Build material and applications thereof

• US 9,394,441 B2
• Filed: 03/09/2011
• Issued: 07/19/2016
• 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:
  US13/043,876
• Publication Number:
  US 20120231232A1
• Time in Patent Office: 1,959 Days
• Field of Search: 264/308
• 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 build material for use in a three-dimensional printing system comprising:

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 build material 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.

3. The build material 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.

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

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

6. The build material of claim 1, wherein the reactive component is solid at about 30°

C.

7. The build material of claim 1, wherein the reactive component is solid at about 40°

C.

8. The build material of claim 1, wherein the reactive component is crystalline or substantially crystalline at about 30°

C.

9. The build material of claim 1, wherein the reactive component is crystalline or substantially crystalline at about 40°

C.

10. The build material of claim 1, wherein the reactive component is crystalline or substantially crystalline at about 50°

C.

11. The build material 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 build material 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 build material 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 build material of claim 1, wherein the reactive component comprises a nitrogen-containing ring.

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

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

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

18. The build material of claim 1, wherein the reactive component comprises about 5 to about 30 percent by weight of the build material.

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

20. The build material of claim 1, wherein the reactive component exhibits a melting point range of about 1°

C. to about 10°

C.

21. The build material of claim 1, wherein the reactive component exhibits a melting point range centered between about 40°

C. and about 100°

C.

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

23. The build material of claim 1, wherein the build material when cured exhibits a tensile modulus of about 1500-2200 MPa when measured according to ASTM D 638.

24. The build material of claim 1, wherein the build material when cured exhibits a tensile modulus of about 1500-1900 MPa when measured according to ASTM D 638.

25. The build material of claim 1, wherein the build material when cured exhibits a tensile modulus of about 1550-1850 MPa when measured according to ASTM D 638.

26. The build material of claim 1, wherein the build material when cured exhibits a break elongation of about 10-24% when measured according to ASTM D 638.

27. The build material of claim 1, wherein the build material when cured exhibits a break elongation of about 12-22% when measured according to ASTM D 638.

28. The build material of claim 1, wherein the build material when cured exhibits a break elongation of about 14-20% when measured according to ASTM D 638.

29. The build material of claim 1, wherein the build material when cured exhibits a heat deflection temperature ranging from about 45°

C. to about 100°

C. when tested according to ASTM D 648.

30. The build material of claim 1, wherein the build material exhibits a melting point range centered between about 45°

C. and about 55°

C.

31. The build material of claim 1, wherein the build material exhibits a melting point range centered between about 50°

C. and about 65°

C.

32. The build material of claim 1, wherein the build material exhibits a melting point range centered between about 50°

C. and about 80°

C.

33. The build material of claim 1, wherein the build material exhibits a melting point range centered at a temperature greater than about 40°

C.

34. A composition comprising:

a three-dimensionally printed article comprising a build material, the build material comprising 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.

35. The composition of claim 34, 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.

36. The composition of claim 34, wherein the reactive component is substantially crystalline at 25°

C.

37. The composition of claim 34, 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.

38. The composition of claim 34, wherein the oligomeric curable material and the reactive component each contain one or more acrylate or (meth)acrylate moieties.

39. The composition of claim 34, wherein the build material when cured exhibits a tensile modulus of 1500-2200 when measured according to ASTM D 638.

40. The composition of claim 34, wherein the build material when cured exhibits a break elongation of 10-24% when measured according to ASTM D 638.