Claims
- 1. A photosensitive composition comprising:
(a) 30-70% by weight of an epoxide-containing material; (b) 5-35% by weight of an acrylic material selected from aromatic acrylic material, cycloaliphatic acrylic material, or combinations thereof; (c) 0-40% by weight of a hydroxyl-containing material; (d) at least one cationic photoinitiator; and (e) at least one free-radical photoinitiator, wherein said composition, after exposure to actinic radiation, has: (i) an elongation at yield in the range of 7% to no yield; (ii) a tensile modulus in the range of 1000 to 1600 N/mm2; (iii) an average elongation at break of at least 10%; or (iv) a yield stress of 28 to 40 N/mm2.
- 2. The composition of claim 1, wherein the epoxide-containing material is selected from bis(2,3-epoxycyclopentyl)ether, 2,3-epoxy cyclopentyl glycidyl ether, 1,2-bis(2,3-epoxycyclopentyloxy)ethane, bis(4-hydroxycyclohexyl)methane diglycidyl ether, 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether, diglycidyl ether of neopentyl glycol, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecaboxylate, di(3,4-epoxycyclohexylmethyl)hexanedioate, di(3,4-epoxy-6-methylcyclohexylmethyl)hexanedioate, ethylenebis(3,4-epoxycyclohexanecarboxylate), ethanedioldi(3,4-epoxycyclohexylmethyl)ether, vinylcyclohexene dioxide, dicyclopentadiene diepoxide, 1,2-epoxytetradecane, a di(oxiranyl) poly(oxy-1,4-butanediyl), a partially acrylated bisphenol A epoxy, and 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,3-dioxane, and combinations thereof.
- 3. The composition of claim 1, wherein the acrylic material is selected from 1,4-dihydroxymethyl-cyclohexane diacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, and ethoxylated bisphenol A diacrylate and combinations thereof.
- 4. The composition of claim 1, wherein the hydroxyl-containing material is selected from 1,4-cyclohexanedimethanol, aliphatic and cycloaliphatic mono hydroxy alkanols, an aliphatic polycarbonate diol, and linear and branched polytetrahydrofuran polyether polyols, and combinations thereof.
- 5. The composition of claim 1, wherein the free-radical photoinitiator is a 1-hydroxyphenyl ketone.
- 6. The composition of claim 1, wherein the free-radical photoinitiator is selected from an alpha-hydroxyphenyl ketone, benzil dimethyl ketal or 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
- 7. The composition of claim 1, wherein the composition comprises 32-48% by weight of an epoxide-containing material.
- 8. The composition of claim 1, wherein the composition comprises 10-20% by weight of an acrylic material selected from aromatic acrylic material, cycloaliphatic acrylic material, or combinations thereof.
- 9. The composition of claim 1, wherein the composition comprises 10-39% by weight of a hydroxyl-containing material.
- 10. The composition of claim 1, wherein the composition comprises 35-69.9% by weight of an epoxide-containing material, 10-20% by weight of an acrylic material selected from aromatic acrylic material, cycloaliphatic acrylic material, or combinations thereof, and 10-39% by weight of a hydroxyl-containing material.
- 11. The composition of claim 10, wherein the epoxide-containing material includes 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 1,2-epoxytetradecane, diglycidyl ether of neopentyl glycol, or α-(oxiranylmethyl)-ω-(oxiranylmethoxy) poly(oxy-1,4-butanediyl), or combinations thereof.
- 12. The composition of claim 1, wherein the hydroxyl-containing material includes a polytetrahydrofuran polyol, 1,4-cyclohexanedimethanol, or an aliphatic polycarbonate diol, or combinations thereof.
- 13. A three-dimensional article formed from a photosensitive composition comprising:
(a) 30-70% by weight of an epoxide-containing material; (b) 5-35% by weight of an acrylic material selected from aromatic acrylic material, cycloaliphatic acrylic material, or combinations thereof; (c) 0-40% by weight of a hydroxyl-containing material; (d) at least one cationic photoinitiator; and (e) at least one free-radical photoinitiator, wherein the article has: (i) an elongation at yield in the range of 7% to no yield; (ii) a tensile modulus in the range of 1000 to 1600 N/mm2; (iii) an average elongation at break of at least 10%; or (iv) a yield stress of 28 to 40 N/mm2.
- 14. The article of claim 13, wherein the composition comprises 35-69.9% by weight of an epoxide-containing material, 10-20% by weight of an acrylic material selected from aromatic acrylic material, cycloaliphatic acrylic material, or combinations thereof, and 10-39% by weight of a hydroxyl-containing material.
- 15. The article of claim 13, wherein the epoxide-containing material includes 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 1,2-epoxytetradecane, diglycidyl ether of neopentyl glycol, or α-(oxiranylmethyl)-ω-(oxiranylmethoxy) poly(oxy-1,4-butanediyl), or combinations thereof.
- 16. The article of claim 13, wherein the hydroxyl-containing material includes a polytetrahydrofuran polyol, 1,4-cyclohexanedimethanol, or an aliphatic polycarbonate diol, or combinations thereof.
- 17. A process for forming a three-dimensional article comprising:
(1) coating a layer of a composition onto a surface, the composition comprising:
(a) 30-70% by weight of an epoxide-containing material; (b) 5-35% by weight of an acrylic material selected from aromatic acrylic material, cycloaliphatic acrylic material, or is combinations thereof; (c) 0-40% by weight of a hydroxyl-containing material; (d) at least one cationic photoinitiator; and (e) at least one free-radical photoinitiator, (2) exposing the layer imagewise to actinic radiation to form an imaged cross-section, wherein the radiation is of sufficient intensity to cause substantial curing of the layer in the exposed areas; (3) coating a layer of the composition onto the previously exposed imaged cross-section; (4) exposing said thin layer from step (3) imagewise to actinic radiation to form an additional imaged cross-section, wherein the radiation is of sufficient intensity to cause substantial curing of the thin layer in the exposed areas and to cause adhesion to the previously exposed imaged cross-section; (5) repeating steps (3) and (4) a sufficient number of times in order to build up the three-dimensional article, wherein the article has: (i) an elongation at yield in the range of 7% to no yield; (ii) a tensile modulus in the range of 1000 to 1600 N/mm2; (iii) an average elongation at break of at least 10%; or (iv) a yield stress of 28 to 40 N/mm2.
- 18. The process of claim 17, wherein the actinic radiation is in the range of 280-650 nm.
- 19. The process of claim 17 wherein the exposure energy is in the range of 10-150 mJ/cm.
- 20. The process of claim 17, wherein the epoxide-containing material includes 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 1,2-epoxytetradecane, diglycidyl ether of neopentyl glycol, or α-(oxiranylmethyl)-ω-(oxiranylmethoxy) poly(oxy-1,4-butanediyl), or combinations thereof and the hydroxyl-containing material includes a polytetrahydrofuran polyol, 1,4-cyclohexanedimethanol, or an aliphatic polycarbonate diol, or combinations thereof.
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present Application is a Continuation-in-Part of U.S. application Ser. No. 09/113,271, filed Jul. 10, 1998, which is hereby incorporated in its entirety by reference. The present Application is furthermore a Continuation-in-Part of U.S. application Ser. No. 09/538,940, filed Mar. 31, 2000, which is hereby also incorporated in its entirety by reference.
Continuation in Parts (2)
|
Number |
Date |
Country |
Parent |
09113271 |
Jul 1998 |
US |
Child |
09948713 |
Sep 2001 |
US |
Parent |
09538940 |
Mar 2000 |
US |
Child |
09948713 |
Sep 2001 |
US |