Soluble material and process for three-dimensional modeling

• US 20050004282A1
• Filed: 07/26/2004
• Published: 01/06/2005
• Est. Priority Date: 04/20/1999
• Status: Active Grant

• Current Assignee: Stratasys Incorporated
• Original Assignee: Stratasys Incorporated
• Inventors: Priedeman, William R. Jr., Brosch, Andrea L.
• Granted Patent: US 7,754,807 B2
• Time in Patent Office: Days
• US Class Current: 524/115
• CPC Class Codes: B29C 41/08 Coating a former, core or other substrate by spraying or fluidisation, e.g. spraying powder spray-up of reinforcing fibres B29C70/305
• CPC Class Codes: B29C 41/36 Feeding the material on to the mould, core or other substrate
• CPC Class Codes: B29C 41/50 Shaping under special conditions, e.g. vacuum
• CPC Class Codes: B29C 64/106 using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
• CPC Class Codes: B29C 64/118 using filamentary material being melted, e.g. fused deposition modelling [FDM]
• CPC Class Codes: B29C 64/40 Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
• CPC Class Codes: B29K 2055/02 ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
• CPC Class Codes: B29K 2105/0008 Anti-static agents
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: C08K 5/0016 Plasticisers
• CPC Class Codes: C08L 33/02 Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Abstract

The present invention is a composition for making a three-dimensional object. The composition comprises a plasticizer and a base polymer, where the base polymer comprises a carboxylic acid, where the composition is soluble in an alkaline solution.

Claims

1. A composition for making a three-dimensional object, the composition comprising a plasticizer and a base polymer, the base polymer comprising a carboxylic acid, wherein the composition is soluble in an alkaline solution.

2. The composition of claim 1, wherein the plasticizer constitutes from about 0.01% to about 50.0% by weight of the composition, based on a total weight of the composition.

3. The composition of claim 2, wherein the plasticizer constitutes from about 5.0% to about 25.0% by weight of the composition, based on the a total weight of the composition.

4. The composition of claim 1, wherein the plasticizer is selected from a group consisting of p-t-butylphenyl diphenyl phosphate;

butyl benzyl phthalate;

7-(2,6,6,8-tetramethyl-4-oxa-3-oxononyl) benzyl phthalate;

C7/C9 alkyl benzyl phthalate;

2-ethylhexyl diphenyl phosphate;

isodecyl diphenyl phosphate, and combinations thereof.

5. The composition of claim 1, wherein the carboxylic acid comprises methacrylic acid.

6. The composition of claim 5, wherein the carboxylic acid constitutes from about 15.0% to about 60.0% by weight of the base polymer, based on a total weight of the base polymer.

7. The composition of claim 1, wherein the base polymer further comprises an alkyl methacrylate.

8. The composition of claim 7, wherein the alkyl methacrylate comprises a methyl methacrylate.

9. The composition of claim 1, wherein the composition exhibits a glass transition temperature ranging from of about 49°

C. to about 160°

C.

10. The composition of claim 1, wherein the composition exhibits a melt flow index ranging from of about 1 gram/10 minutes to about 10 grams/10 minutes when tested pursuant to ASTM D1238 under a 1.2 kilogram load at 230°

C.

11. The composition of claim 10, wherein the composition exhibits a melt flow index ranging from of about 5 grams/10 minutes to about 10 grams/10 minutes when tested pursuant to ASTM D1238 under a 1.2 kilogram load at 230°

C.

12. A composition for making a three-dimensional object, the composition comprising a carboxylic acid-containing polymer, wherein the composition is soluble in an alkaline solution, and wherein the composition exhibits a melt flow index of about 10 grams/10 minutes or less when tested pursuant to ASTM D1238 under a 1.2 kilogram load at 230°

C.

13. The composition of claim 12 further comprising a plasticizer.

14. The composition of claim 13, wherein the plasticizer constitutes about 25.0% by weight of the composition or less, based on a total weight of the composition.

15. The composition of claim 12, wherein the composition exhibits a glass transition temperature of about 100°

C. or greater.

16. The composition of claim 12, wherein the composition exhibits a melt flow index ranging from of about 5 grams/10 minutes to about 10 grams/10 minutes when tested pursuant to ASTM D1238 under a 1.2 kilogram load at 230°

C.

