Production of three-dimensional objects

• US 5,677,107 A
• Filed: 05/06/1996
• Issued: 10/14/1997
• Est. Priority Date: 10/02/1991
• Status: Expired due to Term

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: Spectra Group Limited, Inc. (Formlabs Incorporated)
• Inventors: Neckers, Douglas C.
• Primary Examiner(s): CHAPMAN, MARK A
• Application Number:
  US08/643,790
• Time in Patent Office: 526 Days
• Field of Search: 430/269, 430/138, 430/270.1, 430/281.1, 430/292, 264/22
• US Class Current: 430/269
• CPC Class Codes: B29C 35/08 by wave energy or particle radiation B29C64/00, B29C71/04 take precedence
• CPC Class Codes: B29C 41/003 characterised by the choice of material
• CPC Class Codes: B29C 64/135 the energy source being concentrated, e.g. scanning lasers or focused light sources
• CPC Class Codes: B29C 64/165 using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
• CPC Class Codes: B29C 64/268 using laser beams; using electron beams [EB]
• CPC Class Codes: B29K 2105/0032 Pigments, colouring agents or opacifiyng agents
• CPC Class Codes: B29K 2995/002 Coloured
• 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 7/105 having substances, e.g. indicators, for forming visible images

Abstract

A method for producing a three-dimensional object having selected elements which are colored differently than other elements of the object comprising the steps of: (a) providing a film of a photohardenable composition containing a photoresponsive agent; (b) irradiating the film in a cross-sectional pattern of the object to be formed; (c) selectively irradiating one or more portions of the cross-sectional pattern corresponding to the selected elements which are desired to be colored differently with radiation which activates the photoresponsive agent, the photoresponsive agent thereby producing color in or removing color from the selected irradiated portions of the cross-sectional pattern; (d) repeating the steps a, b and c to form successive adjacent cross-sectional patterns of the object; and (e) integrating the cross-sectional patterns together to provide the object.

Claims

1. A method for producing a three-dimensional object having selected elements which are colored differently than other elements of said object comprising the steps of:

a. providing a film of a photohardenable composition containing a photoresponsive agent,

b. irradiating said film in a cross-sectional pattern of the object to be formed,

c. selectively irradiating one or more portions of said cross-sectional pattern corresponding to said selected elements which are desired to be colored differently with radiation which activates said photoresponsive agent, said photoresponsive agent thereby producing color in or removing color from said selected irradiated portions of said cross-sectional pattern,

d. repeating said steps a, b and c to form successive adjacent cross-sectional patterns of said object, and

e. integrating said cross-sectional patterns together to provide said object.

2. The method of claim 1 wherein said three-dimensional object is prepared by stereolithography.

3. The method of claim 1 wherein said irradiation is accomplished using at least one laser.

4. The method of claim 1 wherein said photoresponsive agent is a compound whose color changes upon irradiation.

5. The method of claim 4 wherein said photoresponsive agent is a triphenylmethane which ionizes upon irradiation.

6. The method of claim 4 wherein said photoresponsive agent is a triphenylacetonitrile.

7. The method of claim 4 wherein said photoresponsive agent is a triphenylcarbinol.

8. The method of claim 4 in wherein said photoresponsive compound is a benzospiropyran.

9. The method of claim 8 wherein said photoresponsive agent is 1,3-dihydro-6'"'"',8'"'"'-dichloro-1-hexyl-3,3-dimethylspiro 2H-indole-2,2'"'"'- 3H!benzopyran! or 1,3-dihydro-6'"'"'-nitro-8'"'"'-bromo-1-hexyl,3,3-dimethylspiro 2H-indole-2,2'"'"'- 3H!benzopyran!.

10. The method of claim 4 wherein said photoresponsive agent is a fulgide.

11. The method of claim 4 wherein said photoresponsive agent compound is one whose omission spectra changes with changes in the viscosity or degree of cure or ionic character of the photohardenable composition.

12. The method of claim 11 wherein said photoresponsive agent is used in combination with the polymer poly 2- N,N-dimethyl, n-(p-benzoyl)benzylammonium(triphenyl-n-butylborate!ethyl acrylate.

13. The method of claim 11 wherein said photoresponsive compound is solvatochromic.

14. The method of claim 11 wherein said photoresponsive compound is chosen from a group known as twisted intramolecular charge transfer emitters.

15. The method of claim 11 wherein said photoresponsive compound is dimethylaminonitrostilbene.

16. The method of claim 11 wherein said photoresponsive compound is N,N-dibutyldansylamide.

17. The method of claim 4 wherein said photoresponsive agent is a lumiphore.

18. The method of claim 7 wherein said photoresponsive agent is a fluorescein and an iodonium salt.

19. The method of claim 4 wherein said photoresponsive agent comprises a photosensitive acid generator or a photosensitive base generator and an indicator dye.

