Filaments for use as a support material in fused deposition modeling

Abstract

The present invention relates to the use of a filament comprising a core material (CM) comprising a ceramic material precursor (CMP) and the core material (CM) is coated with a layer of shell material (SM) comprising a thermoplastic polymer as a support material in a fused filament fabrication process. Further, the invention relates to three-dimensional objects and a process for the preparation thereof.

1 .- 15 . (canceled) 
     
     
         16 . A three-dimensional brown body, prepared by a process, comprising the steps:
 i) depositing a support material into a build chamber using a layer-based additive technique to form a support structure,   ii) depositing a modeling material into the build chamber using the layer based additive technique to form the three-dimensional object (the three-dimensional green body), wherein the three-dimensional object comprises at least one region supported by the support structure,   iii) debinding the three-dimensional object obtained in step ii) to remove organic polymer to form the three-dimensional brown body,   
       wherein the support material comprises a filament comprising a core material (CM) coated with a layer of shell material (SM), wherein 
       the core material (CM) comprises the components a) to c)
 a) 30 to 80% by volume, based on the total volume of the core material (CM) of at least ceramic material precursor (CMP), 
 b) 20 to 70% by volume, based on the total volume of the core material (CM) of at least one binder (B) comprising component b1) 
 b1) at least one polymer (P) 
 c) 0 to 20% by volume, based on the total volume of the core material (CM) of at least one additive (A), 
 
       and the shell material(SM) comprises the components d) to f)
 d) 75 to 100% by volume, based on the total volume of the shell material (SM) of at least one thermoplastic polymer (TP), 
 e) 0 to 20% by volume, based on the total volume of the shell material (SM) of the at least one ceramic material precursor (CMP), 
 f) 0 to 25% by volume, based on the total weight of the shell material (SM) of the at least one additive (A), wherein the thickness of the layer of shell material is 0.05 to 0.5 mm. 
 
     
     
         17 . The three-dimensional brown body according to  claim 16 , wherein the modeling material comprises a filament comprising a core material (CM) coated with a layer of shell material (SM), wherein 
       the core material (CM) comprises the components a) to c)
 a) 30 to 80% by volume, based on the total volume of the core material (CM) of a powder of at least one metal, or metal alloy (ME), 
 b) 20 to 70% by volume, based on the total volume of the core material (CM) of at least one binder (B) comprising component b1), 
 b1) at least one polymer (P), 
 c) 0 to 20% by volume, based on the total volume of the core material (CM) of at least one additive (A), 
 
       and the shell material(SM) comprises the components d) to f),
 d) 75 to 100% by volume, based on the total volume of the shell material (SM) of at least one thermoplastic polymer (TP), 
 e) 0 to 20% by volume, based on the total volume of the shell material (SM) of the at least one metal, or metal alloy, 
 f) 0 to 25% by volume, based on the total weight of the shell material (SM) of the at least one additive (A), wherein the thickness of the layer of shell material is 0.05 to 0.5 mm. 
 
     
     
         18 . The three-dimensional brown body according to  claim 16 , wherein the binder (B)
 i) comprises from 50 to 96% by weight or the at least one polymer (P), based on the total weight of the binder, and/or   ii) the at least one polymer (P) is a polyoxymethylene (POM).   
     
     
         19 . The three-dimensional brown body according to  claim 16 , wherein the binder (B) in the core material (CM) further comprises components b2) and/or b3)
 b2) at least one polyolefin (PO),   b3) at least one further polymer (FP), in case component b) is a polyoxymethylene (POM).   
     
     
         20 . The three-dimensional brown body according to  claim 18 , wherein the binder (B) comprises 2 to 35% by weight of component b2), based on the total weight of the binder (B), and/or from 2 to 40% by weight of component b3), based on the total weight of the binder (B). 
     
