Stereolithography method

• US 5,167,882 A
• Filed: 02/05/1991
• Issued: 12/01/1992
• Est. Priority Date: 12/21/1990
• Status: Expired due to Fees

• Current Assignee: Loctite Corporation (Henkel AG & Co KGaA)
• Original Assignee: Loctite Corporation (Henkel AG & Co KGaA)
• Inventors: Jacobine, Anthony F., Glaser, David M., Rakas, Margaret A.
• Primary Examiner(s): Tentoni, Leo B.
• Application Number:
  US07/651,271
• Time in Patent Office: 665 Days
• Field of Search: 264/22, 264/308, 156/273.3, 156/273.5, 156/275.5, 156/307.1, 427/43.1, 427/53.1, 427/54.1, 250/492.1, 522/24, 522/64, 522/66, 522/99, 522/167, 522/168, 522/169, 522/173, 522/180, 522/910, 526/281, 528/25, 528/26, 528/30, 528/128, 528/173, 528/205, 528/344, 528/360, 528/361, 528/364, 528/376
• US Class Current: 264/401
• CPC Class Codes: B29C 64/106 using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: C08G 75/045 from mercapto compounds and unsaturated compounds
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: G03F 7/0275 with dithiol or polysulfide compounds
• CPC Class Codes: Y10S 522/91 Treatment through an external filter or mask, nonphotograghic process

Abstract

An improved stereolithography method for building a three-dimensional article including the steps of patternwise curing successive layers of a bath of curable liquid resin formulation until the article has been completely built up, removing the article from the liquid resin bath and then post-curing the article, wherein the liquid resin is a "thiol/nene" formulation including:

(a) a first compound having a plurality of norbornene groups thereon;

(b) a second compound having a plurality of thiol groups therein; and

(c) a free radical photoinitiator,

the total functionality of the formulation being greater than 4.

Claims

1. In a stereolithography method for building a three-dimensional article comprising the steps of patternwise curing successive layers of a bath of curable liquid resin formulation until the article has been completely built up, removing the article from the liquid resin bath and then post-curing the article, the improvement wherein the liquid resin is a thiol/nene formulation comprising:

(a) a first compound having a plurality of norbornene groups thereon;

(b) a second compound having a plurality of thiol groups therein; and

(c) a free radical photoinitiator,

the total functionality of the formulation being greater than 4.

2. A method as in claim 1 wherein said first compound is a norbornene carboxylate polyol ester.

3. A method as in claim 2 wherein said first compound is a norbornene carboxylate ester of trimethylolpropane, hexanediol, ethoxylated bisphenol A or mixtures thereof.

4. A method as in claim 2 wherein said second compound is a α

- or β

-mercaptocarboxylate polyol ester.

5. A method as in claim 4 wherein said second compound is an α

- or β

-mercaptopropionate ester of tri or higher functional alcohol.

6. A method as in claim 5 wherein said second compound is pentaerythritol tetrakis β

-mercaptopropionate.

7. A method as in claim 1 wherein the thickness of each said layer is less than 40 mils.

8. A method as in claim 7 wherein the said layer thickness is about 20 mils or less.

9. A method as in claim 7 wherein said patternwise curing is accomplished by successively tracing sectional images of said article onto the surface of the liquid resin with a UV laser bath to provide a cured sectional layer of said article on said bath surface and incrementally lowering the article one layer depth below the surface of the bath after each layer is cured until the entire article has been built up.

10. A method as in claim 1 wherein the thiol/nene formulation further comprises a shelf-life stabilizing effective amount of a polyiodide.

11. A method as in claim 10 wherein the polyiodide stabilizer is KI/I₂ in an approximate weight ratio of 1:

2 and is present at a level of about 10-2,000 ppm I₂.