17. The composition of claim 12, wherein the carboxylic acid comprises methacrylic acid.

18. The composition of claim 12, wherein the base polymer further comprises an alkyl methacrylate.

19. The composition of claim 18, wherein the alkyl methacrylate comprises a methyl methacrylate.

20. The composition of claim 18, wherein the carboxylic acid constitutes from about 15.0% to about 60.0% by weight of the carboxylic acid and the alkyl methacrylate, based on a total weight of the carboxylic acid and the alkyl methacrylate.

21. The composition of claim 18, wherein the carboxylic acid and the alkyl methacrylate are polymerized.

22. A method of making a three-dimensional article, the method comprising:

depositing a composition comprising a base polymer derived from a carboxylic acid, wherein the composition is soluble in an alkaline solution, and wherein the composition exhibits a melt flow index of about 10 grams/10 minutes or less when tested pursuant to ASTM D1238 under a 1.2 kilogram load at 230°

C.; and

allowing the composition to solidify.

23. The method of claim 22, wherein the composition is deposited and solidified in a plurality of steps so as to make a plurality of layers, wherein the layers define the three-dimensional article.

24. The method of claim 22, wherein the composition further comprises a plasticizer.

25. The method of claim 24, wherein the plasticizer constitutes about 25.0% by weight of the composition or less, based on a total weight of the composition.

26. The method of claim 24, wherein the composition is deposited in a build envelope that exhibits a build envelope temperature, and wherein the plasticizer is concentrated in the composition at effective levels to allow the composition to exhibit a glass transition temperature greater than the build envelope temperature.

27. The method of claim 24, wherein the plasticizer constitutes about 25.0% by weight of the composition or less, based on a total weight of the composition.

28. The method of claim 27, wherein the composition exhibits a glass transition temperature of about 100°

C. or greater.

29. The method of claim 27, wherein the composition exhibits a melt flow index ranging from of about 5 grams/10 minutes to about 10 grams/10 minutes when tested pursuant to ASTM D1238 under a 1.2 kilogram load at 230°

C.

30. The composition of claim 22, wherein the carboxylic acid comprises methacrylic acid.

31. The composition of claim 22, wherein the base polymer is further derived from an alkyl methacrylate.

32. The composition of claim 31, wherein the alkyl methacrylate comprises a methyl methacrylate.

33. In a process for making a three-dimensional object by dispensing solidifiable modeling material in a predetermined pattern so as to define the three-dimensional object in coordination with dispensing solidifiable support material so as to define a support structure for the three-dimensional object, the support structure thereby having portions thereof in contact with the object, the improvement comprising:

forming at least those portions of the support structure contacting the object from a thermoplastic material comprising a carboxylic acid-containing polymer, wherein the composition is soluble in an alkaline solution, and wherein the composition exhibits a melt flow index of about 10 grams/10 minutes or less when tested pursuant to ASTM D1238 under a 1.2 kilogram load at 230°

C.

34. The process of claim 33, wherein the thermoplastic material further comprises a plasticizer constituting from about 0.01% to about 50.0% by weight of the thermoplastic material, based on a total weight of the thermoplastic material.

35. An additive process for making three-dimensional objects, comprising:

dispensing an alkali-insoluble modeling material in a predetermined pattern defining a three-dimensional object having overhanging portions that require support during formation; and

dispensing a support material in the space beneath the overhanging portions of the three-dimensional object in coordination with the dispensing of the modeling material to form a three-dimensional support structure for the object, the support material comprising a carboxylic acid-containing polymer, wherein the composition is soluble in an alkaline solution, and wherein the composition exhibits a melt flow index of about 10 grams/10 minutes or less when tested pursuant to ASTM D1238 under a 1.2 kilogram load at 230°

C.;

whereby the support material may be dissolved from the three-dimensional object by application of an alkaline solution.

36. The process of claim 35, wherein the support material further comprises a plasticizer.

37. The process of claim 35, wherein the support material exhibits a glass transition temperature of about 100°

C. or greater.

38. In a process for making three-dimensional objects by depositing solidifiable material onto a base, the improvement comprising:

providing as the solidifiable material a carboxylic acid-containing polymer, wherein the composition is soluble in an alkaline solution, and wherein the composition exhibits a melt flow index of about 10 grams/10 minutes or less when tested pursuant to ASTM D1238 under a 1.2 kilogram load at 230°

C.