     
         21 . The three-dimensional brown body according to  claim 16 , wherein
 i) the diameter of the filament is 1.5 to 3.5 mm, and/or   ii) the diameter of the core material is 1.5 to 3.0 mm, and/or   iii) the thickness of the layer of shell material (SM) is 0.04 to 0.5 mm, and/or   iv) the particle size of the ceramic material precursor is from 0.1 to 80 μm, and/or   v) the ceramic material precursor is selected from the group consisting of SiO 2 , CaCO 3 , CaSiO 3 , CaO, Al 2 O 3 , xAl 2 O 3 .ySiO 2 .zH 2 O, TiO 2 , NaAlSi 3 O 8 , KAlSi 3 O 8 , CaAl 2 Si 2 O 8 , CaAl 2 Si 2 O 8 , iron oxide (FeO, Fe 2 O 3 , Fe 3 O 4 ), BaO, and K 2 O and mixtures thereof, and/or   vi) the at least one thermoplastic polymer (TP) of the shell material (SM) is selected from the group of polyoxymethylene (POM), polyolefins (PE) such as polypropylene or polyethylene, polyurethanes (PU), polyamides (PA), polyethers (PETH), polycarbonates (PC), and/or polyesters (PES) such as polylactic acid and blends thereof.   
     
     
         22 . The three-dimensional brown body according to  claim 16 , wherein the polymer (P) in component (b1) is a polyoxymethylene (POM) copolymer which is prepared by polymerization of
 from at least 50 mol-% of a formaldehyde source (b1a),   from 0.01 to 20 mol-% of at least one first comonomer (b1b) of the general formula (II)   
       
         
           
           
               
               
           
         
       
       wherein
 R 1  to R 4  are each independently of one another selected from the group consisting of H, C 1 -C 4 -alkyl and halogen-substituted C 1 -C 4 -alkyl; 
 R 5  is selected from the group consisting of a chemical bond, a (—CR 5a R 5b —) group and a (—CR 5a R 5b O—) group, wherein 
 R 5a  and R 5b  are each independently of one another selected from the group consisting of H and unsubstituted or at least monosubstituted C 1 -C 4 -alkyl, 
 
       wherein the substituents are selected from the group consisting of F, Cl, Br, OH and C 1 -C 4 -alkyl;
 n is 0, 1, 2 or 3; and 
 from 0 to 20 mol-% of at least one second comonomer (b1c) selected from the group consisting of a compound of formula (III) and a compound of formula (IV) 
 
       
         
           
           
               
               
           
         
       
       wherein
 Z is selected from the group consisting of a chemical bond, an (—O—) group and an (—O—R 6 —O—) group, wherein 
 R 6  is selected from the group consisting of unsubstituted C 1 -C 8 -alkylene and C 3 -C 8 -cycloalkylene. 
 
     
     
         23 . The three-dimensional brown body according to  claim 16 , wherein the further polymer (FP) is at least one further polymer (FP) selected from the group consisting of a polyether, a polyurethane, a polyepoxide, a polyamide, a vinyl aromatic polymer, a poly(vinyl ester), a poly(vinyl ether), a poly(alkyl (meth)acrylate) and copolymers thereof 
     
     
         24 . A process, in which the three-dimensional brown body according to  claim 16  is sintered to form a three-dimensional sintered object (three-dimensional sintered body) and the support structure is removed from the three-dimensional sintered object. 
     
     
         25 . A filament comprising a core material (CM) coated with a layer of shell material (SM), wherein the core material (CM) comprises the components a) to c)
 a) 30 to 80% by volume, based on the total volume of the core material (CM) of ceramic material precursor (CMP) which is selected from the group consisting of SiO 2  and CaCO 3  and mixtures thereof (IP),   b) 20 to 70% by volume, based on the total volume of the core material (CM) of at least one binder (B) comprising component b1),   b1) at least one polymer (P),   c) 0 to 20% by volume, based on the total volume of the core material (CM) of at least one additive (A),   and the shell material(SM) comprises the components d) to f),   d) 75 to 100% by volume, based on the total volume of the shell material (SM) of at least one thermoplastic polymer (TP),   e) 0 to 20% by volume, based on the total volume of the shell material (SM) of the at least one ceramic material precursor (CMP), and   f) 0 to 25% by volume, based on the total weight of the shell material (SM) of the at least one additive (A), wherein the thickness of the layer of shell material is 0.05 to 0.5 mm.   
     
