Build materials for printing 3D articles
Polymerizable liquids are described herein which, in some embodiments, can produce 3D printed articles of high resolution and desirable mechanical properties. In one aspect, a polymerizable liquid comprises an acrylate component, and a composite resin comprising a curable carrier and polymeric particles dispersed in the curable carrier. The polymerizable liquid also comprises a photoinitiator component.
1. A polymerizable liquid comprising:
an acrylate component;
a composite resin comprising a curable carrier and polymeric particles dispersed in the curable carrier; and
a photoinitiator component,
wherein the acrylate component is present in an amount of 30-70 wt. % based on a total weight of the polymerizable liquid, and
wherein the curable carrier is polymerizable via free radical polymerization.
2. The polymerizable liquid of claim 1 , wherein the polymerizable liquid further comprises a UV-absorber and/or a light stabilizer.
3. The polymerizable liquid of claim 1 , wherein the acrylate component comprises a monofunctional acrylate, a difunctional acrylate, or mixtures thereof.
4. The polymerizable liquid of claim 1 , wherein the acrylate component comprises a trifunctional or higher functional acrylate.
5. The polymerizable liquid of claim 1 , wherein the polymeric particles of the composite resin comprise an elastomer.
6. The polymerizable liquid of claim 1 , wherein the polymeric particles exhibit a core-shell architecture.
7. The polymerizable liquid of claim 6 , wherein the polymeric particles comprise an elastomeric core.
8. The polymerizable liquid of claim 7 , wherein the polymeric particles comprise a thermoplastic shell.
9. A polymerizable liquid comprising:
an acrylate component;
a composite resin comprising a curable carrier and polymeric particles dispersed in the curable carrier; and
a photoinitiator component,
wherein the acrylate component is present in an amount of 30-70 wt. % based on a total weight of the polymerizable liquid;
wherein the polymeric particles exhibit a core-shell architecture;
wherein the polymeric particles comprise an elastomeric core; and
wherein the polymeric particles comprise a thermoset shell.
10. The polymerizable liquid of claim 1 , wherein the polymeric particles are present in an amount of 20-60 wt. % based on a total weight of the composite resin.
11. The polymerizable liquid of claim 1 , wherein the polymeric particles have an average size less than 1 μm.
12. The polymerizable liquid of claim 1 , wherein the polymeric particles have an average size of 50 nm to 500 nm.
13. The polymerizable liquid of claim 1 , wherein the curable carrier comprises unsaturated polyester, vinyl ester, or mixtures thereof.
14. The polymerizable liquid of claim 1 , wherein the curable carrier is copolymerizable with the acrylate component.
15. The polymerizable liquid of claim 1 , wherein the curable carrier is not copolymerizable with the acrylate component.
16. The polymerizable liquid of claim 1 , wherein the composite resin is present in an amount of 20-70 wt. % based on a total weight of the polymerizable liquid.
17. A method of printing a three-dimensional article comprising:
providing the polymerizable liquid of claim 1 , and
irradiating the polymerizable liquid with light to form the article, the article comprising a polymeric composite material including a polymeric matrix comprising an acrylate phase and a cured carrier phase, wherein the polymeric particles are disposed in the polymeric matrix.
18. A method of printing a three-dimensional article comprising:
providing a polymerizable liquid comprising an acrylate component, a composite resin comprising a curable carrier and polymeric particles dispersed in the curable carrier, and a photoinitiator component, wherein the acrylate component is present in an amount of 30-70 wt. % based on a total weight of the polymerizable liquid, and
irradiating the polymerizable liquid with light to form the article, the article comprising a polymeric composite material including a polymeric matrix comprising an acrylate phase and a cured carrier phase, wherein the polymeric particles are disposed in the polymeric matrix;
wherein:
the polymerizable liquid is provided in a layer-by-layer process;
the composite resin is present in the polymerizable liquid in an amount of 20-70 wt. % based on total weight of the polymerizable liquid;
the polymeric particles of the composite resin comprise an elastomer;
the polymeric particles are present in the composite resin in an amount of 20-60 wt. % based on total weight of the composite resin;
the polymeric particles have an average size less than 1 μm; and
the curable carrier comprises unsaturated polyester, vinyl ester, or mixtures thereof.