Stabilized matrix-filled liquid radiation curable resin compositions for additive fabrication
Matrix-filled liquid radiation curable resin compositions for additive fabrication are described and claimed. Such resins include a cationically polymerizable component that is an aliphatic epoxide, a multifunctional (meth)acrylate component, a cationic photoinitiator, a free-radical photo initiator, and a matrix of inorganic fillers, wherein the matrix further constitutes prescribed ratios of at least one microparticle constituent and at least one nanoparticle constituent. Also described and claimed is a process for using the matrix-filled liquid radiation curable resins for additive fabrication to create three dimensional parts, and the three-dimensional parts made from the liquid radiation curable resins for additive fabrication.
1. A liquid radiation curable composition for additive fabrication comprising:
(a) a cationically polymerizable component;
(b) a (meth)acrylate component;
(c) a cationic photoinitiator;
(d) a free-radical photoinitiator;
(e) a filled matrix, further comprising
a filled particle dispersion containing
a nanoparticle constituent made up of a plurality of silica nanoparticles having an average particle size of at least about 50 nanometers, and a solvent, and
a microparticle constituent made up of a plurality of inorganic microparticles;
wherein the ratio by weight of the microparticle constituent to the nanoparticle constituent is from about 1:1 to about 12:1,
wherein the nanoparticle constituent has a particle dispersion pH from 7.0 to 8.0.
2. The liquid radiation curable composition for additive fabrication of claim 1 , wherein
said plurality of silica nanoparticles have an average particle size of from about 50 nanometers to about 100 nanometers;
said plurality of inorganic microparticles have an average particle size of from about 0.2 microns to 20 microns; and
wherein the particle dispersion pH of the nanoparticle constituent is from 7.0 to 7.5.
3. The liquid radiation curable composition for additive fabrication of claim 2 , wherein the filled matrix is present in an amount by weight, relative to the entire composition, of from about 50 wt % to about 70 wt %.
4. The liquid radiation curable composition for additive fabrication of claim 3 , wherein
the ratio of the average particle size of the inorganic microparticles in the microparticle constituent to the average particle size of the silica nanoparticles in the nanoparticle constituent is from about 6.46:1 to about 100:1; and
the ratio by weight of the microparticle constituent to the nanoparticle constituent is from about 4:1 to about 8:1.
5. The liquid radiation curable composition for additive fabrication of claim 4 , wherein the solvent is selected from one or more of the group consisting of methyl ethyl ketone, isopropanol, an epoxide, an oxetane, and an acrylate.
6. The liquid radiation curable composition for additive fabrication of claim 5 , wherein the solvent is a 3,4-epoxycyclohexylmethyl 3′,4′-epoxycyclohexanecarboxylate.
7. The liquid radiation curable composition for additive fabrication of claim 6 , wherein component (c) is an R-substituted aromatic thioether triaryl sulfonium or iodonium tetrakis(pentafluorophenyl) borate cationic photoinitiator with a tetrakis(pentafluorophenyl)borate anion and a cation of the following formula (I):
wherein Y1, Y2, and Y3 are the same or different and wherein Y1, Y2, or Y3 are R-substituted aromatic thioether with R being an acetyl or halogen group.
8. The liquid radiation curable composition for additive fabrication of claim 6 , wherein component (c) is a fluoroalkyl-substituted fluorophosphate with a cation of the following general formula (II):
wherein R 1 , R 2 , R 3 , R 5 and R 6 each independently represent an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, R 4 represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylthio group, a heterocyclic hydrocarbon group, an alkylsulfinyl group, an alkylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, m 1 to m 6 each represent the number of occurrences of each of R 1 to R 6 , m 1 , m 4 , and m 6 each represent an integer of 0 to 5, and m 2 , m 3 , and m 5 each represent an integer of 0 to 4.
9. The liquid radiation curable composition for additive fabrication of claim 1 , wherein said plurality of silica nanoparticles have an average particle size of from about 50 nanometers to about 100 nanometers, wherein said plurality of inorganic microparticles have an average particle size of from about 0.2 microns to 20 microns.
10. The liquid radiation curable composition for additive fabrication of claim 9 , wherein
the ratio of the average particle size of the inorganic microparticles in the microparticle constituent to the average particle size of the silica nanoparticles in the nanoparticle constituent is from about 6.46:1 to about 100:1; the ratio by weight of the microparticle constituent to the nanoparticle constituent is from about 4:1 to about 8:1, and the filled matrix is present in an amount by weight, relative to the entire composition, of from about 50 wt % to about 70 wt %.
11. The liquid radiation curable composition for additive fabrication of claim 10 , wherein the solvent is selected from one or more of the group consisting of methyl ethyl ketone, isopropanol, an epoxide, an oxetane, and an acrylate.
12. The liquid radiation curable composition for additive fabrication of claim 11 , wherein the solvent is a 3,4-epoxycyclohexylmethyl 3′,4′-epoxycyclohexanecarboxylate.
13. The liquid radiation curable composition for additive fabrication of claim 1 , wherein the filled matrix further comprises a settling additive.
14. The liquid radiation curable composition for additive fabrication of claim 13 , wherein the settling additive is a fumed silica.
15. The liquid radiation curable composition for additive fabrication of claim 13 , wherein the fumed silica settling additive is hydrophilic.
16. The liquid radiation curable composition for additive fabrication of claim 1 , wherein the filled matrix further comprises at least one alternative inorganic filler substance.
17. The liquid radiation curable composition for additive fabrication of claim 16 , wherein the alternative inorganic filler substance comprises glass powder, alumina, alumina hydrate, magnesium oxide, magnesium hydroxide, barium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, silicate mineral, diatomaceous earth, silica sand, silica powder, oxidation titanium, aluminum powder, bronze, zinc powder, copper powder, lead powder, gold powder, silver dust, glass fiber, titanic acid potassium whiskers, carbon whiskers, sapphire whiskers, boron carbide whiskers, silicon carbide whiskers, or silicon nitride whiskers.
18. The liquid radiation curable composition for additive fabrication of claim 16 , wherein the alternative inorganic filler substance comprises alumina, alumina hydrate, or aluminum powder.