Polymers as support material for use in fused filament fabrication

• US 10,421,269 B2
• Filed: 02/17/2015
• Issued: 09/24/2019
• Est. Priority Date: 02/19/2014
• Status: Active Grant

• Current Assignee: BASF SE
• Original Assignee: BASF SE
• Inventors: Hermant, Marie-Claire, Nestle, Nikolaus, Hueffer, Stephan
• Primary Examiner(s): Calandra, Anthony
• Assistant Examiner(s): Hernandez, Jerzi H Moreno
• Application Number:
  US15/120,051
• Publication Number:
  US 20170057176A1
• Time in Patent Office: 1,680 Days
• 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 2105/08 of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
• CPC Class Codes: B29K 2839/06 Polymers of N-vinyl-pyrrolidones
• CPC Class Codes: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: C08F 218/08 Vinyl acetate
• CPC Class Codes: C08F 218/10 of monocarboxylic acids containing three or more carbon atoms
• CPC Class Codes: C08F 226/06 by a heterocyclic ring containing nitrogen
• CPC Class Codes: C08F 226/10 N-Vinyl-pyrrolidone

Abstract

The present invention relates to the use of a polymer comprising polymerized units (A) and (B): (A) at least one first monomer of the formula (I) where n is 3 to 12; m is 0 to 3; R¹ is C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, aryl or aralkyl; R², R³ and R⁴ are each, independently of one another, hydrogen, C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, aryl or aralkyl; and (B) at least one second monomer of the formula (II) where R⁵, R⁶ and R⁷ are each, independently of one another, hydrogen, C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, aryl or aralkyl; R⁸ is C₁-C₂₀-alkyl, C₂-C₁₀alkenyl, aryl or aralkyl; as a support material in a fused filament fabrication process.

Claims

1. A process for producing a three-dimensional solid object, the process comprising:

i) depositing a support material into a build chamber with a layer-based additive technique to form a solid support structure;

ii) depositing a modeling material into the build chamber with the layer-based additive technique to form the three-dimensional solid object, wherein the three-dimensional solid object comprises at least one region supported by the solid support structure; and

iii) removing the solid support structure from the three-dimensional solid object with an aqueous solution,

wherein each layer deposited with a layer-based additive technique is solidified before depositing each additional layer thereon; and

wherein the support material comprises a polymer comprising polymerized units (A) and (B);

(A) at least one first monomer of formula (I);

2. The process according to claim 1, wherein the polymer comprises at least 20% by weight of polymerized unit (A), based on the total weight of the polymer.

3. The process according to claim 1, wherein the polymer comprisesto 80% by weight of polymerized unit (A) andto 20% by weight of polymerized unit (B),

based on the total weight of the polymer.

4. The process according to claim 1, wherein polymerized unit (A) comprises at least one monomer selected from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, and N-vinylcaprolactame.

5. The process according to claim 1, wherein polymerized unit (A) comprises

at least 80% by weight of N-vinylpyrrolidone, and

0 to 20% by weight of at least one monomer of formula (I) which is different from N-vinylpyrrolidone,

based on the total weight of component (A).

6. The process according to claim 1, wherein polymerized unit (A) comprises

at least 80% by weight of N-vinylpyrrolidone, and

0 to 20% by weight of N-vinylcaprolactam,

based on the total weight of component (A).

7. The process according to claim 1, wherein polymerized unit (B) comprises

at least 80% by weight of vinyl acetate, and

0 to 20% by weight of at least one monomer of formula (II) which is different from N-vinyl acetate,

based on the total weight of component (B).

8. The process according to claim 1, wherein polymerized unit (B) comprises

at least 80% by weight of vinyl acetate, and

0 to 20% by weight of at least one monovinyl ester of a C₄ to C₂₀ monocarboxylic acid,

based on the total weight of component (B).

9. The process according to claim 1, wherein the polymer has a mass average molecular (Mw) in the range of 30 to 1000 kg/mol.

10. The process according to claim 1, wherein the polymer has a glass transition temperature in the range of 40 to 200°

C.

11. The process according to claim 1, wherein the viscosity of the polymer is in the range of 1 to 10,000 Pa·

s, measured at 240°

C. at a shear rate of 10 rad/s.

12. The process according to claim 1, wherein the polymer comprises:

20 to 80% by weight of polymerized unit (A) consisting of N-vinylpyrrolidone and

80 to 20% by weight of polymerized unit (B) consisting of vinyl acetate,

based on the total weight of the polymer.

13. The process according to claim 1, wherein the polymer comprisesto 80% by weight of polymerized unit (A) consisting of N-vinylpyrrolidone,to 20% by weight of polymerized unit (B) consisting of vinyl acetate and

1 to 10% by weight of a polymerized unit (C) consisting of N-vinylcaprolactam,

based on the total weight of the polymer.

14. The process according to claim 1, wherein the polymer comprisesto 80% by weight of polymerized unit (A) consisting of N-vinylpyrrolidone,to 20% by weight of polymerized unit (B) consisting of vinyl acetate and

1 to 10% by weight of a polymerized unit (C) consisting of at least one monovinyl ester of formula (III)

15. A fused filament fabrication process, the process comprising:

depositing a modeling material into a build chamber with a layer-based additive technique to form a three-dimensional structure around a solid support material preformed in the build chamber,

wherein the solid support material comprises a polymer comprising polymerized units (A) and (B);

(A) at least one first monomer of formula (I);