3D-PRINTING METHODS AND SYSTEMS
The present invention belongs to the field of three-dimensional printing methods. It relates to a method for printing a three-dimensional article made of polycyanoacrylate. It also relates to a method for recycling a three-dimensional article made of polycyanoacrylate.
1 . A method for printing a three-dimensional (3D) article, comprising the steps of:
a) providing a volume of liquid resin comprising cyanoacrylate-based monomers, a photoinitiating system and an acidic inhibitor, held in a tank, said tank comprising at least one optically transparent portion;
b) defining a polymerization zone;
c) emitting and controlling light and transmitting it to the liquid resin through the optically transparent portion for selectively polymerizing the liquid resin in the polymerization zone; and
d) obtaining a three-dimensional article made of a polymerized resin;
e) treating the obtained three-dimensional article with a non-nucleophilic rinsing solvent for removing the excess liquid resin; and,
f) optionally exposing the obtained three-dimensional article with an additional light source for rendering the article non tacky.
2 . A printing method according to claim 1 , in which the cyanoacrylate-based monomers are selected from the group consisting of mono-functional cyanoacrylate monomers, multi-functional cyanoacrylate monomers including bifunctional cyanoacrylate monomers, hybrid cyanoacrylate monomers, and mixtures thereof.
3 . A printing method according to claim 1 ,
in which the cyanoacrylate-based monomers are exclusively mono-functional cyanoacrylate monomers.
4 . A printing method according to claim 1 , in which the cyanoacrylate-based monomers are selected from 2-methoxyethyl cyanoacrylate, methyl cyanoacrylate, ethyl cyanoacrylate, n-propyl cyanoacrylate, iso-propyl cyanoacrylate or mixtures thereof.
5 . A printing method according to claim 1 , in which the liquid resin comprises additional photopolymerizable monomers.
6 . A printing method according to claim 1 , in which the photoinitiator system is an anionic or zwitterionic photoinitiating system.
7 . A printing method according to claim 6 , in which the anionic or zwitterionic photoinitiating system comprises the combination of a metallocene compound and a radical photoinitiator.
8 . A printing method according to claim 1 , in which the non-nucleophilic solvent is selected from the group consisting of non-basic solvents, non-ionic solvents (or solutions) and mixtures thereof.
9 . A printing method according to claim 1 , in which the non-nucleophilic rinsing solvent is selected from the group consisting of hydrocarbon and perfluorinated hydrocarbon solvents, ether solvents, acetate solvents, chlorohydrocarbon solvents, polar aprotic solvents, and mixtures thereof.
10 . A printing method according to claim 1 , in which the step of treating the three-dimensional article with a non-nucleophilic rinsing solvent is carried out during a period of 10 minutes or less.
11 . A printing method according to claim 1 , in which the step of treating the three-dimensional article with a non-nucleophilic rinsing solvent is carried out by dipping the three-dimensional article into the non-nucleophilic solvent for a period of 15 seconds or less.
12 . A printing method according to claim 1 , in which the step of exposing the three-dimensional article to an additional light source is carried out at a wavelength from 380 nm to 470 nm.
13 . A printing method according to claim 1 , in which the step of exposing the three-dimensional article to an additional light source is carried out for a period of 60 seconds or less.
14 . A method for recycling a three-dimensional article made of polycyanoacrylate, obtained exclusively from mono-functional cyanoacrylate monomers, comprising the step of treating the three-dimensional article with a dissolving solvent for a time sufficient for dissolving it.
15 . A recycling method according to claim 14 , in which the step of treating the three-dimensional article with a dissolving solvent is carried out during a period of 60 minutes or more.
16 . A printing method according to claim 1 , in which the cyanoacrylate-based monomers are multi-functional cyanoacrylate monomers, hybrid cyanoacrylate monomers or mixtures thereof and optionally mono-functional cyanoacrylate monomers.
17 . A printing method according to claim 1 , in which the cyanoacrylate-based monomers are selected from 2-methoxyethyl cyanoacrylate, methyl cyanoacrylate or mixtures thereof.
18 . A printing method according to claim 1 , in which the liquid resin comprises additional photopolymerizable monomers being (meth)acrylate monomers.
19 . A printing method according to claim 1 , in which the step of treating the three-dimensional article with a non-nucleophilic rinsing solvent is carried out during a period of 4 minutes or less.
20 . A printing method according to claim 1 , in which the step of exposing the three-dimensional article to an additional light source is carried out for a period from 1 to 30 seconds.