Radiation curable resin composition and rapid three-dimensional imaging process using the same

• US 8,501,033 B2
• Filed: 03/12/2010
• Issued: 08/06/2013
• Est. Priority Date: 03/13/2009
• Status: Active Grant

• Current Assignee: Stratasys Incorporated
• Original Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Inventors: Southwell, John, Register, Brett A., Sarmah, Satyendra Kumar, Steeman, Paulus Antonius Maria, Keestra, Beert Jacobus, Driessen, Marcus Matheus
• Primary Examiner(s): Reddy, Karuna P
• Application Number:
  US13/001,655
• Publication Number:
  US 20110104500A1
• Time in Patent Office: 1,243 Days
• Field of Search: 106/182.11, 106/182.12, 106/182.13, 106/183.11, 526/317.1, 526/318, 526/309, 524/599, 524/612, 252/182.11, 252/182.12, 252/182.13, 252/183.11
• US Class Current: 252/182.13
• CPC Class Codes: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: B33Y 80/00 Products made by additive manufacturing
• CPC Class Codes: C08G 65/18 Oxetanes
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: G03F 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence
• CPC Class Codes: G03F 7/038 Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021
• CPC Class Codes: Y10T 428/31511 Of epoxy ether

Abstract

The invention relates to a liquid radiation curable resin capable of curing into a solid upon irradiation comprising: (A) from about 0 to about 12 wt % of a cycloaliphatic epoxide having a linking ester group; (B) from about 30 to about 65 wt % of one or more epoxy functional components other than A; (C) from about 10 to about 30 wt % of one or more oxetanes; (D) from, about 1 to about 10 wt % of one or more polyols; (E) from about 2 to about 20 wt % of one or more radically curable (meth)acrylate components; (F) from about 2 to about 12 wt % of one or more impact modifiers; (G) from about 0.1 to about 8 wt % of one or more free radical photoinitiators; and (H) from about 0.1 to about 8 wt % of one or more cationic photoinitiators; wherein the liquid radiation curable resin has a viscosity at 30° C. of from about 600 cps to about 1300 cps.

Claims

1. A liquid radiation curable resin comprising:

(A) from about 0 to about 12 wt % of a cycloaliphatic epoxide having a linking ester group;

(B) from about 30 to about 65 wt % of one or more epoxy functional components, wherein element (B) is not the same as element (A);

(C) from about 10 to about 30 wt % of one or more oxetanes;

(D) from about 1 to about 10 wt % of one or more polyols;

(E) from about 2 to about 20 wt % of one or more radically curable (meth)acrylate components;

(F) from about 2 to about 12 wt % of one or more impact modifiers;

(G) from about 0.1 to about 8 wt % of one or more free radical photoinitiators; and

(H) from about 0.1 to about 8 wt % of one or more cationic photoinitiators;

wherein the one or more epoxy functional components other than (A) comprises from about 0.25 wt % to about 1.0 wt % of a mono-functional epoxy with an ethylhexyl chain; and

wherein the liquid radiation curable resin has a viscosity at 30°

C. of from about 200 cps to about 1300 cps.

2. The liquid radiation curable resin of claim 1, comprising:

(A) from about 5 to about 10 wt % of a cycloaliphatic epoxide having a linking ester group;

(B) from about 35 to about 45 wt % of one or more epoxy functional components, wherein element (B) is not the same as element (A);

(C) from about 15 to about 30 wt % of one or more oxetanes;

(D) from about 1 to about 8 wt % of one or more polyols;

(E) from about 2 to about 20 wt % of one or more radically curable (meth)acrylate components;

(F) from about 2 to about 10 wt % of one or more impact modifiers; and

(G) from about 0.1 to about 5 wt % of one or more free radical photoinitiators.

3. The liquid radiation curable resin of claim 1 wherein the liquid radiation curable resin, after full cure, has a Young'"'"'s modulus of from about 2 GPa to about 3 GPa, a notched Izod impact strength of from about 0.30 J/cm to about 0.60 J/cm, a heat deflection temperature of from about 40°

C. to about 65°

C., and a 24-hour water absorption value of from about 0.2 weight % to about 0.7 weight %.