     
         26 . The filament according to  claim 25 , wherein the binder (B)
 i) comprises from 50 to 96% by weight or the at least one polymer (P), based on the total weight of the binder, and/or   ii) the at least one polymer (P) is a polyoxymethylene (POM).   
     
     
         27 . The filament according to  claim 25 , wherein the binder (B) in the core material (CM) further comprises components b2) and/or b3)
 b2) at least one polyolefin (PO),   b3) at least one further polymer (FP), in case component b) is a polyoxymethylene (POM).   
     
     
         28 . The filament according to  claim 25 , wherein the binder (B) comprises 2 to 35% by weight of component b2), based on the total weight of the binder (B), and/or from 2 to 40% by weight of component b3), based on the total weight of the binder (B). 
     
     
         29 . The filament according to  claim 25 , wherein
 i) the diameter of the filament is 1.5 to 3.5 mm, and/or   ii) the diameter of the core material is 1.5 to 3.0 mm, and/or   iii) the thickness of the layer of shell material (SM) is 0.04 to 0.5 mm, and/or   iv) the particle size of the ceramic material precursor is from 0.1 to 80 μm, and/or   v) the ceramic material precursor is selected from the group consisting of SiO 2  and CaCO 3  and mixtures thereof, and/or   vi) the at least one thermoplastic polymer (TP) of the shell material (SM) is selected from the group of polyoxymethylene (POM), polyolefins (PE) such as polypropylene or polyethylene, polyurethanes (PU), polyamides (PA), polyethers (PETH), polycarbonates (PC), and/or polyesters (PES) such as polylactic acid and blends thereof.   
     
     
         30 . The filament according to  claim 25 , wherein the polymer (P) in component (b1) is a polyoxymethylene (POM) copolymer which is prepared by polymerization of
 from at least 50 mol-% of a formaldehyde source (b1a),   from 0.01 to 20 mol-% of at least one first comonomer (b1b) of the general formula (II)   
       
         
           
           
               
               
           
         
       
       wherein
 R 1  to R 4  are each independently of one another selected from the group consisting of H, C 1 -C 4 -alkyl and halogen-substituted C 1 -C 4 -alkyl; 
 R 5  is selected from the group consisting of a chemical bond, a (—CR 5a R 5b —) group and a (—CR 5a R 5b O—) group, wherein 
 R 5a  and R 5b  are each independently of one another selected from the group consisting of H and unsubstituted or at least monosubstituted C 1 -C 4 -alkyl, 
 
       wherein the substituents are selected from the group consisting of F, Cl, Br, OH and C 1 -C 4 -alkyl;
 n is 0, 1, 2 or 3; and 
 from 0 to 20 mol-% of at least one second comonomer (b1c) selected from the group consisting of a compound of formula (III) and a compound of formula (IV) 
 
       
         
           
           
               
               
           
         
       
       wherein
 Z is selected from the group consisting of a chemical bond, an (—O—) group and an (—O—R 6 —O—) group, wherein 
 R 6  is selected from the group consisting of unsubstituted C 1 -C 8 -alkylene and C 3 -C 8 -cycloalkylene. 
 
     
     
         31 . The filament according to  claim 25 , wherein the further polymer (FP) is at least one further polymer (FP) selected from the group consisting of a polyether, a polyurethane, a polyepoxide, a polyamide, a vinyl aromatic polymer, a poly(vinyl ester), a poly(vinyl ether), a poly(alkyl (meth)acrylate) and copolymers thereof.