US 12,390,987 B2
Hybrid resin composition for the 3D-printing of objects
Christian Frank, Vienna (AT); and Christian Gorsche, Vienna (AT)
Assigned to CUBICURE GMBH, Vienna (AT)
Appl. No. 18/279,083
Filed by CUBICURE GMBH, Vienna (AT)
PCT Filed Feb. 24, 2022, PCT No. PCT/IB2022/051638
§ 371(c)(1), (2) Date Aug. 28, 2023,
PCT Pub. No. WO2022/180566, PCT Pub. Date Sep. 1, 2022.
Claims priority of application No. 21020110 (EP), filed on Feb. 26, 2021.
Prior Publication US 2024/0198582 A1, Jun. 20, 2024
Int. Cl. B33Y 70/00 (2020.01); B29C 64/124 (2017.01); B29C 64/129 (2017.01); B29C 64/264 (2017.01); B29C 64/295 (2017.01); B33Y 10/00 (2015.01); B33Y 80/00 (2015.01); C08F 2/50 (2006.01); C08F 222/10 (2006.01); B29K 233/04 (2006.01); B33Y 30/00 (2015.01)
CPC B29C 64/129 (2017.08) [B29C 64/124 (2017.08); B29C 64/264 (2017.08); B29C 64/295 (2017.08); B33Y 10/00 (2014.12); B33Y 70/00 (2014.12); B33Y 80/00 (2014.12); C08F 2/50 (2013.01); C08F 222/1065 (2020.02); B29K 2233/04 (2013.01)] 29 Claims
OG exemplary drawing
 
1. A hybrid resin composition for the 3D-printing of objects, the hybrid resin composition comprising components A, B and C for forming cured material constituting an interpenetrating polymer network, a semi-interpenetrating polymer network, a sequential interpenetrating polymer network, or a polymer blend, wherein,
a) component A is at least one monofunctional, light-curable component having the formula (I) comprising a reactive species Y that is susceptible of radical polymerization and a side group X, said component A upon light-induced curing forming a polymer backbone of the cured material,
X—Y  Formula (I)
b) component B is at least one mono- or multifunctional, light-curable component, which copolymerizes with component A and has a molecular weight of >500 g mol−1, said component B upon the light-induced curing forming a first polymerized network of the cured material with an elongation at break >10% and a Tg>0° C., and
c) component C comprises a multifunctional, heat-curable component forming a second polymerized network of the cured material serving as a Tg-enhancer with a Tg>100° C.,
wherein the amount of the light-curable component A ranges from 5 wt % to 80 wt %, the amount of the light-curable component B ranges from 10 wt % to 90 wt %, and the amount of the heat-curable component C ranges from 1 wt % to 50 wt %, based on the total weight of components A, B, and C; and
wherein the component C comprises one or more compound(s) selected from the group consisting of allyl, vinyl, maleimide, citraconimide, benzoxazine, epoxy, phenol, cyanate ester, phthalonitrile, and oligomers or polymers thereof and/or isomers thereof, comprising one or more chemical species chosen from the group consisting of monomers and/or oligomers and/or prepolymers of maleimide and citraconimide derivatives according to formula (II),

OG Complex Work Unit Chemistry
as well as isomers thereof, wherein
n is an integer between 1 and 10,
R1 represents H, CH3 or CH2,
R2 independently represents a linear, branched, or cy-clic C5-C40 aliphatic or aromatic residue of one or more of the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, octyl, decanyl, dodecanyl, acetic, propanoic, butanoic, pentanoic, undecanoic, dodecanoic, benzoic acid and corresponding esters, alkyl or aromatic esters, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-isobutylcyclohexyl, cycloheptyl, cyclooctyl, adamantyl, isobornyl, salicyl, cholesteryl, phenyl, benzyl, phenethyl, propenyl, biphenyl, naphthyl, anthracenyl, pyrenyl, bis(methylene) oxy, bis(ethylene) oxy, bis (phenyl) methane, bis (phenyl) ethane, bis (phenyl) propane, bis (phenyl) butane, bis (phenyl) ether, bis (phenyl) thioether, bis (phenyl) amino and bis (phenyl) sulfone, where one or more of these groups are optionally, individually linked via an ester, amide, urea, urethane, carbonate, ether, thioether group, which are optionally substituted with one or more C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioether, halogen, —NO2, —SO3H, —CF3, —OH, —NH2, —SH, —CN, -trimethoxysilyl, -triethoxysilyl or a polymerisable group from the substance classes of maleimide and citraconimide compounds and/or isomers thereof.