Stereolithographic resins with high temperature and high impact resistance
View Patent ↗A liquid radiation-curable composition that comprises (A) at least one polymerizing organic substance comprising a mixture of (1) at least one alicyclic epoxide having at least two epoxy groups; and (2) at least one difunctional or higher functional glycidylether of a polyhydric compound; (B) at least one free-radical polymerizing organic substance comprising a mixture of (1) optionally, at least one trifunctional or higher functional (meth)acrylate compound; and (2) at least one aromatic di(meth)acrylate compound; (C) at least one cationic polymerization initiator; (D) at least one free-radical polymerization initiator; (E) optionally, at least one hydroxyl-functional aliphatic compound; and (F) at least one hydroxyl-functional aromatic compound; wherein the concentration of hydroxyl groups in the radiation-curable composition is at least about 1.1 equivalent OH groups per kilogram; wherein the concentration of epoxy groups in the radiation-curable composition is at least about 5.5 equivalent epoxy groups per kilogram; and wherein the amount of trifunctional or higher functional (meth)acrylate compound (B)(1) is from 0% to about 3% of the composition and the amount of aromatic di(meth)acrylate compound (B)(2) is at least 10% of the composition.
1. A liquid radiation-curable composition that comprises
(A) at least one polymerizing organic substance comprising a mixiure of
(1) at least one alicyclic epoxide having at least two epoxy groups; and
(2) at least one difunctional or higher functional glycidylether of a polyhydric compound;
(B) at least one free-radical polymerizing organic substance comprising a mixture of
(1) at least one aromatic di(meth)acrylate compound; and
(2) optionally, at least one trifunctional or higher functional (meth)acrylate compound; and
(C) at least one cationic polymerization initiator;
(D) at least one free-radical polymerization initiator;
(E) optionally at least one hydroxyl-functional aliphatic compound; and
(F) at least one hydroxyl-functional aromatic compound selected from the ground consisting of bisphenol A, bisphenol S, ethoxylated bisphenol A, and ethoxylated bisphenol S;
wherein the concentration of hydroxyl groups in the radiation-curable composition is at least about 1.1 equivalent OH groups per kilogram; wherein the concentration of epoxy groups in the radiation-curable composition is at least about 5.5 equivalent epoxy groups per kilogram; and wherein the amount of trifunctional or higher functional (meth)acrylate compound (B)(2) is from 0% to about 3% of the composition and the amount of aromatic di(meth)acrylate compound (B)(1) is at least 10% of the composition.
2. The composition of claim 1 wherein component (A)(1) is 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate.
3. The composition of claim 1 wherein component (A)(1) constitutes from about 50% to about 60% by weight of the total liquid radiation-curable composition.
4. The composition of claim 1 wherein component (A)(2) is trimethylol propane triglycidylether.
5. The composition of claim 1 wherein component (A)(2) constitutes about 10% to about 25% by weight of the total liquid-radiation curable composition.
6. The composition of claim 1 wherein the component (A)(1) constitutes about 5% to about 90% by weight and the component (A)(2) constitutes about 10% to about 50% by weight, based on the total cationic polymerizing organic substance (A).
7. The composition of claim 1 wherein component (B)(1) is a di(meth)acrylate of an aromatic diol.
8. The composition of claim 7 wherein the di(meth)acrylate of an aromatic diol is bisphenol A diglycidylether diacrylate.
9. The composition of claim 1 wherein component (B)(1) constitutes about 10% to about 20% by weight of the total liquid radiation-curable composition.
10. The composition of claim 1 wherein component (B)(2) is present and is a tri-, tetra or pentafunctional monomeric or oligomeric aliphatic, cycloaliphatic, or aromatic (meth)acrylate.
11. The composition of claim 10 wherein component (B)(2) is dipentaerythritol monohydroxy-pentaacrylate.
12. The composition of claim 1 wherein component (B)(2) is present and its amount is from about 1% to about 3% by weight of the total liquid radiation-curable composition.
13. The composition of claim 1 wherein component (C) is triarylsulfonium hexafluoroantimonate.
14. The composition of claim 1 wherein component (C) constitutes from about 0.1 to about 5% by weight of the total liquid radiation-curable composition.
15. The composition of claim 1 wherein component (D) is 1-hydroxycyclohexyl phenyl ketone.
16. The composition of claim 1 wherein component (D) constitutes from about 0.1 to about 5% by weight of the total liquid radiation-curable composition.
17. The composition of claim 1 wherein component (E) is present and is trimethylolpropane.
18. The composition of claim 17 wherein component (E) is present from about 1% to about 3% by weight of the total liquid radiation-curable composition.
19. The composition of claim 1 wherein component (F) is an ethoxylated bisphenol A.
20. The composition of claim 1 wherein component (F) constitutes from about 5% to about 20% by weight of the total liquid radiation-cured composition.
21. The composition of claim 1 wherein the curable composition additionally contains a sensitizer.
22. The composition of claim 21 wherein sensitizer is pyrene.
23. The composition of claim 1 wherein the curable composition additionally contains a cationic stabilizer.
24. The composition of claim 23 wherein the cationic stabilizer is benzyldimethylamine.
25. A liquid radiation-curable composition useful for the production of three dimensional articles by stereolithography that comprises
(A) at least one cationically polymerizing organic substance comprising a mixture of:
(1) 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate; and
(2) trimethylol propane triglycidylether;
(B) at least one free-radical polymerizing organic substance comprising a mixture of:
(1) at least one di(meth) acrylate of an aromatic diol; and
(2) at least one tri-, tetra or pentafunctional monomeric or oligomeric aliphatic, cycloaliphatic or aromatic (meth)acrylate;
(C) at least one cationic polymerization initiator;
(D) at least one free radical polymerization initiator;
(B) trimethylolpropane; and
(F) ethoxylated bisphenol A;
wherein the concentration of hydroxyl groups in the radiation-curable composition is at least 1.1 equivalent OH groups per kilogram, wherein the concentration of epoxy groups in the radiation-curable composition is at least about 5.5 equivalent epoxy group per kilogram; and the amount of component B(2) is from about 1% to 3% of the total compositions and the amount of component B(1) is from about 10% to about 20% by weight of the total composition.
26. A process for forming a three-dimensional article, said process comprising the steps:
(1) coating a thin layer of a composition onto a surface;
(2) exposing said thin layer imagewise to actinic radiation to form an imaged cross-section, wherein the radiation is of sufficient intensity to cause substantial curing of the thin layer in the exposed areas;
(3) coating a thin 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 composition is that which is described in claim 1 .