Methods for reactive three-dimensional printing by inkjet printing

Patent metadata

Field	Value
Publication number	US-11220610-B2
Application number	US-201515528462-A
Country	US
Kind code	B2
Filing date	Nov 24, 2015
Priority date	Nov 24, 2014
Publication date	Jan 11, 2022
Grant date	Jan 11, 2022

Abstract

Methods of printing a three-dimensional object using co-reactive components are disclosed. Thermosetting compositions for three-dimensional printing are also disclosed.

First claim

What is claimed is:

1. A method of three-dimensional printing an object comprising:
(a) combining a first reactive component comprising a first functional group and a second component comprising a second functional group to form a coreactive composition, wherein,
the second functional group is reactive with the first functional group; and
at least one of the first functional group and the second functional group comprises a saturated functional group; and
the first functional group and the second functional group are reactive at a temperature of less than 50° C.; and

(b) depositing by inkjet printing the coreactive composition to build a three-dimensional printed object, wherein,
depositing comprises depositing the coreactive composition through a single nozzle:
depositing by inkjet printing comprises depositing the coreactive composition as discrete droplets; and
the coreactive composition is at least partially reacted before depositing by inkjet printing.

2. The method of claim 1 , wherein an initial equivalent ratio of the first functional group to the second functional group is from 1.5:1 to 1:1.5.

3. The method of claim 1 , wherein,
the first reactive component comprises a polyamine and the second reactive component comprises a polyisocyanate;
the first reactive component comprises a polyalkenyl compound and the second reactive component comprises a polythiol;
the first reactive component comprises a polyepoxide and the second reactive component comprises a polythiol; or
the first reactive component comprises a Michael addition acceptor and the second reactive component comprises a Michael addition donor, wherein the Michael addition acceptor is selected from a vinyl ketone, a vinyl sulfone, a quinone, an enamine, a ketimine, an aldimine, an oxazolidine, an acrylonitrile, an acrylamide, a maleimide, a vinyl phosphonate, and a vinyl pyridine.

4. The method of claim 1 , wherein each of the first reactive component and the second reactive component comprises less than 5 wt % solvent, where wt % is based on the total weight of the respective reactive component.

5. The method of claim 1 , wherein,
the first reactive component comprises an isocyanate-functional prepolymer; and
the second functional group comprises a primary amine, a secondary amine, a hydroxyl, or a combination of any of the foregoing.

6. The method of claim 1 , wherein the coreactive composition is characterized by a viscosity less than 30 cP.

7. The method of claim 1 , wherein the saturated functional group comprises a thiol group, a primary amine group, a secondary amine group, or a combination of any of the foregoing.

8. The method of claim 1 , wherein depositing comprises depositing at room temperature.

9. The method of claim 1 , wherein at least one of the first functional group and the second functional group comprises an unsaturated functional group.

10. The method of claim 9 wherein the unsaturated functional group comprises an alkenyl group, a maleoyl group, a fumaroyl group, an acid group, an isocyanate group, an acyclic carbonate group, an acetoacetate group, a carboxylic acid group, a vinyl ether group, a malonoyl group, or a combination of any of the foregoing.

11. The method of claim 1 , wherein the coreactive composition comprises a rheology modifier, flow control agent, a plasticizer, a stabilizer, a wetting agent, a dispersing auxiliary, a deformer, an adhesion promoter, or a combination of any of the foregoing.

12. The method of claim 1 , wherein the coreactive composition comprises from 1 wt % to 40 wt % filler, wherein wt % is based on the total weight of the coreactive composition.

13. The method of claim 1 , wherein the coreactive composition comprises a low-density filler.

14. The method of claim 1 , wherein the coreactive composition comprises an electrically conductive filler.

15. The method of claim 9 , wherein,
the saturated functional group comprises a carboxylic acid group and the unsaturated functional group comprises an epoxy group;
the saturated functional group comprises a maleic group, a fumaric group, an isocyanate group, a cyclic carbonate group, an acetoacetate group, an epoxy group, or a combination of any of the foregoing; and the unsaturated functional group comprises a primary amine, a secondary amine, or a combination thereof;
the saturated functional group comprises a thiol group, and the unsaturated functional group comprises an alkenyl group, a vinyl ether group, a (meth)acrylate group or a combination of any of the foregoing; or
the saturated functional group comprises a maleoyl group, or a combination thereof, and the unsaturated functional group comprises a malonyl group.

16. The method of claim 1 , wherein each of the first reactive component and the second reactive component independently comprise a prepolymer, a monomer, or a combination thereof.

17. The method of claim 1 , wherein,
depositing comprises depositing successive layers; and
an underlying layer comprises functional groups reactive with functional groups in an overlying layer.

18. The method of claim 1 , wherein, the first functional group and the second functional group are capable of reacting at a temperature of less than 30° C.

19. The method of claim 1 , wherein the coreactive composition is at least partially reacted during deposition.

20. The method of claim 1 , wherein a reaction between the first functional group and the second functional group does not involve a free radical-initiated reaction.

21. The method of claim 1 , wherein one or both of the first reactive component and the second reactive component comprise a catalyst capable of catalyzing the reaction between the first functional group and the second functional group.

22. A three-dimensional object formed using the method of claim 1 .

23. The object of claim 22 , wherein adjoining layers of the object are covalently bonded.

Assignees

• Ppg Ind Ohio Inc
• Univ Nottingham

Inventors

• Fenn David R
• Olson Kurt G
• Rock Reza M
• Hague Richard J M
• Tuck Christopher John
• Ma Le
• Wildman Ricky Darren
• He Yinfeng

Classifications

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• B29C64/10 Primary

  Processes of additive manufacturing · CPC title

• C08G18/3821

  Carboxylic acids; Esters thereof with monohydroxyl compounds · CPC title

• C08G18/325

  containing secondary or tertiary amino groups (C08G18/3228, C08G18/3234, C08G18/3246 take precedence) · CPC title

• C08G18/3228

  acyclic · CPC title