3D printed composites from a single resin by patterned light exposures

Patent metadata

Field	Value
Publication number	US-10495973-B2
Application number	US-201816024555-A
Country	US
Kind code	B2
Filing date	Jun 29, 2018
Priority date	Jun 30, 2017
Publication date	Dec 3, 2019
Grant date	Dec 3, 2019

Abstract

Provided herein are processes for the generation of composite polymer materials utilizing a single resin. The processes utilize diffusion between a region undergoing a polymerization reaction preferentially polymerizing one monomer component and an unreactive region. Diffusion and subsequent/concurrent polymerization results in a higher concentration of the more reactive monomer component in the reacting region and a higher concentration of the less reactive monomer components in the unreactive region. The unreactive region may be later polymerized. In embodiments, photopolymerization is used and the regions are generated by a mask or other mechanism to pattern the light.

First claim

What is claimed is:

1. A method of making a composite polymer composition from a single resin, the process comprising:
providing a resin, the resin comprising a first monomer component and a second monomer component, the resin characterized by a resin ratio of the first monomer component to the second monomer component;
polymerizing the first monomer component by exposing the resin to a first exposure of light;
forming a first region having a first ratio of the first monomer component to the second monomer component, wherein the first region has a vertical dimension between 50 μm and 250 μm; and
forming a second region having a second ratio of the first monomer component to the second monomer component, wherein the resin ratio, the first ratio, and the second ratio are different.

2. The method of claim 1 , further comprising polymerizing the second monomer component.

3. The method of claim 1 , wherein the polymerizing the first monomer component comprises exposing the resin to a source of radiation.

4. The method of claim 3 , wherein the source of radiation comprises ultraviolet light, visible light, infrared light, microwave irradiation, laser exposure, holography, DLP projection, optical lithography, pulsed light, or a combination thereof.

5. The method of claim 2 , wherein the polymerizing the first monomer component forms a first polymer and wherein the polymerizing the second monomer component forms a second polymer.

6. The method of claim 2 , wherein the polymerizing the second monomer component results in a polymerization-induced phase separation along one or more lateral directions.

7. The method of claim 5 , wherein the first region and the second region are separated by a concentration gradient, wherein the concentration gradient comprises the concentrations of the first monomer component, the second monomer component, the first polymer, and the second polymer.

8. The method of claim 2 , wherein:
the polymerizing the first monomer component uses a source of radiation; and
the polymerizing the second monomer component uses a secondary photopolymerization, wherein the secondary photopolymerization uses a second source of radiation, said second source of radiation comprising ultraviolet light, visible light, infrared light, microwave irradiation, or a combination thereof.

9. The method of claim 2 , wherein:
the polymerizing the first monomer component comprises using a source of radiation; and
the polymerizing the second monomer component comprises using the same source of radiation.

10. The method of claim 1 , wherein the first monomer component and the second monomer component are miscible.

11. The method of claim 5 , wherein the second monomer component is immiscible in the first polymer.

12. The method of claim 1 , wherein the first monomer component comprises one or more of a methacrylate monomer, an acrylate monomer, a thiol monomer, a vinyl acetate monomer, a styrene monomer, a vinyl ether monomer, a derivative thereof, or a combination thereof.

13. The method of claim 1 , wherein the second monomer component comprises one or more of an acrylate monomer, a thiol monomer, an allyl ether monomer, a vinyl acetate monomer, a vinyl chloride monomer, an acrylonitrile monomer, a vinyl ether monomer, a vinyl silane monomer, a vinyl siloxane monomer, a butadiene monomer, a norbornene monomer, a maleate monomer, a fumarate monomer, an epoxide monomer, an anhydride monomer, a hydroxyl monomer, a derivative thereof, or a combination thereof.

14. The method of claim 1 , wherein from 10 to 90 wt % of the resin consists of the first monomer component.

15. The method of claim 1 , wherein from 10 to 90 wt % of the resin consists of the second monomer component.

16. The method of claim 1 , wherein the first monomer component is from 5-fold to 1000-fold more reactive than the second monomer component.

17. The method of claim 1 , wherein the first monomer component and the second monomer component have a difference in reactivity, wherein the difference in the reactivity of the first monomer component and the reactivity of the second monomer component comprises a difference in a polymerization rate coefficient, a difference in concentration, a difference in functionality, a difference in solubility, a difference in diffusivity of the first monomer component, a difference in diffusivity of the second monomer component, or any combination thereof.

18. The method of claim 1 , wherein the first monomer component and the second monomer component have a difference in reactivity, wherein the difference in the reactivity of the first monomer component and the reactivity of the second monomer component comprises a difference in oxygen inhibition, a difference in light absorption, a difference in photoinitator concentration, or a combination thereof.

19. The method of claim 1 , wherein the first region has at least one lateral dimension less than or equal to 100 μm.

20. The method of claim 1 , wherein the second region has at least one lateral dimension less than or equal to 300 μm.

21. The method of claim 3 , wherein the source of radiation initiates polymerization of the first monomer component in a first exposure region, wherein the first exposure region is exposed to a first light intensity of less than 20 mW/cm 2 .

22. The method of claim 21 , wherein the source of radiation initiates polymerization of the second monomer component in a second exposure region, wherein the second exposure region is exposed to a second light intensity, and wherein the second light intensity is equal to or greater than the first light intensity.

23. The method of claim 22 , wherein the first exposure region is exposed to the source of radiation more than once before the second exposure region is exposed to the source of radiation.

24. The method of claim 1 , wherein the composite polymer composition comprises an orthodontic appliance.

25. A composite material made by the method of claim 5 .

26. The composite material of claim 25 , wherein the first polymer comprises a storage modulus at least 200 MPa greater than the storage modulus of the second polymer.

27. The composite material of claim 25 , wherein the first polymer comprises a fracture strain that is from 30% to 1,000% greater than the elongation to break of the second polymer.

28. The method of claim 1 , wherein the second region has a vertical dimension between 50 μm and 250 μm.

29. The method of claim 1 , wherein the first ratio is greater than the resin ratio, and the resin ratio is greater than the second ratio.

Assignees

• Align Technology Inc

Inventors

• Cole Michael Christopher

Classifications

• C08F220/1811 Primary

  C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate · CPC title

• C08F220/1804 Primary

  C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate · CPC title

• C08F220/10

  Esters · CPC title

• C08F218/10

  of monocarboxylic acids containing three or more carbon atoms · CPC title

• C08F2/48

  by ultraviolet or visible light · CPC title