Resin suitable for three-dimensional printing
A polymeric resin that includes a photocured reaction product of at least one urethane (meth)acrylate polymer that includes at least one polycarbonate unit; at least one monofunctional monomer; and at least one crosslinking agent.
1 . A method comprising:
mixing together at least one urethane (meth)acrylate polymer that includes at least one polycarbonate unit; at least one monofunctional monomer; at least one crosslinking agent; and at least one photoinitiator, wherein the resulting mixture has a viscosity of 200 cP at 25° C. to 3000 cP at 25° C.; and
introducing the resulting mixture into a three-dimensional printer, and
printing the mixture while irradiating the mixture.
2 . The method of claim 1 , comprising irradiating the mixture at a wavelength of 365 to 405 nm.
3 . The method of claim 1 , wherein the urethane (meth)acrylate polymer has a polymer backbone, wherein the polymer backbone includes the at least one polycarbonate unit.
4 . The method of claim 1 , wherein the urethane (meth)acrylate polymer includes at least one of a co-polymeric polycarbonate unit and a co-reacted urethane acrylate unit.
5 . The method of claim 1 , wherein the urethane (meth)acrylate polymer has the formula (III):
(Acr) y (A)(Q)(PC)[(Q)(PC)] x (Q)(A)(Acr) y
wherein
(Acr) y (A) is the residue of hydroxyalkyl acrylate or hydroxyalkyl methacrylate having an alkyl moiety, A, and where said alkyl, A, has 2 to 5 carbon atoms and wherein Acr is an acrylate or methacrylate moiety; y is the number of acrylate or methacrylate groups linked to moiety A;
Q is the residue of one or more organic diisocyanates, which are connected with A via a urethane linkage;
PC is the residue of an alkylene diol polycarbonate of the formula (IV):
HO(ROCOO) n ROH
wherein
R is one or more (C 2 to C 10 ) alkylene or one or more (C 6 to C 12 ) aromatic group;
y is an integer from 1 to 5;
x is from 1 to 20;
n is an integer from 1 to 10,000; and
PC and Q are connected via a urethane group.
6 . The method of claim 1 , wherein the monofunctional monomer has a glass transition temperature (T g ) of greater than 50° C.
7 . The method of claim 1 , wherein the monofunctional monomer has a viscosity of less than 100 cP at 25° C.
8 . The method of claim 1 , wherein the monofunctional monomer is hydrophobic.
9 . The method of claim 1 , wherein the monofunctional monomer has a single (meth)acrylate group.
10 . The method of claim 1 , wherein the monofunctional monomer is isobornyl acrylate (IBOA), isobornyl methacrylate (IBOMA), dihydrodicyclopentadienyl acrylate (DCPA), tert-butyl methacrylate (TBMA), cyclohexyl methacrylate (CHMA), benzyl methacrylate (BzMA), or a mixture thereof.
11 . The method of claim 1 , wherein the crosslinking agent is a difunctional or multifunctional monomer.
12 . The method of claim 1 , wherein the crosslinking agent has a viscosity of less than 1000 cP at 25° C.
13 . The method of claim 1 , wherein the crosslinking agent is hydrophobic.
14 . The method of claim 1 , wherein the crosslinking agent is trimethylolpropane trimethacrylate (TMPTMA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxy triacrylate (TMPEOTA), pentaerythritol triacrylate (PETA), tripropyleneglycol diacrylate (TPGDA), hexanediol diacrylate (HDDA), or a mixture thereof.
15 . The method of claim 1 , further comprising a UV blocker.
16 . The method of claim 1 , wherein a body formed from the mixture after printing and irradiating has a degree of polymerization conversion of at least 90%, as measured by ATR-FTIR.
17 . The method of claim 1 , wherein a body formed from the mixture after printing and irradiating has a tensile strength of 20 to 50 MPa, as measured via ASTM D638-14.
18 . The method of claim 1 , wherein a body formed from the mixture after printing and irradiating has an elongation to break of 50 to 200%, as measured via ASTM D638-14.
19 . The method of claim 1 , wherein a body formed from the mixture after printing and irradiating has a flexural strength of 20 to 70 MPa as measured via ASTM D790-17.
20 . The method of claim 1 , wherein a body formed from the mixture after printing and irradiating has a flexural modulus of 1000 to 2000 MPa, as measured via ASTM D790-17.
21 . The method of claim 1 , wherein a body formed from the mixture after printing and irradiating has an impact strength of 15 to 75 J/m, as measured via ASTM D256-10 (Notched Izod).