Solid imaging method using compositions containing core-shell polymers

• US 5,002,854 A
• Filed: 04/21/1989
• Issued: 03/26/1991
• Est. Priority Date: 04/21/1989
• Status: Expired due to Term

• Current Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Fryd, Michael, Fan, Roxy N.
• Primary Examiner(s): BRAMMER, JACK
• Application Number:
  US07/341,347
• Time in Patent Office: 704 Days
• Field of Search: 430/269, 430/270, 430/945, 425/162, 425/174, 425/174.4, 522/2, 264/22
• US Class Current: 430/270.1
• CPC Class Codes: B29C 64/135 the energy source being concentrated, e.g. scanning lasers or focused light sources
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: Y10S 430/148 Light sensitive titanium compound containing
• CPC Class Codes: Y10S 430/15 Lithographic emulsion

Abstract

A three-dimensional object formed from a photohardenable composition containing deflecting matter of core-shell polymers. A preferred material for the polymeric core is crosslinked to an extent to be nonswellable and insoluble in solvent for noncrosslinked polymer material while the shell polymer has no pendant acid groups.

Claims

1. A method for accurately fabricating an integral three-dimensional object from successive layers of a photohardenable liquid composition comprising the steps of:

(a) forming a layer of a photohardenable liquid;

(b) photohardening at least a portion of the layer of photohardenable liquid by exposure to actinic radiation;

(c) introducing a new layer of photohardenable liquid onto the layer previously exposed to actinic radiation; and

(d) photohardening at least a portion of the new liquid layer by exposure to actinic radiation, with the requirement that the photohardenable composition contains deflecting matter which comprises an ethylenically unsaturated monomer, a photoinitiator, and radiation deflecting matter comprising a polymer having a core formed from monomers comprising

(i) a monofunctional ethylenically unsaturated monomer, constituting 5%-97% of the total core by weight;

(ii) a multifunctional ethylenically unsaturated monomer or oligomer constituting 2%-70% of the total core by weight; and

(iii) an ethylenically unsaturated monomer with a grafting site constituting 1%-25% of the total core by weight,

wherein the deflecting matter has a first index of refraction, and the rest of the composition having a second index of refraction, the absolute value of the difference between the first index of refraction and the second index of refraction difference by at least 0.01.

2. The method of claim 1 wherein (ii) is present in a range from 4% to 70% and (iii) is present in a range from 5% to 25%.

3. The method of claim 2 wherein (ii) is present in a range from 4% to 6% and (iii) is present in a range from 15 to 25%.

4. The method of claim 2 wherein the deflecting matter comprises a core of said polymer and an outer shell.

5. The method of claim 1 wherein the outer shell is a polymer formed from at least one monofunctional monomer.

6. The method of claim 4 wherein the core shell weight ratio is 2:

1 or greater.

7. The method of claim 6, wherein the core to shell weight ratio is within regions of 2:

1 to 7;

1 and greater than 9;

1.

8. The method of claim 6, wherein steps (c) and (d) are successively repeated.

9. The method of claim 1, wherein the composition also comprises a plasticizer.

10. The method of claim 1, wherein the actinic radiation is in the form of a beam.

11. The method of claim 4 wherein the core is crosslinked polymer which is nonswellable and insoluble in a solvent for noncrosslinked polymer material.

12. The method of claim 4 wherein the core contains no pendant acid groups.

13. The method of claim 1 wherein the core contains no pendant acid groups.

14. An article made by the method of claim 13.