Radiation curable resin composition and rapid three dimensional imaging process using the same
The invention relates to a radiation curable resin composition comprising a cationically polymerizable component, a cationic photoinitiator, a hydroxy component, an impact modifier and wherein the resin composition after full cure has a modulus of >2 GPa; a yield stress <70 MPa; and a K 1c value >1.3 MPa·(m) 1/2 or an Izod value >0.45 J/cm. The resin composition can preferably be used in the preparation of three dimensional objects.
1. A process for making a three-dimensional article comprising the steps of:
(1) coating a first layer of a composition onto a surface;
(2) exposing said first layer imagewise to actinic radiation to form an imaged cross-section;
(3) coating an additional layer of the composition onto the previously exposed imaged cross-section;
(4) exposing said additional layer from step (3) imagewise to actinic radiation to form an additional imaged cross-section, wherein the additional imaged cross-section adheres to the previously exposed imaged cross-section;
(5) repeating steps (3) and (4) a sufficient number of times in order to build up the three-dimensional article, wherein the composition comprises:
a cationically polymerizable component comprising at least one epoxy group;
a cationic photoinitiator;
an impact modifier that is a miscible compound with a hydroxy functional group that demixes into rubbery domains upon curing;
a radically polymerizable compound; and
a free radical photoinitiator;
wherein a cationically polymerizable/hydroxy ratio of the composition is in a range of from 2 to 5 and a cationically polymerizable/radically polymerizable ratio is in a range of from 4.5 to 15, wherein the cationically polymerizable/hydroxy ratio is an amount of cationically polymerizable functional groups divided by an amount of hydroxy functional groups present in the composition and the cationically polymerizable/radically polymerizable ratio is the amount of cationically polymerizable functional groups divided by an amount of radically polymerizable groups present in the composition.
2. The process of claim 1 , wherein the impact modifier that is a miscible compound with a hydroxy functional group that demixes into rubbery domains upon curing possesses a number average molecular weight of greater than 1500 g/mol and contains at least one elastomeric block with a Tg below 0° Celsius.
3. The process of claim 2 , wherein the impact modifier that is a miscible compound with a hydroxy functional group that demixes into rubbery domains upon curing comprises a polypropylene glycol, a polytetramethylene glycol, a poly(oxyethylene-oxybutylene) random or block copolymer, a poly(-methyl-1,4-butanediol)(tetramethyleneglycol), a poly(-methyl-1,4-butanediol)(tetramethyleneglycol), a hydroxy-terminated polyester, a hydroxy-terminated polylactone, a hydroxy-functionalized polyalkadiene, an aliphatic polycarbonate polyol, or a hydroxy-terminated polyether.
4. The process of claim 1 , wherein the three-dimensional article possesses, at room temperature, a tensile modulus of at least 2 GPa.
5. The process of claim 1 , wherein the three-dimensional article possesses, at room temperature, a yield stress of less from about 34 MPa to about 70 Mpa.
6. The process of claim 1 , wherein the three-dimensional article possesses, at room temperature, a K 1c value of greater than 1.3 MPa·(m) 1/2 or an Izod value of greater than 0.45 J/cm.
7. The process of claim 6 , wherein the three-dimensional article possesses, at room temperature, a K 1c value of less than about 3.0 MPa·(m) 1/2 or an Izod value of less than about 0.7 J/cm.
8. The process of claim 1 , wherein the composition possesses a storage modulus E′ at 200° Celsius, as measured with dynamic mechanical analysis in tension with a frequency of 1 Hz of between 2 MPa and 35 MPa.
9. The process of claim 1 , wherein the composition comprises, relative to the weight of the entire composition,
from 5-90 wt. % of the cationically polymerizable component comprising at least one epoxy group;
from 0.1-10 wt. % of the cationic photoinitiator;
from 1-30 wt. % of the impact modifier that is a miscible compound with a hydroxy functional group that demixes into rubbery domains upon curing;
from 1-35 wt. % of the radically polymerizable compound; and
from 0.1-15 wt. % of the free radical photoinitiator.
10. The process of claim 1 , wherein the composition further comprises an additional hydroxy functional component.
11. The process of claim 10 , wherein the additional hydroxy functional component is an alkoxylated aromatic diol or an ethoxylated aromatic diol.
12. The process of claim 10 , wherein the additional hydroxy functional component is selected from the group consisting of polyoxyethylene and polyoxypropylene glycols of molecular weights from about 200 to about 10,000; polytetramethylene glycols; poly(oxyethylene-oxybutylene) random or block copolymers; hydroxy-terminated polyesters and hydroxy-terminated polylactones; hydroxy-functionalized polyalkadienes; aliphatic polycarbonate polyols; hydroxy-terminated polyethers; and alkoxylated aromatic diols represented by the chemical structure shown:
wherein R3=-CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CCI 2 —, —O—, —S—, and R4=-CH 2 CH 2 — or —CH 2 CH(CH 3 )—, and n and m are 1 through 10.
13. The process of claim 1 , wherein the cationically polymerizable component comprising at least one epoxy group comprises a cycloaliphatic diepoxide or an epoxy material based on a polynuclear phenol.
14. The process of claim 1 , wherein the cationically polymerizable component possesses an epoxy equivalent weight from 44 to 1000 g/mol, wherein the epoxy equivalent weight is a number average molecular weight divided by a number of reactive epoxy groups.
15. The process of claim 13 , wherein the composition further comprises an oxetane component, wherein the oxetane component further comprises one oxetane ring in the molecule.
16. The process of claim 15 , wherein the cationic photoinitiator comprises a diaryl iodonium salt or a triaryl sulfonium salt.
17. The process of claim 16 , wherein the radically polymerizable compound comprises bisphenol A diglycidylether diacrylate, bisphenol A diglycidylether mono-acrylate, dipentaerithritol hexacrylate, dipentaerithritol pentacrylate, trimethylolpropane triacrylate, neopentylglycol propoxylated diacrylate, or isobornyl acrylate.
18. The process of claim 17 , wherein the cationically polymerizable/hydroxy ratio of the composition is from 2.4 to 4.5, and the cationically polymerizable/radically polymerizable ratio is from 5 to 9.
19. The process of claim 18 , wherein the composition comprises, relative to the weight of the entire composition,
from 30-80 wt. % of the cationically polymerizable component comprising at least one epoxy group;
from 1-10 wt. % of the cationic photoinitiator;
from 5-25 wt. % of the hydroxyl functional component;
from 1-30 wt. % of the radically polymerizable compound; and
from 1-10 wt. % of the free radical photoinitiator.
20. The process of claim 19 , wherein a total content of aromatic and cycloaliphatic groups of the composition is between 0.3 and 0.45, wherein the total content of aromatic and cycloaliphatic groups of the composition is determined by summing a weight of each component in 100 g composition, multiplied by a weight fraction aromatic/cycloaliphatic of each component in the composition.