Stabilized matrix-filled liquid radiation curable resin compositions for additive fabrication

Patent metadata

Field	Value
Publication number	US-10526469-B2
Application number	US-201815917928-A
Country	US
Kind code	B2
Filing date	Mar 12, 2018
Priority date	Nov 5, 2013
Publication date	Jan 7, 2020
Grant date	Jan 7, 2020

Abstract

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 photoinitiator, 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.

First claim

What is claimed is:

1. A radiation curable composition for additive fabrication comprising:
(a) a cationically polymerizable aliphatic epoxide;
(b) a multifunctional (meth)acrylate component;
(c) a cationic photoinitiator;
(d) a free-radical photoinitiator; and
(e) a filled matrix comprising
a nanoparticle constituent comprising a plurality of inorganic nanoparticles, and
a microparticle constituent comprising a plurality of inorganic microparticles;

wherein the ratio by weight of the microparticle constituent to the nanoparticle constituent is from 1:1 to 12:1;
wherein the ratio of the average particle size of the microparticle constituent to the average particle size of the nanoparticle constituent is from 2.41:1 to less than 200:1;
and wherein the composition possesses a viscosity, when measured at 30 degrees Celsius at a shear rate of 50 s −1 , of between 200 centipoise and 2000 centipoise.

2. The radiation curable composition for additive fabrication of claim 1 , wherein
the nanoparticle constituent possesses an average particle size from 20 nanometers to 200 nanometers; and
the microparticle constituent possesses an average particle size from 2 microns to 8 microns.

3. The radiation curable composition for additive fabrication of claim 2 , wherein at least one of the microparticle constituent or the nanoparticle constituent comprises spherical particles selected from the group consisting of ceramics, glass, and metal.

4. The radiation curable composition for additive fabrication of claim 3 , wherein
the ratio by weight of the microparticle constituent to the nanoparticle constituent is from 4:1 to 8:1; and
the ratio of the average particle size of the microparticle constituent to the average particle size of the nanoparticle constituent is from 6.46:1 to 100:1.

5. The radiation curable composition for additive fabrication claim 4 , wherein the aliphatic epoxide component is a cycloaliphatic epoxy selected from the group consisting of: 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)-cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, vinylcyclohexene dioxide, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3′,4′-epoxy-6′-methylcyclohexanecarboxylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylates, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylates, β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexcylmethyl-3′,4′-epoxycyclohexane carboxylates, methylenebis(3,4-epoxycyclohexane), bicyclohexyl-3,3′-epoxide, bis(3,4-epoxycyclohexyl) with a linkage of —O—, —S—, —SO—, —SO 2 —, —C(CH 3 ) 2 —, —CBr 2 —, —C(CBr 3 ) 2 —, —C(CF 3 ) 2 —, —C(CCl 3 ) 2 —, or —CH(C 6 H 5 )—, dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis(3,4-epoxycyclohexanecarboxylate), and epoxyhexahydrodioctylphthalate.

6. The radiation curable composition for additive fabrication of claim 5 , wherein the ratio by volume of the microparticle constituent to the nanoparticle constituent is from about 1:1 to about 12:1.

7. The radiation curable composition for additive fabrication of claim 6 , wherein the ratio by number of the inorganic nanoparticles in the nanoparticle constituent to the inorganic microparticles in the microparticle constituent is from about 50:1 to about 1,000,000:1.

8. The radiation curable composition for additive fabrication of claim 7 , wherein the ratio by number of the inorganic nanoparticles in the nanoparticle constituent to the inorganic microparticles in the microparticle constituent is from about 5,000:1 to about 50,000:1.

9. The radiation curable composition for additive fabrication of claim 5 , wherein, relative to the total weight of the entire composition:
component (a) is present in an amount of from 10 wt % to 30 wt %;
component (b) is present in an amount of from 2 wt % to 10 wt %;
component (c) is present in an amount of from 1 wt % to 10 wt %;
component (d) is present in an amount of from 0.1 wt % to 5 wt %; and
component (e) is present in an amount of from 30 wt % to 80 wt %.

10. The radiation curable composition for additive fabrication of claim 9 , further comprising a multifunctional glycidyl ether that is devoid of cyclohexane groups.

11. The radiation curable composition for additive fabrication of claim 10 , wherein the multifunctional glycidyl ether that is devoid of cyclohexane groups is a neopentyl glycol diglycidyl ether.

12. The radiation curable composition for additive fabrication of claim 11 further comprising an oxetane, and 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.

13. The radiation curable composition of claim 11 further comprising an oxetane, wherein component (c) possesses an anion represented by SbF 6 − , PF 6 − , BF 4 − , (CF 3 CF 2 ) 3 PF 3 − , (C 6 F 5 ) 4 B − , ((CF 3 ) 2 C 6 H 3 ) 4 B − , (C 6 F 5 ) 4 Ga − , ((CF 3 ) 2 C 6 H 3 ) 4 Ga − , trifluoromethanesulfonate, nonafluorobutanesulfonate, methanesulfonate, butanesulfonate, benzenesulfonate, or p-toluenesulfonate, and a cation of the following formula (II):

wherein in formula (II), 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.

14. The radiation curable composition for additive fabrication of claim 11 , wherein the composition after full cure with actinic radiation and 60 min UV and thermal postcure, has the following properties:
(a) a heat distortion temperature at 1.82 MPa of between 80 degrees C. and 120 degrees C., and
(b) a flexural modulus of between 8,000 MPa and 12,000 MPa.

15. The radiation curable composition of claim 11 , further comprising a second aliphatic epoxide component, and wherein
the microparticle constituent consists of colloidal silica microparticles,
and the nanoparticle constituent consists of colloidal silica nanoparticles.

16. A process of forming a three-dimension

Assignees

• Dsm Ip Assets Bv

Inventors

• He Mingbo
• Rundlett Beth
• Ren Kangtai
• Liu Caroline
• Lee Taiyeon
• Seurer Brad
• Papachristopoulos Robin

Classifications

• B29C64/135

  the energy source being concentrated, e.g. scanning lasers or focused light sources · CPC title

• G03F7/0045

  with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors · CPC title

• G03F7/027

  Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence) · CPC title

• C08K2201/011

  Nanostructured additives · CPC title

• G03F7/0047

  characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing · CPC title