ADDITIVE MANUFACTURING COMPOSITIONS
Disclosed are additive manufacturing compositions comprising: A) 100 to 30 weight percent of a polyamide composition comprising: a) 95 to 5 weight percent of at least one semi-crystalline copolyamide having a melting point, said semi-crystalline copolyamide comprising: i) 5 to 40 mole percent aromatic repeat units derived from one or more aromatic dicarboxylic acids with 8 to 20 carbon atoms and at least one aliphatic diamine with 4 to 20 carbon atoms; and ii) 60 to 95 mole percent aliphatic repeat units derived from one or more aliphatic dicarboxylic acids with 6 to 20 carbon atoms and one or more aliphatic diamines with 4 to 20 carbon atoms; b) 5 to 95 weight percent of at least one amorphous copolyamide comprising: iii) 60 to 90 mole percent aromatic repeat units derived from isophthalic acid and at least one aliphatic diamine with 4 to 20 carbon atoms; and iv) 10 to 40 mole percent aromatic repeat units derived from terephthalic acid and at least one aliphatic diamine with 4 to 20 carbon atoms; and B) 0 to 70 weight percent of at least one additive. These compositions provide 3D printed articles having improved physical properties.
1 . A 3D printed article comprising:
A) 100 to 30 weight percent of a polyamide composition comprising:
a) 95 to 5 weight percent of at least one semi-crystalline copolyamide having a melting point, said semi-crystalline copolyamide comprising:
i) 5 to 40 mole percent aromatic repeat units derived from one or more aromatic dicarboxylic acids with 8 to 20 carbon atoms and at least one aliphatic diamine with 4 to 20 carbon atoms; and
ii) 60 to 95 mole percent aliphatic repeat units derived from one or more aliphatic dicarboxylic acids with 6 to 20 carbon atoms and one or more aliphatic diamines with 4 to 20 carbon atoms;
b) 5 to 95 weight percent of at least one amorphous copolyamide comprising:
iii) 60 to 90 mole percent aromatic repeat units derived from isophthalic acid and at least one aliphatic diamine with 4 to 20 carbon atoms; and
iv) 10 to 40 mole percent aromatic repeat units derived from terephthalic acid and at least one aliphatic diamine with 4 to 20 carbon atoms;
wherein the weight percent of (a) and (b) total 100 weight percent of polyamide composition (A); and
B) 0 to 70 weight percent of at least one additive; and
wherein the weight percent of (A) and (B) total 100 weight percent of the 3D printed article.
2 . The 3D printed article of claim 1 wherein semi-crystalline copolyamide (a) is selected from the group consisting of PA 66/6T, PA 610/6T, PA 612/6T, PA 614/6T, PA 616/6T, and PA 618/6T.
3 . The 3D printed article of claim 1 wherein amorphous copolyamide (b) is PA 6I/6T.
4 . A 3D printed article comprising:
A) 99 to 30 weight percent of a polyamide composition comprising:
a) 85 to 65 weight percent of at least one semi-crystalline copolyamide having a melting point, said semi-crystalline copolyamide comprising:
i) 5 to 40 mole percent aromatic repeat units derived from one or more aromatic dicarboxylic acids with 8 to 20 carbon atoms and at least one aliphatic diamine with 4 to 20 carbon atoms; and
ii) 60 to 95 mole percent aliphatic repeat units derived from one or more aliphatic dicarboxylic acids with 6 to 20 carbon atoms and one or more aliphatic diamines with 4 to 20 carbon atoms;
b) 15 to 35 weight percent of at least one amorphous copolyamide comprising:
iii) 60 to 90 mole percent aromatic repeat units derived from isophthalic acid and at least one aliphatic diamine with 4 to 20 carbon atoms; and
iv) 10 to 40 mole percent aromatic repeat units derived from terephthalic acid and at least one aliphatic diamine with 4 to 20 carbon atoms;
wherein the weight percent of (a) and (b) total 100 weight percent of polyamide composition (A); and
B) 1 to 70 weight percent of at least one additive; and
wherein the weight percent of (A) and (B) total 100 weight percent of the 3D printed article.
5 . The 3D printed article of claim 4 wherein additive (B) is selected from the group consisting of reinforcing agents, tougheners, fillers, adhesion promoters, compatibilizers, crystallization accelerators, crystallization retarders, flow aids, lubricants, mold-release agents, colorants, plasticizers, antioxidants, heat stabilizers, processing aids, flame retardants, antistatic agents, high temperature copolyamides, aliphatic polyamides, and combinations of these.
