Build material and applications thereof

• US 9,604,408 B2
• Filed: 06/03/2016
• Issued: 03/28/2017
• Est. Priority Date: 03/09/2011
• Status: Active Grant

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Inventors: Xu, Pingyong, Stockwell, John
• Primary Examiner(s): THROWER, LARRY W
• Application Number:
  US15/172,347
• Publication Number:
  US 20160279870A1
• Time in Patent Office: 298 Days
• US Class Current: 1/1
• CPC Class Codes: B29C 64/112 using individual droplets, e.g. from jetting heads
• CPC Class Codes: B29C 64/135 the energy source being concentrated, e.g. scanning lasers or focused light sources
• CPC Class Codes: B29C 64/188 involving additional operations performed on the added layers, e.g. smoothing, grinding or thickness control surface shaping B29C59/00; after-treatment of articles without altering their shape B29C71/00
• 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: B33Y 10/00 Processes of additive manufacturing
• 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: C08F 290/067 Polyurethanes; Polyureas
• CPC Class Codes: C08G 18/42 Polycondensates having carboxylic or carbonic ester groups in the main chain
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08G 18/8175 with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08L 75/16 having terminal carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09D 11/101 Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
• CPC Class Codes: C09D 11/34 Hot-melt inks
• CPC Class Codes: Y10T 428/24802 Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Abstract

In one aspect, build materials operable for use in 3D printing systems are described herein. In some embodiments, a build material comprises an oligomeric curable material, a reactive component that is solid at 25° C., and at least one diluent, wherein the reactive component comprises at least one chemical moiety that is polymerizable with a chemical moiety contained in the oligomeric curable material and/or the at least one diluent.

Claims

1. A method of printing a three dimensional article comprising:

selectively depositing layers of a fluid build material to form the three dimensional article on a substrate,

wherein the build material comprises;

an oligomeric curable material;

a reactive component;

a non-reactive component comprising one or more urethane waxes; and

at least one diluent,

wherein the reactive component comprises at least one chemical moiety that is polymerizable with a chemical moiety contained in the oligomeric curable material and/or the at least one diluent and wherein the reactive component is present in the build material as crystalline regions.

2. The method of claim 1, wherein the layers of the build material are deposited according to an image of the three dimensional article in a computer readable format.

3. The method of claim 1 further comprising supporting at least one of the layers of the build material with a support material.

4. The method of claim 1 further comprising curing the build material.

5. The method of claim 1, wherein the build material solidifies upon deposition.

6. The method of claim 1, wherein the build material remains substantially fluid upon deposition.

7. The method of claim 1, wherein the non-reactive component does not comprise a chemical moiety that is polymerizable with a chemical moiety contained in the oligomeric curable material or the at least one diluent.

8. The method of claim 1, wherein the build material further comprises one or more additives selected from the group consisting of photoinitiators, inhibitors, stabilizing agents, sensitizers, and combinations thereof.

9. The method of claim 1, wherein the oligomeric curable material is a urethane (meth)acrylate having a viscosity ranging from 10,000 cps to 300,000 cps.

10. The method of claim 1, wherein the oligomeric curable material and the reactive component each contain one or more acrylate or (meth)acrylate moieties.

11. The method of claim 1, wherein the reactive component comprises more than one chemical moiety that is polymerizable with a chemical moiety contained in the oligomeric curable material and/or the at least one diluent.

12. The method of claim 1, wherein the reactive component comprises at least one of the following:

a urethane (meth)acrylate, a urea (meth)acrylate, and an isocyanurate (meth)acrylate.

13. The method of claim 1, wherein the reactive component is selected from the group consisting of:

(i) an isocyanurate tri(meth)acrylate;

(ii) a species defined by the formula R¹—

NHCOO—

R²—

R³, wherein R¹ is C_nH_(2n+2) (wherein n=4-36), R² is C_nH_(2n+2) (wherein n=2-36), and R³ is —

OCOCH═

CH₂ or —

OCOC(CH₃)═

CH₂;

(iii) a species defined by the formula R¹—

R²—

NHCOO—

R³—

OOC—

NH—

R²—

R¹, wherein R¹ is —

OCOCH═

CH₂ or —

OCOC(CH₃)═

CH₂, R² is C_nH_(2n+2) (wherein n=2-36), and R³ is C_nH_(2n+2) (wherein n=2-36);

(iv) a species defined by the formula R¹—

NHCONH—

R²—

R³, wherein R¹ is C_nH_(2n+2) (wherein n=4-36), R² is C_nH_(2n+2) (wherein n=2-36), and R³ is —

OCOCH═

CH₂ or —

OCOC(CH₃)═

CH₂; and

(v) a species defined by the formula R¹—

R²—

NHCONH—

R³—

OOC—

NH—

R²—

R¹, wherein R¹ is —

OCOCH═

CH₂ or —

OCOC(CH₃)═

CH₂, R² is C_nH_(2n+2) (wherein n=2-36), and R³ is C_nH_(2n+2) (wherein n=2-36).

14. The method of claim 1, wherein the reactive component comprises a nitrogen-containing ring.

15. The method of claim 1, wherein the reactive component is an isocyanurate.

16. The method of claim 1, wherein the reactive component is tris(2-hydroxy ethyl)isocyanurate triacrylate.

17. The method of claim 1, wherein the reactive component comprises 5 to 50 percent by weight of the build material.

18. The method of claim 1, wherein the reactive component comprises 5 to 15 percent by weight of the build material.

19. The method of claim 1, wherein the reactive component exhibits a melting point range of 1°

C. to 10°

C., centered between 40°

C. and 100°

C.

20. The method of claim 1, wherein the at least one diluent contains one or more (meth)acrylate moieties.