20. The method of claim 19 wherein said photoresponsive agent is a leuco dye and a photosensitive acid generator.

21. The method of claim 20 wherein said photoresponsive agent is a triphenylcarbinol in combination with a photosensitive acid generator.

22. The method of claim 19 wherein said photoresponsive agent is a dye precursor lactone and a photosensitive acid generator.

23. The method of claim 19 wherein said photoresponsive agent is 6-(dimethylamino)-3,3-bis 4- dimethylamino)phenyl!-1(3H)-isobenzofuranone, 3,3-Bis 4-(dimethylamino)phenyl!-1(3H)-isobenzofuranone, 2'"'"'- bis(phenylmethyl)amino!-6'"'"'(diethylamino)-3'"'"'-methyl 2'"'"'-phenylamino-spiro isobenzofuran-1(3H), 9'"'"'- 9H!xanthen!-3-one, 3- bis(4-octylphenyl)amino!-3- 4-dimethylamino)phenyl!-1(3H)-isobenzofuranone, 3,3-bis(1-butyl-2-methyl-1H-indol-3-yl)-1(3H)-isobenzofuranone, or 3,3-bis(1-octyl-2-methyl-1H-indo-3-yl)-1(3H)-isobenzofuranone in combination with an onium salt.

24. The method of claim 19 wherein the acid generator is a diazoketone.

25. The method of claim 19 wherein said photoresponsive agent is methyl red or bromothymol blue and 2-nitrobenzaldehyde.

26. The method of claim 19 wherein said photoresponsive agent is an aryldiazonium salt.

27. The method of claim 19 wherein the photoresponsive base generator produces an amine and the indicator is a phenol.

28. The method of claim 1 wherein said photoresponsive agent includes a color precursor and an oxidizing agent.

29. The method of claim 28 wherein the photoresponsive agent includes a color precursor and an onium salt.

30. The method of claim 29 wherein said photoresponsive agent includes a color precursor and an iodonium salt.

31. The method of claim 28 wherein said photoresponsive agent includes a color precursor and a transition metal salt.

32. The method of claim 28 wherein said photoresponsive agent includes a color precursor and a ferrous salt or a uranyl salt.

33. The method of claim 1 wherein said photoresponsive agent is a photobleachable dye.

34. The method of claim 33 wherein said photoresponsive agent is a dye bleachable by photoreduction.

35. The method of claim 33 wherein said photoresponsive agent is a dye bleachable by photooxidation.

36. The method of claim 35 wherein said photoresponsive agent is a xanthene dye and an iodonium salt.

37. The method claim 36 wherein said photoresponsive agent is a Rose Bengal, Eosin, erythrosin or phyloxin, and an iodonium salt.

38. The method of claim 33 wherein said photoresponsive agent is a dye bleachable by the formation of acid.

39. The method of claim 1 in which the photoresponsive agent undergoes a decomposition reaction.

40. The method of claim 39 in which the photoresponsive agent is a peroxide.

41. The method of claim 40 in which photoresponsive agent is rubrene peroxide.

42. The method of claim 39 in which the photoresponsive agent is a quinone ether.

43. The method of claim 42 in which the photoresponsive agent is a benzoquinone ether, an anthraquinone ether, a phenanthraquinone ether, or a naphthoquinone ether.

44. The method of claim 43 in which the photoresponsive agent is benzoquinone dibenzyl ether.

45. The method of claim 1 in which the photoresponsive agent undergoes a ligand exchange reaction.

46. The method of claim 1 wherein said photohardenable composition contains a plurality of photoresponsive agents, each agent controlling the formation of a different color such that selected portions of said objects may be colored differently.

47. The method of claim 46 wherein said photoresponsive agent is a photobleachable dye.

48. The method of claim 46 wherein said photoresponsive agent comprises a photosensitive acid generator or a photosensitive base generator and an indicator dye.

49. The method of claim 46 wherein said photoresponsive agent includes a color precursor and a photoactivated oxidizing agent.

50. The method of claim 46 wherein said photoresponsive agent includes a color precursor and a photoactivated reducing agent.

51. The method of claim 46 wherein said photoresponsive agent is a dye bleachable by the formation of acid.

52. The method of claim 46 wherein said photoresponsive agent is a combination of cyan, magenta and yellow photobleachable initiators.

53. The method of claim 46 wherein said photoresponsive compound is one whose emission spectra changes with changes in the viscosity or degree of cure or ionic character of the photohardenable composition.

54. The method of claim 1 wherein said step c is performed simultaneously with step b.