Stereolithography using vinyl ether-epoxide polymers

• US 5,437,964 A
• Filed: 02/24/1994
• Issued: 08/01/1995
• Est. Priority Date: 05/01/1991
• Status: Expired due to Term

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: Alliedsignal Inc. (Honeywell International Inc.)
• Inventors: Green, George D., Lapin, Stephen C., Sitzmann, Eugene V., Snyder, James R., Barnes, Darryl K.
• Primary Examiner(s): Chapman, Mark A.
• Application Number:
  US08/201,146
• Time in Patent Office: 523 Days
• Field of Search: 522/170, 522/168, 430/269, 430/280
• US Class Current: 430/280.1
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: C08G 59/18 Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
• CPC Class Codes: C08G 59/68 characterised by the catalysts used
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: G03F 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence
• CPC Class Codes: G03F 7/038 Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021
• CPC Class Codes: G03F 7/0385 using epoxidised novolak resin

Abstract

Polymer precursor formulations suitable for stereolithography may be prepared from compositions containing vinyl ether functionalized compounds and epoxy functionalized compounds plus an effective amount of a cationic photoinitiator.

Claims

1. A polymer precursor composition for forming three-dimensional objects by stereolithography consisting essentially of

(a) vinyl ether functionalized compounds;

(b) epoxy functionalized compounds;

(c) an effective amount of a cationic photoinitiator;

said vinyl ether compounds and epoxy compounds both being curable by acids released by said photoinitiator and having proportions selected to provide a three-dimensional polymeric object having suitable green strength with minimal curl distortion when said composition is polymerized in stereolithography by a light source selected from the group consisting of UV and visible light lasers and defined by the formula M=F/E

where

M is the vinyl ether equivalent weight of the composition and has a value between 80 and 800

F is the total weight in grams of the composition

E is the number of vinyl ether equivalents in the composition.

2. A polymer precursor composition of claim 1 wherein said vinyl ether compounds are derived from at least one member of the groups consisting of urethanes, phenols, esters, ethers, siloxanes, carbonates, and aliphatic or aromatic hydrocarbons.

3. The polymer precursor composition of claim 2 wherein the vinyl ether compounds comprise oligomers having the formula

4. The composition of claim 3 wherein said vinyl ether oligomers are derived from a urethane obtained by reacting

(i) an hydroxyl terminated polyester having the formula ##STR14## where X and Y are divalent radicals having a molecular weight of 28 to about 500 and selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene radicals m has an average value of 1 to about 100 and

(ii) a diisocyanate having the formula

5. The composition of claim 3 wherein said vinyl ether oligomers are derived from a urethane obtained by reacting

(i) an hydroxyl terminated polyether having the formula

6. The composition of claim 3 wherein said vinyl ether oligomers are derived from a polyester obtained by reacting

(a) a dicarboxylic acid having the formula ##STR15## where X and Y are divalent radicals having a molecular weight of about 28 to 500 and selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene radicals

m has an average value of about 1 to 100

(b) with a hydroxy monovinyl ether having the formula

7. The composition of claim 3 wherein said vinyl ether oligomers are derived from a polysiloxane defined as

8. The composition of claim 3 wherein said vinyl ether oligomers are derived from a phenol defined as

9. The composition of claim 3 wherein said vinyl ether oligomers are derived from a polyether by reacting at least one of the groups consisting of poly(ethylene oxy), poly(propylene oxy), or poly(butylene oxy) glycols, where m has an average value from about 2 to 50 with acetylene or a vinyl oxy alkyl halide.

10. The polymer precursor composition of claim 3 wherein the vinyl ether oligomers are derived from a carbonate defined as ##STR16## where p is 4 to 10

Z is a divalent radical having a molecular weight of about 28 to 250 and selected from the group consisting of alkylene, cycloalkylene or polyalkylene ether radicals

X is a diester, diol, or polyol moiety.

11. The composition of claim 2 wherein R'"'"' and R" are hydrogen.

12. The composition of claim 2 wherein R'"'"' is methyl and R" is hydrogen.

13. The polymer precursor composition of claim 2 wherein the vinyl ether compounds comprise monomers having the formula

14. The composition of claim 13 wherein R'"'"' and R" are hydrogen.

15. The composition of claim 13 wherein R'"'"' is methyl and R" is hydrogen.

16. The composition of claim 13 wherein said vinyl ether monomers are derived from esters and having the formula ##STR17## where n is 1 to 4,

M₁ is a mono, di, tri, or tetra functional radical having a molecular weight of 15 to 180 and selected from the group consisting of alkylene, arylene, aralkylene and cycloalkylene radicals

Z is a divalent radical having a molecular weight of 28 to 290 and selected from the group consisting of alkylene, cycloalkylene, or polyalkylene ether radicals

R'"'"' and R" are monovalent radicals selected from the group consisting of H and alkyl groups having 1-10 carbon atoms.

17. The composition of claim 13 wherein said vinyl ether monomers are derived from ethers by reacting at least one of the group consisting of poly(ethyleneoxy), poly(propyleneoxy), or poly(butyleneoxy) glycols, where m has an average value from about 1 to about 5 with acetylene or a vinyl oxy alkyl halide.

18. The composition of claim 13 wherein said vinyl ether monomers are derived from aliphatic hydrocarbons described by the formula

19. The composition of claim 13 wherein said vinyl ether monomers are derived from aromatic hydrocarbons described by the formula

20. The composition of claim 13 wherein said vinyl ether monomers are derived from a polysiloxane defined as

21. The composition of claim 13 wherein said vinyl ether monomers are derived from a carbonate defined as ##STR18## where p is 0 to 3

Z is a divalent radical having a molecular weight of about 28 to 250 and selected from the group consisting of alkylene, cycloalkylene or polyalkylene ether radicals

X is a diester, diol, or polyol moiety.

22. A polymer precursor composition of claim 1 wherein said epoxy compounds are derived from at least one member of the group consisting of phenols, novolacs, aliphatic or cycloaliphatic polyols, and polyether polyols and siloxanes.