LIQUID RADIATION CURABLE RESINS FOR ADDITIVE FABRICATION COMPRISING A TRIARYL SULFONIUM BORATE CATIONIC PHOTOINITIATOR

• US 20120251841A1
• Filed: 12/16/2010
• Published: 10/04/2012
• Est. Priority Date: 12/17/2009
• Status: Abandoned Application

• Current Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Original Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Inventors: Xu, Jigeng, Ren, Kangtai, Dake, Ken, East, Sam, Southwell, John Edmund
• Application Number:
  US13/515,664
• Publication Number:
  US 20120251841A1
• Time in Patent Office: Days
• US Class Current: 428/704
• CPC Class Codes: B29C 2033/0005 with transparent parts, e.g. permitting visual inspection of the interior of the cavity
• CPC Class Codes: B29C 2035/0827 using UV radiation
• CPC Class Codes: B29C 64/135 the energy source being concentrated, e.g. scanning lasers or focused light sources
• CPC Class Codes: B29C 64/245 Platforms or substrates support structures intended to be sacrificed after manufacture B29C64/40
• CPC Class Codes: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: G03F 7/0045 with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• CPC Class Codes: G03F 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence
• CPC Class Codes: G03F 7/029 Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• CPC Class Codes: G03F 7/038 Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021
• CPC Class Codes: Y10T 428/31515 As intermediate layer

Abstract

Liquid radiation curable resins for additive fabrication comprising an R-substituted aromatic thioetber triaryl sulfonmm tetrakis(pentafluorophenyl)borate cationic photoinitiator is disclosed. A process for using the liquid radiation curable resins for additive fabrication and three-dimensional articles made from the liquid radiation curable resins for additive fabrication are also disclosed.

Claims

1. A liquid radiation curable resin for additive fabrication comprising an R-substituted aromatic thioether triaryl sulfonium tetrakis(pentafluorophenyl)borate cationic photoinitiator with a tetrakis(pentafluorophenyl)borate anion and a cation of the following formula (I):

2. The liquid radiation curable resin for additive fabrication of claim 1 wherein the R-substituted aromatic thioether triaryl sulfonium tetrakis(pentafluorophenyl)borate cationic photoinitiator is present in an amount from about 0.1 wt % to about 20 wt %, preferably from about 0.1 wt % to about 10 wt %, more preferably from about 0.1 wt % to about 7 wt %, more preferably from about 0.2 wt % to about 4 wt % of the liquid radiation curable resin for additive fabrication.

3. The liquid radiation curable resin for additive fabrication of claim 2 further comprising:

a. from 2 to 40 wt % of a radically polymerizable compound

b. from 10 to 80 wt % of a cationically polymerizable compound and

c. from 0.1 to 10 wt % of a radical photoinitiator.

4. The liquid radiation curable resin for additive fabrication of claim 1 wherein R is an acetyl group.

5. The liquid radiation curable resin for additive fabrication of claim 1 wherein Y1, Y2, and Y3 are the same.

6. The liquid radiation curable resin for additive fabrication of claim 1 wherein the R-substituted aromatic thioether triaryl sulfonium tetrakis(pentafluorophenyl)borate cationic photoinitiator is tris(4-(4-acetylphenyl)thiophenyl)sulfonium tetrakis(pentafluorophenyl)borate.

7. The liquid radiation curable resin for additive fabrication of claim 1 wherein the R-substituted aromatic thioether triaryl sulfonium tetrakis(pentafluorophenyl)borate cationic photoinitiator is present in an amount from 0.1 wt % to 2 wt %.

8. The liquid radiation curable resin for additive fabrication of claim 1 further comprising a cationic photoinitiator that is not an R-substituted aromatic thioether triaryl sulfonium tetrakis(pentafluorophenyl)borate cationic photoinitiator.

9. The liquid radiation curable resin for additive fabrication of claim 1 further comprising a photosensitizer.

10. The liquid radiation curable resin for additive fabrication of claim 1 further comprising an inorganic filler, preferably present in an amount from about 5 wt % to about 90 wt %, more preferably from about 10 wt % to about 75 wt %, more preferably from about 30 wt % to about 75 wt %.

11. The liquid radiation curable resin for additive fabrication of claim 10 wherein the inorganic filler is silica nanoparticles comprising at least 80 wt % silica, preferably 90 wt % silica, more preferably 95 wt % silica.

12. The liquid radiation curable resin for additive fabrication of claim 1 further comprising from about 0.1 to about 1 wt % of a stabilizer.

13. The liquid radiation curable resin of claim 12 wherein the stabilizer is a liquid Na₂CO₃ solution.

15. A process of forming a three-dimensional object comprising the steps of forming and selectively curing a layer of the liquid radiation curable resin composition for additive fabrication of claim 1 with actinic radiation and repeating the steps of forming and selectively curing a layer of the liquid radiation curable resin composition for additive fabrication of claim 1 a plurality of times to obtain a three-dimensional object.

16. The process of claim 15 wherein the source of actinic radiation is one or more LEDs.

17. The process of claim 16 wherein the one or more LEDS emit light at a wavelength of 200 nm-460 nm, preferably from 300 nm-400 nm, more preferably from 340 nm to 370 nm, mire preferably having a peak at 365 nm.

18. A three-dimensional object formed from the liquid radiation curable resin of claim 1.

14. A liquid radiation curable resin for additive fabrication comprising 5 wt % to about 90 wt %, preferably from 10 wt % to 75 wt %, more preferably from 30 to 75 wt % of inorganic filler, said inorganic filler preferably comprising greater than 80 wt %, preferably greater than 90 wt %, more preferably greater than 95 wt % of silica, that has a Dp of from about 4.5 mils to about 7.0 mils wherein the liquid radiation curable resin for additive fabrication, when placed on a shaker table set at 240 rpm and exposed to two 15 watt plant and aquarium lamps hung 8 inches above the surface of the liquid radiation curable resin for additive fabrication, has a gel time of greater than 200 hours, preferably greater than 250 hours.

19. The use of an R-substituted aromatic thioether triaryl sulfonium tetrakis(pentafluorophenyl)borate cationic photoinitiator with a tetrakis(pentafluorophenyl)borate anion and a cation of the following formula (I):