polyisocyanate.

8. The resin of claim 7 , wherein said vinyl amide blocked polyisocyanate comprises an N-vinyl formamide blocked polyisocyanate.

9. The resin of claim 1 , wherein said reactive diluent is present and comprises an acrylate, a methacrylate, a styrene, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, or a combination of two or more of the foregoing.

10. The resin of claim 1 , wherein said polyol is a diol or a triol.

11. The resin of claim 1 , wherein the metal of the metal carboxylate is zinc.

12. The resin of claim 1 , wherein the carboxylate is octoate, neodecanoate, naphthenate, stearate, or oxalate.

13. A packaged product useful for the production of three-dimensional objects by additive manufacturing, said product comprising a single container having a single chamber and a resin in the chamber, the resin comprising a resin of claim 1 , with all components mixed together.

14. A method of making a three-dimensional object, comprising:
(a) dispensing the resin of claim 1 into an additive manufacturing apparatus;
(b) producing an intermediate object from said resin by photopolymerization; and then
(c) heating and/or microwave irradiating said intermediate object to further polymerize said resin and form said three-dimensional object.

15. The method of claim 14 , wherein:
said producing step (b) is carried out by photopolymerizing said reactive blocked prepolymer to form a polymer scaffold carrying said polyol; and
said heating and/or microwave irradiating step (c) is carried out under conditions in which said polymer scaffold at least partially degrades and regenerates said prepolymer, said prepolymer in turn polymerizing with said polyol to form said three-dimensional object.

16. The resin of claim 1 , wherein the metal of the metal carboxylate is bismuth.

17. A method of making a three-dimensional object, comprising:
(a) dispensing a resin from the packaged product of claim 13 into an additive manufacturing apparatus;
(b) producing an intermediate object from said resin by photopolymerization; and then
(c) heating and/or microwave irradiating said intermediate object to further polymerize said resin and form said three-dimensional object.

18. The method of claim 17 , wherein:
said producing step (b) is carried out by photopolymerizing said reactive blocked prepolymer to form a polymer scaffold carrying said polyol; and
said heating and/or microwave irradiating step (c) is carried out under conditions in which said polymer scaffold at least partially degrades and regenerates said prepolymer, said prepolymer in turn polymerizing with said polyol to form said three-dimensional object.

19. The resin of claim 4 , wherein the amine (meth)acrylate monomer blocking agent is a tertiary-butylaminoethyl methacrylate (TBAEMA), tertiary pentylaminoethyl methacrylate (TPAEMA), tertiary hexylaminoethyl methacrylate (THAEMA), tertiary-butylaminopropyl methacrylate (TBAPMA), tertiary-octylaminoethyl methacrylate (TOAEMA), or an acrylate analog thereof.

20. The resin of claim 1 , wherein said reactive diluent is present and comprises an acrylonitrile, styrene, divinyl benzene, vinyl toluene, methyl acrylate, ethyl acrylate, butyl acrylate, a fatty alcohol (meth)acrylate such as lauryl acrylate, isobornyl acrylate (IBOA), isobornyl methacrylate (IBOMA), an alkyl ether of mono-, di- or triethylene glycol acrylate or methacrylate, a fatty alcohol acrylate or methacrylate such as lauryl (meth)acrylate, or a mixture of two or more thereof.

Assignees

• Carbon Inc

Inventors

• Pinschmidt Jr Robert K
• Wright Andrew Gordon
• Rolland Jason P

Classifications

• C08F290/067 Primary

  Polyurethanes; Polyureas · CPC title

• C08F2/50

  with sensitising agents · CPC title

• C08L75/16

  having terminal carbon-to-carbon unsaturated bonds · CPC title

• C08F2/44

  Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers · CPC title

• C08G18/0857

  the solvent being a polyol · CPC title