Fused filament printing
The invention relates to a method for forming a three-dimensional object by fused filament fabrication comprising the step of selectively dispensing a polymer composition containing a semi-crystalline copolyamide in accordance with the shape of a portion of a three-dimensional object, characterized that the semi-crystalline copolyamide comprises: a) At least 70 wt. % of aliphatic monomeric units derived from i. Aminoacid A, or ii. diamine B and diacid C, and b) At least 0.5 wt. % of further monomeric units derived from a cyclic monomer, wherein wt. % is with respect to the total weight of the semi-crystalline copolyamide. The invention relates also relates to objects attainable by this method and to the use of the said semi-crystalline copolyamide in fused filament fabrication.
1. A method for forming a three-dimensional object by fused filament fabrication comprising the step of selectively dispensing a polymer composition containing a semi-crystalline copolyamide in accordance with the shape of a portion of a three-dimensional object, wherein the semi-crystalline copolyamide comprises:
a) at least 70 wt. % of aliphatic monomeric units derived from
i. aminoacid A, or
ii. diamine B and diacid C, and
b) at least 0.5 wt. % of further monomeric units derived from a cyclic monomer, wherein the weight percentage (wt. %) is with respect to the total weight of the semi-crystalline copolyamide.
2. The method according to claim 1 , wherein the polymer composition comprises at least 30 wt. % of the semi-crystalline copolyamide, wherein wt. % is with respect to the total weight of the polymer composition.
3. The method according to claim 1 , wherein the aliphatic monomeric units are derived from a monomer selected from the group consisting of epsilon-caprolactam, 1,4-diaminobutane and 1,10-decanedioic acid, 1,6-diaminohexane and 1,6-hexanedioic acid.
4. The method according to claim 1 , wherein the cyclic monomer is an aromatic monomer, or a cycloaliphatic monomer, or a combination thereof.
5. The method according to claim 1 , wherein the cyclic monomer is selected from the group consisting of isophoronediamine (IPD), cis-1,4-cyclohexanedicarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid, cis-1,3-cyclohexanedicarboxylic acid and trans-1,3-cyclohexanedicarboxylic acid.
6. The method according to claim 1 , wherein the aliphatic monomeric units derived from A, or B and C, are selected from the group of monomers consisting of epsilon caprolactam, 1,4-diaminobutane and 1,10-decanedioic acid, 1,6-diaminohexane and 1,6-hexanedioic acid and the further monomeric units derived from a cyclic monomer are selected from the group of monomers consisting of isophoronediamine (IPD), cis-1,4-diaminocyclohexane, trans-1,4-diaminocyclohexane, bis-(p-aminocyclohexane)methane (PACM), 2,2-Di-(4-aminocyclohexyl)-propane, 3,3′-dimethyl-4-4′-diaminodicyclohexylmethane (DMDC), p-xylylenediamine, m-xylylenediamine, 3,6-bis(aminomethyl)norbornane, isophthalic acid (I), terephthalic acid (T), 4-methylisophthalic acid, 4-tert-butylisophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid, cis-1,3-cyclohexanedicarboxylic acid and trans-1,3-cyclohexanedicarboxylic acid.
7. The method according to claim 1 , wherein the printing speed is at least 10 mm/s.
8. The method according to claim 1 , wherein the further monomeric units derived from a cyclic monomer comprise isophorone diamine and terephthalic acid.
9. The method according to claim 1 , wherein the filament is supplied from a coil.
10. The method according to claim 1 , wherein the filament is produced by melt-extrusion of a granulate material comprising the polymer composition.
11. The method according to claim 1 , wherein aminoacid A comprises epsilon-caprolactam, aminodecanoic acid, aminoundecanoic acid, or aminododecanoic acid.
12. The method according to claim 11 , wherein diamine B comprises 1,4-diaminobutane, 1,5-diaminopentane, or 1,6-diaminohexane.
13. The method according to claim 12 , wherein diacid C comprises 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic acid, 1,15-pentadecanedioic acid, 1,16-hexadecanedioic acid, 1,17-heptadecanedioic acid, or 1,18-octadecanedioic acid.
14. The method of claim 13 , wherein the cyclic monomer comprises isophoronediamine (IPD), cis-1,4-diaminocyclohexane, trans-1,4-diaminocyclohexane, bis-(p-aminocyclohexane)methane (PACM), 2,2-Di-(4-aminocyclohexyl)-propane, 3,3′-dimethyl-4-4′-diaminodicyclohexylmethane (DMDC), p-xylylenediamine, m-xylylenediamine, 3,6-bis(aminomethyl)norbornane, isophthalic acid (I), terephthalic acid (T), 4-methylisophthalic acid, 4-tert-butylisophthalic acid, 1,4-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid, ¬cis-1,4-cyclohexanedicarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid, cis-1,3-cyclohexanedicarboxylic acid, or trans-1,3-cyclohexanedicarboxylic acid.
15. The method of claim 14 , wherein the semi-crystalline copolyamide comprises between 0.8 to 7 wt. % of further monomeric units derived from at least two different cyclic monomers.
16. The method of claim 1 , wherein the semi-crystalline copolyamide comprises at least 80 wt. % of aliphatic monomeric units derived from
i. aminoacid A, or
ii. diamine B and diacid C; and
between 0.8 to 3 wt. % of further monomeric units derived from a cyclic monomer.
17. The method of claim 16 , wherein the polymer composition comprises at least 60 wt. % of the semi-crystalline polyamide, relative to the total weight of the polymer composition.
18. The method of claim 1 , wherein the polymer composition consists of the semi-crystalline copolyamide.