Photo-curable resin composition used for photo-fabrication of three-dimensional object

• US RE42,593 E1
• Filed: 09/26/2003
• Issued: 08/02/2011
• Est. Priority Date: 12/13/1996
• Status: Expired due to Term

• Current Assignee: DSM IP Assets BV (DSM-Firmenich AG), Japan Fine Coatings Co. Ltd. (JSR Corporation), JSR Corporation
• Original Assignee: DSM IP Assets BV (DSM-Firmenich AG), Japan Fine Coatings Co. Ltd. (JSR Corporation), JSR Corporation
• Inventors: Yamamura, Tetsuya, Ukachi, Takashi, Takeuchi, Akira, Watanabe, Tsuyoshi
• Primary Examiner(s): McClendon; Sanza L
• Application Number:
  US10/671,438
• Time in Patent Office: 2,867 Days
• Field of Search: 522/168, 522/100, 522/166, 522/170, 264/401, 264/494, 264/496, 427/508
• US Class Current: 522/168
• 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: G03F 7/0037 Production of three-dimensional images
• 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: G03F 7/0755 Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds G03F7/0752 takes precedence
• CPC Class Codes: G03F 7/0757 Macromolecular compounds containing Si-O, Si-C or Si-N bonds G03F7/0752 takes precedence

Abstract

A photocurable resin composition suitable for photo-fabrication. The resin composition capable of being promptly cured by photo-irradiation, thereby reducing fabricating time and providing cured products having excellent mechanical strength and minimized shrinkage during curing to ensure high dimensional accuracy. The composition includes (A) an oxetane compound, (B) an epoxy compound, and (C) a cationic photo-initiator.

Claims

1. A composition for use in photo-fabrication of objects comprising:

(a) an oxetane;

(b) an epoxy compound selected from the group consisting of glycidyl esters of fatty acids, epoxidated soybean oil, and epoxidated linseed oil; and

(c) a cationic photoinitiator;

wherein an H-shaped object obtained by curing said composition has a dimensional accuracy value of less than or equal to 0.10 mm.

2. The composition of claim 1, comprising a further epoxy compound, said further epoxy compound being present, relative to the total composition, in an amount of 3-50 wt %.

3. The composition of claim 1, wherein said composition has substantially the same Young'"'"'s Modulus when cured at an irradiation dose of 100 mJ/cm² as at an irradiation dose of 500 mJ/cm².

4. The composition of claim 2, wherein said further epoxy compound has a molecular weight of more than 1,000.

5. The composition of claim 1, wherein said epoxy compound has a molecular weight of less than 1,000.

6. A three-dimensional object comprising a cured photo-curable resin composition according to claims 1.

7. A process for photo-fabricating a three-dimensional object comprising selectively curing the photo-curable resin composition of claim 1.

8. A process for photo-fabricating a three-dimensional object comprising selectively curing a photo-curable resin composition comprising:

(a) an oxetane;

(b) an epoxy compound; and

(c) a cationic photoinitiator.

9. The process of claim 8, wherein said composition comprises 3-50 wt %, relative to the total weight of the composition, of said epoxy compound.

10. The process of claim 8, wherein an H-shaped object obtained by curing said composition has a dimensional accuracy value of less than or equal to 0.10 mm.

11. A three-dimensional object obtained by the process of claim 8.

12. A three-dimensional object obtained by the process of claim 9.

13. A three-dimensional object obtained by the process of claim 10.

14. A three-dimensional object obtained by the process of claim 11.

15. A process for photo-fabricating a three-dimensional object by selectively curing a photo-curable resin composition comprising:

(a) an oxetane having two or more oxetane rings;

(b) an epoxy compound; and

(c) a cationic photoinitiator,

wherein said process comprises

(i) forming a layer of said composition;

(ii) selectively irradiating said layer of said composition to form a solid cured resin layer;

(iii) forming a layer of said composition on the solid cured resin layer; and

(iv) repeating steps (ii) and (iii).

16. A process for photo-fabricating a three-dimensional object by selectively curing a photo-curable resin composition comprising:

(a) an oxetane;

(b) an epoxy compound; and

(c) a cationic photoinitiator,

wherein said process comprises

(i) forming a layer of said composition;

(ii) selectively irradiating said layer of said composition to form a solid cured resin layer;

(iii) forming a layer of said composition on the solid cured resin layer; and

(iv) repeating steps (ii) and (iii);

wherein said oxetane is represented by the following formula (10);

17. The process of claim 16, wherein each R represents an alkyl group having from 1 to 6 carbon atoms.

18. The process of claim 16, wherein each R represents an ethyl group.

19. A process for photo-fabricating a three-dimensional object by selectively curing a photo-curable resin composition comprising:

(a) an oxetane having 3 or more oxetane rings;

(b) an epoxy compound; and

(c) a cationic photoinitiator,

wherein said process comprises

(i) forming a layer of said composition;

(ii) selectively irradiating said layer of said composition to form a solid cured resin layer;

(iii) forming a layer of said composition on the solid cured resin layer; and

(iv) repeating steps (ii) and (iii).

20. A process for photo-fabricating a three-dimensional object comprising selectively curing a photo-curable resin composition comprising:

(a) an oxetane;

(b) an epoxy compound; and

(c) a cationic photoinitiator.

21. The process of claim 20, wherein said composition comprises 3-50 wt %, relative to the total weight of the composition, of said epoxy compound.

22. The process of claim 20, wherein an H-shaped object obtained by curing said composition has a dimensional accuracy value of less than or equal to 0.10 mm.

23. A three-dimensional object obtained by the process of claim 20.

24. A three-dimensional object obtained by the process of claim 21.

25. A three-dimensional object obtained by the process of claim 22.

26. A radiation-curable composition comprising:

(a) an epoxidated compound obtained by a process comprising epoxidating a double bond between carbons of a corresponding compound having an ethylenically unsaturated bond using an appropriate oxidizing agent such as hydrogen peroxide or peroxy acid process;

(b) a polyfunctional monomer;

(c) a polyhydric alcohol;

(d) an oxetane compound having one or more oxetane groups;

(e) one or more free-radical photoinitiators; and

(f) one or more cationic photoinitiators.

27. The radiation-curable composition according to claim 26, wherein said composition further comprises a pigment and/or a dye.

28. The radiation-curable composition according to claim 27, wherein said composition further comprises one or more additives different than the pigment or dye.

29. A radiation-curable composition used in photo-fabrication of an object comprising:

(a) an epoxidated compound obtained by a process comprising epoxidating a double bond between carbons of a corresponding compound having an ethylenically unsaturated bond using an appropriate oxidizing agent such as hydrogen peroxide or peroxy acid process;

(b) pentaerythritol tetra (meth)acrylate;

(c) propoxylated modified glycerol;

(d) 3-ethyl-3-hydroxymethyloxetane;

(e) a free-radical photoinitiator 1-hydroxycyclohexyl phenyl ketone;

(f) a cationic photoinitiator (bis[4-diphenylsulfonio)-phenyl]sulfide bis hexafluoro antimonate; and

(g) a pigment and/or a dye.

30. The radiation-curable composition according to claim 29, wherein said composition further comprises one or more additives different than pigment or dye.

31. The process of claim 20, wherein said process comprises

(i) forming a layer of said composition;

(ii) selectively irradiating said layer of said composition to form a solid cured resin layer;

(iii) forming a layer of said composition on the solid cured resin layer; and

(iv) repeating steps (ii) and (iii).