Claims
- 1. A method for making a structure, comprising:
(a) applying a multiphoton-curable composition to a molded article, wherein the composition comprises a curable species and a multiphoton photoinitiator system; (b) at least partially curing the multiphoton-curable composition to form a structure on the article.
- 2. The method of claim 1, further comprising removing uncured multiphoton-curable composition from the article.
- 3. The method of claim 1, wherein the multiphoton photoinitiator system comprises a multiphoton photosensitizer and an electron acceptor.
- 4. The method of claim 3, wherein the system further comprises an electron donor.
- 5. The method of claim 3, wherein the multiphoton photosensitizer has a two-photon absorption cross-section greater than that of fluorescein.
- 6. The method of claim 3, wherein the multiphoton photosensitizer has a two-photon absorption cross-section at least 1.5 times greater than that of fluorescein.
- 7. The method of claim 3, wherein the photosensitizer is capable of sensitizing 2-methyl-4,6-bis(trichloromethyl)-s-triazine under continuous irradiation in a wavelength range that overlaps the single photon absorption spectrum of the photosensitizer using the test procedure described in U.S. Pat. No. 3,729,313.
- 8. The method of claim 3, wherein the multiphoton photosensitizer is selected from Rhodamine B and (a) molecules in which two donors are connected to a conjugated π-electron bridge; (b) molecules in which two donors are connected to a conjugated π-electron bridge which is substituted with one or more electron accepting groups; (c) molecules in which two acceptors are connected to a conjugated π-electron bridge; and (d) molecules in which two acceptors are connected to a conjugated π-electron bridge which is substituted with one or more electron donating groups.
- 9. The method of claim 3, wherein the multiphoton photosensitizer is Rhodamine B.
- 10. The method of claim 1, wherein the curable species is selected from the group consisting of acrylates, methacrylates, styrenes, epoxies, vinyl ethers, cyanate esters, and mixtures thereof.
- 11. The method of claim 1, wherein the curable species comprises an epoxy.
- 12. The method of claim 1, wherein the composition further comprises a chemically-amplified photoresist.
- 13. The method of claim 3, wherein the electron acceptor is selected from the group consisting of iodonium salts, chloromethylated triazines, diazonium salts, sulfonium salts, azinium salts, triarylimidazolyl dimers, and mixtures thereof.
- 14. The method of claim 4, wherein the electron donor compounds are selected from the group consisting of amines, amides, ethers, ureas, sulfinic acids and their salts, salts of ferrocyanide, ascorbic acid and its salts, dithiocarbamic acid and its salts, ferrocene, salts of xanthates, salts of ethylene diamine tetraacetic acid, salts of (alkyl)n(aryl)mborates (n+m=4), SnR4 compounds, where each R is alkyl, aralkyl, aryl, or alkaryl, and mixtures thereof.
- 15. The method of claim 1, wherein the molded article comprises a surface with at least one feature, and wherein the composition is applied in the feature.
- 16. The method of claim 15, wherein the feature is microscopic.
- 17. A method of adding a structure to an article, wherein the article has a surface with at least one microscopic feature, the method comprising:
(a) applying a multiphoton-curable composition to the feature, wherein the composition comprises:
(1) a curable species, and (2) a multiphoton photoinitiator system comprising a multiphoton photosensitizer and an electron acceptor; (b) at least partially curing the multiphoton-curable composition to form a structure.
- 18. The method of claim 17 wherein the structure formed is a microstructure.
- 19. The method of claim 17, further comprising removing uncured multiphoton-curable composition from the article.
- 20. The method of claim 17, wherein the system further comprises an electron donor.
- 21. The method of claim 17, wherein the multiphoton photosensitizer has a two-photon absorption cross-section greater than that of fluorescein.
- 22. The method of claim 17, wherein the multiphoton photosensitizer has a two-photon absorption cross-section at least 1.5 times greater than that of fluorescein.
- 23. The method of claim 17, wherein the multiphoton photosensitizer is capable of sensitizing 2-methyl-4,6-bis(trichloromethyl)-s-triazine under continuous irradiation in a wavelength range that overlaps the single photon absorption spectrum of the multiphoton photosensitizer using the test procedure described in U.S. Pat. No. 3,729,313.
