Photocurable resins for volumetric additive manufacturing

Patent metadata

Field	Value
Publication number	US-11639031-B2
Application number	US-202015930822-A
Country	US
Kind code	B2
Filing date	May 13, 2020
Priority date	May 13, 2019
Publication date	May 2, 2023
Grant date	May 2, 2023

Abstract

Methods and materials for volumetric additive manufacturing, including computed axial lithography (“CAL”), using photosensitive resins comprising a photocurable resin prepolymer; a photoinitiator; and (optionally) a curing inhibitor. In various embodiments, such photosensitive polymers comprise (a) one or more monomer (or prepolymer) molecules, which form the backbone of the polymer network of the polymeric material and define its architecture; and (b) a photoinitiator that captures illumination energy and initiates polymerization.

First claim

What is claimed is:

1. A method of forming a three dimensional (3D) object, comprising:
simultaneously directing optical projections of light from optical subsystems at a plurality of angles θ through a volume of photocurable composition contained within an optically transparent resin container, the optical projections further being directed about a z axis extending through the volume of photocurable composition; and
providing each of the optical projections with a calculated three-dimensional intensity distribution acting over a fixed temporal exposure period, which is sufficient to cure selected portions of the volume of photocurable composition, and leave other portions unmodified, to form the 3D object;
wherein the photocurable composition comprises a monomer, a photoinitiator, and a curing inhibitor, and exhibits transparency to the light and a non-linear response to the light.

2. The method of claim 1 , wherein the curing inhibitor is selected from the group consisting of oxygen; (2,2,6,6-Tetramethyl-1-piperidinyloxy); phenothiazine; 4-methoxyphenol; N-Nitroso-N-phenylhydroxylamine aluminum salt; tetraethylthiuram disulfide; Di-tert-butyl nitroxide; 2,2,5-Trimethyl-4-phenyl-3-azahexane-3-nitroxide; and combinations thereof.

3. The method of claim 2 , wherein the curing inhibitor comprises oxygen and the monomer is an acrylate.

4. The method of claim 1 , wherein the photocurable composition further has a viscosity of at least 1000 cP.

5. The method of claim 1 , wherein a change in refractive index of the photocurable composition upon curing is not greater than 0.01.

6. A method of forming a three dimensional (3D) object, comprising:
simultaneously directing optical projections of light from optical subsystems at a plurality of angles θ through a volume of photocurable composition contained within an optically transparent resin container, the optical projections further being directed about a z axis extending through the volume of photocurable composition; and
providing each of the optical projections with a calculated three-dimensional intensity distribution acting over a fixed temporal exposure period, which is sufficient to cure selected portions of the volume of photocurable composition, and leave other portions unmodified, to form the 3D object;
wherein the photocurable composition comprises a monomer, a photoinitiator, and a curing inhibitor, and exhibits transparency to the light and a non-linear response to the light; and
wherein a change in refractive index of the photocurable composition upon curing is not greater than 0.03.

7. The method of claim 6 , wherein the change in refractive index of the photocurable composition upon curing is not greater than 0.01.

8. The method of claim 6 , wherein the curing inhibitor is selected from the group consisting of oxygen; (2,2,6,6-Tetramethyl-1-piperidinyloxy); phenothiazine; 4-methoxyphenol; N-Nitroso-N-phenylhydroxylamine aluminum salt; tetraethylthiuram disulfide; Di-tert-butyl nitroxide; 2,2,5-Trimethyl-4-phenyl-3-azahexane-3-nitroxide; and combinations thereof.

9. The method of claim 7 , wherein the curing inhibitor comprises oxygen and the monomer is an acrylate.

10. The method of claim 6 , wherein the photocurable composition further has a viscosity of at least 1000 cP.

11. The method of claim 6 , wherein the photoinitiator is a Norrish Type I or Type II photoinitiator.

Assignees

• L Livermore Nat Security Llc
• Univ California

Inventors

• Shusteff Maxim
• Oakdale James
• Panas Robert Matthew
• Spadaccini Christopher M
• Taylor Hayden K
• Kelly Brett
• Bhattacharya Indrasen
• Heidari Hossein

Classifications

• B29C64/106

  using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material · CPC title

• B29C64/264

  Arrangements for irradiation · CPC title

• B33Y50/02

  for controlling or regulating additive manufacturing processes · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• B29C64/386

  Data acquisition or data processing for additive manufacturing · CPC title