IP Library Granted Patent US 11,787,878
Granted Patent B2
US 11,787,878 · App. 17/831,554 · Granted Oct 17, 2023

Photocurable compositions for stereolithography, method of forming the compositions, stereolithography methods using the compositions, polymer components formed by the stereolithography methods, and a device including the polymer components

Inventors: Trevor Polidore (Scottsdale, AZ); Dirk Baars (Phoenix, AZ); Thomas A. Koes (Riverside, CA); Bruce Fitts (Phoenix, AZ); Murali Sethumadhavan (Acton, MA)
Assignee: ROGERS CORPORATION
C08F2/50B29C64/106C08F20/18C08F22/1006C08F22/20C08F22/22C08F136/06C08K3/22B29K2033/08B29K2035/00B29K2995/0006B33Y10/00B33Y70/00B33Y80/00C08K2003/2227C08K2003/2237
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Quick Facts
Patent No.
US 11,787,878
App. No.
17/831,554
Granted
Oct 17, 2023
Kind
B2
Abstract

A photocurable composition for stereolithographic three-dimensional printing, wherein the photocurable composition comprises a photoreactive oligomer component comprising a hydrophobic oligomer comprising a photoreactive end group, a photoreactive monomer component comprising a photoreactive monomer having a photoreactive end group, and a photoinitiation composition comprising a photoinitiator; the photocurable composition has a viscosity of 250 to 10,000 centipoise at 22° C., determined using a Brookfield viscometer; and the photocured composition has a dielectric loss of less than 0.010, preferably less than 0.008, more preferably less than 0.006, most preferably less than 0.004, each determined by split-post dielectric resonator testing at 10 gigahertz at 23° C.

Claims (34)

1. A photocurable composition for stereolithographic three-dimensional printing, wherein

the photocurable composition comprises

a photoreactive oligomer component comprising a hydrophobic oligomer comprising a photoreactive end group,

a photoreactive monomer component comprising a photoreactive monomer having a photoreactive end group, wherein the photoreactive monomer comprises an alkenyl functional group, an alkynyl functional group, or a combination thereof, and

a photoinitiation composition comprising a photoinitiator;

the photocured composition has a dielectric loss of less than 0.010, determined by split-post dielectric resonator testing at 10 gigahertz at 23° C.; and

wherein the photocurable composition excludes a photoreactive monomer having a hydroxyl group.

2. The photocurable composition of claim 1 , wherein the photocured composition has a dielectric loss of less than 0.008, determined by split-post dielectric resonator testing at 10 gigahertz at 23° C.

3. The photocurable composition of claim 1 , wherein the photocured composition has a dielectric loss of less than 0.004, determined by split-post dielectric resonator testing at 10 gigahertz at 23° C.

4. The photocurable composition of claim 1 , wherein the photoreactive monomer comprises the alkenyl functional group.

5. The photocurable composition of claim 4 , wherein the photoreactive monomer comprises an allyl, vinyl, or allylether functional group, or a combination thereof.

6. The photocurable composition of claim 1 , wherein the photoreactive monomer is triallyl isocyanurate, pentaerythritol tetraallyl ether, diallyl ether, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, styrene, alpha-methyl styrene, divinylbenzene, divinyltoluene, diallyl phthalate, divinyl xylene, trivinyl benzene, divinyl ether, dipropargyl, phenyl propargyl ether, benzyl propargyl ether, propargyl benzoate, propargyl ether, tripropargyl cyanurate, vinyl acetylene, allyl vinyl acetylene, allyl vinyl ether, or a combination thereof.

7. The photocurable composition of claim 1 , wherein the photoreactive monomer comprises an alkynyl functional group.

8. The photocurable composition of claim 1 , comprising

35 to 85 weight percent of the photoreactive oligomer component,

15 to 65 weight percent of the photoreactive monomer component, and

0.01 to 15 weight percent of the photoinitiation composition,

wherein each weight percent is based on the total weight of the photoreactive oligomer component, the photoreactive monomer component, and the photoinitiation composition, and totals 100 weight percent.

9. The photocurable composition of claim 1 , wherein the hydrophobic oligomer of the photoreactive oligomer component comprises a (meth)acrylate-derivatized polyester.

10. The photocurable composition of claim 1 , wherein the hydrophobic oligomer of the photoreactive oligomer component comprises a (meth)acrylate urethane-derivatized polybutadiene oligomer.

11. The photocurable composition of claim 10 , wherein the (meth)acrylate urethane-derivatized polybutadiene oligomer comprises a (meth)acrylate urethane-derivatized hydrogenated polybutadiene oligomer.

12. The photocurable composition of claim 1 , wherein the hydrophobic oligomer of the photoreactive oligomer component comprises a urethane (meth)acrylate-derivatized polybutadiene oligomer having a number average molecular weight of 500 to 5,000 grams per mole.

13. The photocurable composition of claim 12 , wherein the urethane (meth)acrylate-derivatized polybutadiene oligomer having the number average molecular weight of 500 to 5,000 grams per mole comprises a urethane (meth)acrylate-derivatized hydrogenated polybutadiene oligomer having the number average molecular weight of 500 to 5,000 grams per mole.

14. The photocurable composition of claim 1 , further comprising a particulate filler, wherein the particulate filler comprises alumina.

15. The photocurable composition of claim 1 , further comprising a particulate filler, wherein the particulate filler comprises calcium titanate.

16. The photocurable composition of claim 1 , further comprising a particulate filler, wherein the particulate filler comprises strontium titanate.

17. The photocurable composition of claim 1 , further comprising a particulate filler, wherein the particulate filler comprises barium titanate.

18. The photocurable composition of claim 1 , further comprising a particulate filler, wherein the particulate filler comprises barium nonatitanate.

19. The photocurable composition of claim 1 , further comprising a particulate filler, wherein the particulate filler comprises boron nitride.

20. The photocurable composition of claim 1 , further comprising a particulate filler, wherein the particulate filler comprises aluminum nitride.

21. The photocurable composition of claim 1 , further comprising a particulate filler, wherein the particulate filler has a dielectric constant of 5 or greater.

22. The photocurable composition of claim 1 , having a relative permittivity of 2 to 12 at 10 gigahertz.

23. The photocurable composition of claim 1 , having a viscosity of 250 to 10,000 centipoise at 22° C., determined using a Brookfield viscometer.

24. A three-dimensional structure comprising a photocured product of the composition of claim 1 , wherein the structure is porous.

Assignments (2)
SECURITY INTEREST Recorded Mar 24, 2023
From: ROGERS CORPORATION
To: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 063094/0195 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 3, 2022
From: POLIDORE, TREVOR; BAARS, DIRK; KOES, THOMAS A.; FITTS, BRUCE; SETHUMADHAVAN, MURALI
To: ROGERS CORPORATION
Reel/Frame 060096/0674 →
Continuity (3)
Continuation 16887320 · May 29, 2020
Provisional Application 62854387 · May 30, 2019
Related Publication 20220298270A1 · Sep 22, 2022
Cited By (1)
US 12,206,174