Radiation curable resin composition and rapid three dimensional imaging process using the same

Patent metadata

Field	Value
Publication number	US-9676899-B2
Application number	US-66710807-A
Country	US
Kind code	B2
Filing date	Apr 26, 2007
Priority date	May 1, 2006
Publication date	Jun 13, 2017
Grant date	Jun 13, 2017

Abstract

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.

First claim

The invention claimed is:

1. A radiation curable resin composition for the production of three-dimensional shaped articles by means of layerwise imaging methods comprising
a) a cationically polymerizable component comprising at least one epoxy group,
b) a cationic photoinitiator,
c) a hydroxy functional component,
d) an impact modifier that is a miscible compound that demixes into rubbery domains upon curing,
e) a radically polymerizable compound, and
f) a free radical photoinitiator,
wherein the impact modifier that is a miscible compound that demixes into rubbery domains upon curing possesses a molecular weight of greater than 1500 g/mol and contains at least one elastomeric block with a Tg below 0° C.,
wherein the resin composition after full cure has a tensile 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, and
wherein the cationically polymerizable/hydroxy ratio of the composition is in the range of from 2 to 5 and the cationically polymerizable/radically polymerizable ratio is in the range of from 4.5 to 15, wherein the cationically polymerizable/hydroxy ratio is the amount of cationically polymerizable functional groups divided by the 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 the amount of radically polymerizable groups present in the composition.

2. The composition according to claim 1 , wherein the hydroxy component contains at least one primary hydroxyl group.

3. The composition according to claim 1 , wherein the hydroxy component contains at least two primary hydroxyl groups.

4. The composition according to claim 1 , wherein the hydroxyl component is an alkoxylated aromatic diol or ethoxylated aromatic diol.

5. The composition according to claim 1 , wherein the hydroxy component is selected from the group consisting of polyoxyethylene and polyoxypropylene glycols of molecular weights from about 200 to about 10,000; polytetramethylene glycols of varying molecular weight; poly(oxyethylene-oxybutylene) random or block copolymers; hydroxy-terminated polyesters and hydroxy-terminated polylactones; hydroxy-functionalized polyalkadienes, such as polybutadiene; aliphatic polycarbonate polyols, such as an aliphatic polycarbonate diol; 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.

6. The composition according to claim 1 , wherein the hydroxyl component is an ethoxylated bisphenol A.

7. The composition according to claim 1 , wherein the composition comprises 1-30 wt % of the impact modifier that is a miscible compound that demixes into rubbery domains upon curing.

8. The composition according to claim 7 , wherein upon curing the rubbery domains of the impact modifier possess an average size of between 10 nm and 10 microns.

9. The composition according to claim 8 , wherein the impact modifier that is a miscible compound that demixes into rubbery domains upon curing is an epoxy- or carboxyterminated butadiene-nitrile rubber.

10. The composition according to claim 9 , wherein the impact modifier that is a miscible compound that demixes into rubbery domains upon curing that is an epoxy- or carboxyterminated butadiene-nitrile rubber is also hydroxy-functional.

11. The composition according to claim 9 , wherein the impact modifier that is a miscible compound that demixes into rubbery domains upon curing that is an epoxy- or carboxyterminated butadiene-nitrile rubber is not hydroxy-functional.

12. The composition according to claim 1 , wherein the composition contains 1-30 wt % of radically polymerizable compound and 0.1-15 wt % of free radical photoinitiator.

13. The composition according to claim 12 , wherein the radically polymerizable compound comprises a polyfunctional acrylate.

14. A radiation curable composition comprising
a) 5-90 wt % of an epoxy functional component,
b) 0.1-10 wt % of a cationic photoinitiator,
c) 1-35 wt % of a polyol,
d) 1-30 wt % of core shell particles that have reactive groups incorporated into the shell by copolymerization,
e) 1-35 wt % of a compound having at least one (meth)acrylate group,
f) 0.1-15 wt % of a radical photoinitiator,
g) 0-25 wt % of a compound having at least one radically curable group and one cationically curable group,
wherein the epoxy/hydroxy ratio of the composition is in the range from 2-5, the epoxy/(meth)acrylate ratio is in the range from 4.5-15 and the aromatic/cycloaliphatic content is between 0.2 and 0.6,
wherein the epoxy/hydroxy ratio is the amount of epoxy groups divided by the amount of hydroxy functional groups present in the composition and the epoxy/(meth)acrylate ratio is the amount of epoxy groups divided by the amount of (meth)acrylate groups present in the composition.

15. The radiation curable composition according to claim 14 , wherein component (c) is selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, triethyleneglycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyoxyethylene and polyoxypropylene glycols of molecular weights from about 200 to about 1500 g/mol, 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.

16. The composition according to claim 1 , wherein the composition comprises 1-15 wt % of a component having at least one epoxy group and at least one (meth)acrylate group.

17. The composition according to claim 1 , wherein the composition comprises a aromatic/cycloaliphatic content between 0.2 and 0.6.

18. The composition according to claim 1 , wherein the composition has a storage modulus from DMS at 200° C. and 1 Hz between 2 and 35 MPa.

19. The composition according to claim 1 , wherein the composition contains a filler.

20. A process for making three dimensional articles comprising the steps of
(1) coating a thin layer of a composition onto a surface;
(2) exposing said thin layer imagewise to actinic radiation to form an imaged cross-section, wherein the radiation is of sufficient intensity and time to cause substantial curing of the thin layer in the exposed areas;
(3) coating a thin layer of the composition onto the previously exposed imaged cross-section;
(4) exposing said thin layer from step (3) imagewise to actinic radiation to form an additional imaged cross-section, wherein the radiation is of sufficient intensity and time to cause substantial curing of the thin layer in the exposed areas and to cause adhesion 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 is defined according to claim 1 .

Assignees

• Steeman Paulus Antonius Maria
• Keestra Beert Jacobus
• Driessen Marco Marcus Matheus
• Repko Debra Lynn Fish
• Zussman Melvin
• Dsm Ip Assets Bv

Inventors

• Steeman Paulus Antonius Maria
• Keestra Beert Jacobus
• Driessen Marco Marcus Matheus
• Repko Debra Lynn Fish
• Zussman Melvin

Classifications

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• G03F7/0037

  Production of three-dimensional images · CPC title

• G03F7/038

  Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021) · CPC title

• C08G59/68 Primary

  characterised by the catalysts used · CPC title

• Y10T428/24479

  including variation in thickness · CPC title