6 . The 3D printed article of claim 5 wherein said reinforcing agent is selected from the group consisting of glass fibers, glass beads, carbon fibers, graphite, and combinations of these.
7 . The 3D printed article of claim 5 wherein said toughener is selected from the group consisting of functionalized polymeric tougheners, nonfunctionalized polymeric tougheners, and mixtures of these.
8 . The 3D printed article of claim 4 wherein the ratio of wet:dry tensile moduli of elasticity, as measured at room temperature, is greater than or equal to 0.85 and the ratio of wet:dry maximum tensile strength is greater than or equal to 0.85.
9 . The 3D printed article of claim 1 which is prepared by a material extrusion additive manufacturing process.
10 . The 3D printed article of claim 4 exhibiting a ratio of vertical:flat tensile strength of greater than or equal to 0.5.
11 . The 3D printed article of claim 1 which, when tested according to the Curl Bar Test, exhibits a height displacement of 1 mm or less.
12 . The 3D printed article of claim 1 which, when tested according to the Curl Bar Test, exhibits a height displacement of 0.5 mm or less.
13 . An additive manufacturing composition comprising:
A) 100 to 30 weight percent of a polyamide composition comprising:
a) 95 to 5 weight percent of at least one semi-crystalline copolyamide having a melting point, said semi-crystalline copolyamide comprising:
i) 5 to 40 mole percent aromatic repeat units derived from one or more aromatic dicarboxylic acids with 8 to 20 carbon atoms and at least one aliphatic diamine with 4 to 20 carbon atoms; and
ii) 60 to 95 mole percent aliphatic repeat units derived from one or more aliphatic dicarboxylic acids with 6 to 20 carbon atoms and one or more aliphatic diamines with 4 to 20 carbon atoms;
b) 5 to 95 weight percent of at least one amorphous copolyamide comprising:
iii) 60 to 90 mole percent aromatic repeat units derived from isophthalic acid and at least one aliphatic diamine with 4 to 20 carbon atoms; and
iv) 10 to 40 mole percent aromatic repeat units derived from terephthalic acid and at least one aliphatic diamine with 4 to 20 carbon atoms;
wherein the weight percent of (a) and (b) total 100 weight percent of polyamide composition (A); and
B) 0 to 70 weight percent of at least one additive; and
wherein the weight percent of (A) and (B) total 100 weight percent of the additive manufacturing composition.
14 . The composition of claim 13 in the form of filaments or pellets.
15 . The 3D printed article of claim 4 wherein semi-crystalline copolyamide (a) is selected from the group consisting of PA 66/6T, PA 610/6T, PA 612/6T, PA 614/6T, PA 616/6T, and PA 618/6T.
16 . The 3D printed article of claim 4 wherein amorphous copolyamide (b) is PA 6I/6T.
17 . The 3D printed article of claim 9 wherein the material extrusion additive manufacturing process is a fused filament fabrication process.
18 . The 3D printed article of claim 9 wherein the material extrusion additive manufacturing process is a pellet additive manufacturing process.
19 . The 3D printed article of claim 4 wherein polyamide composition (A) comprises:
a) 5 to 54 weight percent of at least one semi-crystalline copolyamide having a melting point, said semi-crystalline copolyamide comprising:
i) 5 to 40 mole percent aromatic repeat units derived from one or more aromatic dicarboxylic acids with 8 to 20 carbon atoms and at least one aliphatic diamine with 4 to 20 carbon atoms; and
ii) 60 to 95 mole percent aliphatic repeat units derived from one or more aliphatic dicarboxylic acids with 6 to 20 carbon atoms and one or more aliphatic diamines with 4 to 20 carbon atoms;
b) 46 to 95 weight percent of at least one amorphous copolyamide comprising:
iii) 60 to 90 mole percent aromatic repeat units derived from isophthalic acid and at least one aliphatic diamine with 4 to 20 carbon atoms; and
iv) 10 to 40 mole percent aromatic repeat units derived from terephthalic acid and at least one aliphatic diamine with 4 to 20 carbon atoms;
wherein the weight percent of (a) and (b) total 100 weight percent of polyamide composition (A).