4. The liquid radiation curable resin of claim 2 wherein the liquid radiation curable resin, after full cure, has a Young'"'"'s modulus of from about 2 GPa to about 3 GPa, a notched Izod impact strength of from about 0.30 J/cm to about 0.60 J/cm, a heat deflection temperature of from about 40°

C. to about 65°

C., and a 24-hour water absorption value of from about 0.2 weight % to about 0.7 weight %.

5. The liquid radiation curable resin of claim 1 wherein the liquid radiation curable resin has a viscosity at 30°

C. of from about 600 cps to about 1250 cps.

6. The liquid radiation curable resin of claim 1 wherein the liquid radiation curable resin, after full cure, has a Young'"'"'s modulus of from about 2.25 GPa to about 2.80 GPa.

7. The liquid radiation curable resin of claim 1 wherein the liquid radiation curable resin, after full cure, has a notched Izod impact strength of from about 0.30 J/cm to about 0.53 J/cm.

8. The liquid radiation curable resin of claim 1 wherein the liquid radiation curable resin, after full cure, has a heat deflection temperature of from about 55°

C. to about 65°

C.

9. The liquid radiation curable resin of claim 1 wherein the liquid radiation curable resin, after full cure, has a 24-hour water absorption value of from about 0.20 to about 0.61 weight %.

10. The liquid radiation curable resin of claim 1 wherein the liquid radiation curable resin, after full cure, has a strain softening value of from about 20 to about 30% of yield stress.

11. The liquid radiation curable resin of claim 1 wherein the one or more radically curable (meth)acrylate components comprises one or more components with at least two (meth)acrylate groups.

12. The liquid radiation curable resin of claim 1 wherein the one or more impact modifiers comprises one or more elastomers.

13. The liquid radiation curable resin of claim 1 wherein the one or more oxetane functional components comprises from about 0.25 wt % to about 5.0 wt % of a mono-functional oxetane with an ethylhexyl chain.

14. The liquid radiation curable resin of claim 1 wherein the one or more impact modifiers comprises an impact modifier with a dispersed average particle size of from about 50 nm to about 850 nm.

15. The liquid radiation curable resin of claim 1 wherein the one or more impact modifiers comprises a first impact modifier and a second impact modifier wherein the dispersed average particle size of the first impact modifier is different than the dispersed average particle size of the second impact modifier.

16. The liquid radiation curable resin of claim 15 wherein the ratio of diameters of the first impact modifier to the second impact modifier is about 7 to 1 and the ratio of the presence in the liquid radiation curable resin in terms of weight percent of the entire composition of the first impact modifier to the second impact modifier is about 4 to 1.

17. The liquid radiation curable resin of claim 1 wherein the cationically polymerizable/hydroxy ratio of the liquid radiation curable resin is from about 2.0 to about 4.0.

18. A process for making a three-dimensional article comprising the steps of

(1) providing a liquid radiation curable resin;

(2) providing a stereolithography machine;

(3) coating a layer of a liquid radiation curable resin onto a surface;

(4) exposing said layer imagewise to actinic radiation to form a first exposed imaged cross-section, wherein the radiation is of sufficient intensity and time to cause substantial curing of the layer in the exposed areas;

(5) coating an additional layer of the liquid radiation curable resin onto the previously exposed imaged cross-section;

(6) exposing said additional layer imagewise to actinic radiation to form an additional imaged cross-section, wherein the radiation is of sufficient intensity and time to cause substantial curing of the second layer in the exposed areas and to cause adhesion to the previously exposed imaged cross-section; and

(7) repeating steps (5) and (6) a desired number of times to build up the three-dimensional article,

wherein the liquid radiation curable resin is that of claim 1.

19. A three-dimensional article made by a process of claim 18, after full cure, has a Young'"'"'s modulus of from about 2 GPa to about 3 GPa, a notched Izod impact strength of from about 0.30 J/cm to about 0.60 J/cm, a heat deflection temperature of from about 40°

C. to about 65°

C., and a 24-hour water absorption value of from about 0.2 weight % to about 0.7 weight %.

20. A three-dimensional article made from the liquid radiation curable resin of claim 1.

21. A three-dimensional article made from the liquid radiation curable resin of claim 1 that, after full cure,

has a Young'"'"'s modulus of from about 2 GPa to about 3 GPa,

a notched Izod impact strength of from about 0.30 J/cm to about 0.60 J/cm,

a heat deflection temperature of from about 40°

C. to about 65°

C., and

a 24-hour water absorption value of from about 0.2 weight % to about 0.7 weight %.