- 24. The method of claim 17, wherein the multiphoton photosensitizers are selected from Rhodamine B and (a) molecules in which two donors are connected to a conjugated π-electron bridge; (b) molecules in which two donors are connected to a conjugated π-electron bridge which is substituted with one or more electron accepting groups; (c) molecules in which two acceptors are connected to a conjugated π-electron bridge; and (d) molecules in which two acceptors are connected to a conjugated π-electron bridge which is substituted with one or more electron donating groups.
- 25. The method of claim 17, wherein the multiphoton photosensitizer is Rhodamine B.
- 26. The method of claim 17, wherein the curable species is selected from the group consisting of acrylates, methacrylates, styrenes, epoxies, vinyl ethers, cyanate esters, and mixtures thereof.
- 27. The method of claim 17, wherein the curable species comprises an epoxy.
- 28. The method of claim 17, wherein the composition further comprises a non-curable species selected from the group consisting of chemically-amplified photoresists.
- 29. The method of claim 17, wherein the electron acceptor is selected from the group consisting of iodonium salts, chloromethylated triazines, diazonium salts, sulfonium salts, azinium salts, triarylimidazolyl dimers, and mixtures thereof.
- 30. The method of claim 20, wherein the electron donor compounds are selected from the group consisting of amines, amides, ethers, ureas, sulfinic acids and their salts, salts of ferrocyanide, ascorbic acid and its salts, dithiocarbamic acid and its salts, ferrocene, salts of xanthates, salts of ethylene diamine tetraacetic acid, salts of (alkyl)n(aryl)mborates (n+m=4), SnR4 compounds, where each R is independently chosen from among alkyl, aralkyl, aryl, and alkaryl, and mixtures thereof.
- 31. The method of claim 17, wherein the feature is selected from the group consisting of a channel, a post, and a cavity.
- 32. The method of claim 17, wherein the structure is selected from the group consisting of a valve, a gear, a sphere, a cover, a cap, a cantilever, and a lens.
- 33. The method of claim 17, wherein the structure is flow control device.
- 34. A method of adding a structure to an optical fiber, the method comprising:
(a) applying a multiphoton-curable composition to the optical fiber, wherein the composition comprises:
(1) a curable species, and (2) a multiphoton photoinitiator system comprising a multiphoton photosensitizer and an electron acceptor; (b) at least partially curing the multiphoton-curable composition to form a structure.
- 35. The method of claim 34 wherein the structure is at least one optical device selected from the group consisting of a lens, a prism, a diffuser, and a diffractive optical element.
- 36. A method for making a diffraction grating on a substrate, comprising
applying a multiphoton-curable composition on the surface, wherein the composition comprises:
a curable species, and a multiphoton photoinitiator system comprising a multiphoton photosensitizer and an electron acceptor; and at least partially curing the multiphoton-curable composition to form a diffraction grating on the surface.
- 37. The method of claim 36, further comprising removing uncured composition from the surface.
- 38. A method of filling a cavity with a multiphotoncured material comprising
providing a multiphoton curable composition, wherein the composition comprises a curable species and a multiphoton photoinitiator system, said multiphoton photoinitiator system comprising a multiphoton photosensitizer and an electron acceptor; providing a substrate with a cavity; exposing the multiphoton curable composition to a light source sufficient to cause multiphoton absorption.
- 39. The method of claim 38 wherein the light source is focused at the interface between a surface of the substrate and a portion of the curable composition.
- 40. The method of claim 38 further comprising:
adding additional multiphoton curable composition; and exposing the multiphoton curable composition to a light source sufficient to cause multiphoton absorption.
- 41. The method of claim 38 further comprising:
repeating the adding and exposing steps.
- 42. A method of repairing a tooth, comprising:
applying a multiphoton-curable composition to the tooth, wherein the composition comprises:
a curable species, and a multiphoton photoinitiator system comprising a multiphoton photosensitizer and an electron acceptor; at least partially curing the multiphoton-curable composition.
- 43. The method of claim 42, further comprising removing uncured multiphoton-curable composition from the tooth.
- 44. The method of claim 42 further comprising a non-curable species.
RELATED APPLICATIONS
[0001] This application claims priority from U.S. Provisional Application Nos. 60/211,588 and 60/211,706, both of which were filed Jun. 15, 2000 and are hereby incorporated by reference.
PCT Information
Filing Document |
Filing Date |
Country |
Kind |
PCT/US01/40988 |
6/14/2001 |
WO |
|