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

Patent metadata

Field	Value
Publication number	US-9228073-B2
Application number	US-201414533238-A
Country	US
Kind code	B2
Filing date	Nov 5, 2014
Priority date	Nov 5, 2013
Publication date	Jan 5, 2016
Grant date	Jan 5, 2016

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 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.

First claim

What is claimed is:

1. A liquid 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 about 1:1 to about 12:1; and
wherein the ratio of the average particle size of the inorganic microparticles in the microparticle constituent to the average particle size of the inorganic nanoparticles in the nanoparticle constituent is from about 2.41:1 to about 200:1 less than 200:1.

2. The liquid radiation curable composition for additive fabrication of claim 1 , wherein
the inorganic nanoparticles of the nanoparticle constituent have an average particle size of from about 50 nanometers to about 100 nanometers; and
the inorganic microparticles of the microparticle constituent have an average particle size of from about 2 microns to about 8 microns.

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

5. The liquid 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 liquid 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 liquid 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 liquid 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 liquid radiation curable composition for additive fabrication of claim 7 , wherein, relative to the total weight of the entire composition:
component (a) is present in an amount of from about 10 wt % to about 30 wt %;
component (b) is present in an amount of from about 2 wt % to about 10 wt %;
component (c) is present in an amount of from about 1 wt % to about 10 wt %;
component (d) is present in an amount of from about 0.1 wt % to about 5 wt %; and
component (e) is present in an amount of from about 30 wt % to about 80 wt %.

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

11. The liquid 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 liquid 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 liquid 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 liquid radiation curable composition for additive fabrication of claim 11 , wherein the composition has a viscosity of between about 600 cPs and about 1200 cPs, and 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 about 80 degrees C. and about 120 degrees C., and
(b) a flexural modulus of between about 8,000 MPa and about 12,000 MPa.

Assignees

• Dsmip Assets B V
• Dsm Ip Assets Bv

Inventors

• He Mingbo
• Rundlett Beth
• Ren Kangtai
• Liu Caroline
• Lee Tai Yeon

Classifications

• B29K2105/246

  Uncured, e.g. green · CPC title

• C08F2/50

  with sensitising agents · CPC title

• G03F7/0037

  Production of three-dimensional images · CPC title

• C08K2201/011

  Nanostructured additives · CPC title

• B29K2063/00

  Use of {EP, i.e.} epoxy resins {or derivatives thereof}, as moulding material · CPC title