Stable emissive toner composition system and method

• US 10,082,744 B2
• Filed: 11/20/2017
• Issued: 09/25/2018
• Est. Priority Date: 08/21/2007
• Status: Active Grant

• Current Assignee: Angstrom Technologies, Inc.
• Original Assignee: Angstrom Technologies, Inc.
• Inventors: Coyle, William J., Stramondo, Anthony
• Primary Examiner(s): Vajda, Peter L
• Assistant Examiner(s): Alam, Rashid A
• Application Number:
  US15/818,315
• Publication Number:
  US 20180074423A1
• Time in Patent Office: 309 Days
• Field of Search: 430 451
• CPC Class Codes: G03G 9/0821 characterised by physical parameters magnetic parameters G03G9/083
• CPC Class Codes: G03G 9/08704 Polyalkenes
• CPC Class Codes: G03G 9/08711 with esters of acrylic or methacrylic acid
• CPC Class Codes: G03G 9/0926 characterised by physical or chemical properties
• CPC Class Codes: G03G 9/0928 Compounds capable to generate colouring agents by chemical reaction
• CPC Class Codes: G03G 9/09733 Organic compounds G03G9/08782 takes precedence
• CPC Class Codes: G03G 9/16 Developers not provided for in groups G03G9/06 - G03G9/135, e.g. solutions, aerosols

Abstract

A method of producing an emissive toner composition including selecting a photoluminescent agent, a charge control agent, and one or more additives and combining the photoluminescent agent, charge control agent, and one or more additives to form an emissive toner composition that when printed to produce an image component on a substrate, the emission spectra of the image component for irradiation with a first excitation energy includes only dominant emission peaks corresponding to one or more dominant emission peaks of the photoluminescent agent. The photoluminescent agent is selected such that it emits light having one or more dominant emission peaks in a first emission spectral region when irradiated with the first excitation energy. The charge control agent and one or more additives are selected such that they do not emit light in the visible spectrum when irradiated with visible light and does not emit light in the first emission spectral region when irradiated with the first excitation energy.

Claims

1. A method of marking an article with an image indicia for authentication, information, or decoration, the method comprising:

providing at least one toner composition that includes;

a photoluminescent agent that emits light having one or more emission peaks in a first emission spectral region, each of the one or more emission peaks centered at a corresponding respective emission wavelength, when irradiated with a first excitation energy;

a charge control agent; and

one or more additives,

the photoluminescent agent, charge control agent, and one or more additives being selected and present in an amount in the toner composition such that when the toner composition is printed to produce an image component on a substrate, the emission spectra of the image component when irradiated with the first excitation energy includes only dominant emission peaks in the first emission spectral region corresponding to the one or more emission peaks of the photoluminescent agent; and

printing at least one image component using the at least one toner composition, the at least one image component making up at least a portion of the image indicia on a substrate.

2. A method according to claim 1, further comprising converting a color image to be printed to a negative form and printing the negative form using the at least one toner composition.

3. A method according to claim 1, wherein the at least one toner composition includes a plurality of toner compositions, wherein the printing includes using the plurality of toner compositions to produce at least three image components associated with at least three different colors.

4. A method according to claim 1, wherein the at least one toner composition includes a plurality of toner compositions and the first emission spectral region is an ultraviolet spectral region, wherein the printing includes using the plurality of toner compositions to produce at least one image component associated with the color black.

5. A method according to claim 1, wherein the at least one toner composition is an emissively black toner composition that produces an emissively black image component on the substrate such that the emission spectra of said emissively black image component includes no dominant emission peaks in the first emission spectral region when irradiated with said first excitation energy.

6. A method according to claim 1, wherein the image component is reflectively visible.

7. A method according to claim 5, wherein the emissively black toner composition does not include an emissively black agent or other pigment.

8. A method according to claim 1, wherein the first emission spectral region is an ultraviolet spectral region and printing using the at least one toner composition produces at least one image component associated with the color brown.

9. A method according to claim 1, wherein printing using the at least one toner composition produces at least one image component that appears to the unaided human eye as the color brown.

10. A method according to claim 9, wherein said color brown has an RGB colorspace of about (150, 75, 0).

11. A method according to claim 9, wherein said color brown has an RGB colorspace of about (164, 84, 30).

12. A method according to claim 1, wherein the first emission spectral region is a spectral region selected from the group consisting of a visible spectral region, an infrared spectral region, an ultraviolet spectral region, and any combinations thereof.

13. A method according to claim 1, wherein the photoluminescent agent is an organic photoluminescent agent.

16. The method according to claim 1, wherein the at least one image component has a photoluminescent toner stability factor of about greater than or equal to 25, wherein the photoluminescent toner stability factor is calculated according to the following equation:

PTSF=((1−

ALF-XE)×

ALF-QUV/CP)×

100,

where PTSF is the photoluminescent toner stability factor, ALF-XE is the average loss in photoluminescence of the image component from day 3 to day 7 of a seven day xenon-arc exposure at 0.35 W/m² at 340 nm with the image component distanced from the xenon arc exposure at 10 inches and a temperature of 50 degrees Celcius, ALF-QUV is the average loss in photoluminescence of the image component from day 3 to day 7 of submission of the image component to QUV exposure conditions, and CP is a number of dominant emission peaks in a desired spectral region of an emission spectra for the image component when irradiated with the first excitation energy prior to the xenon-arc exposure and the QUV exposure.

17. The method according to claim 1, wherein the one or more emission peaks include only a single emission peak.

18. The method according to claim 1, wherein the photoluminescent agent does not emit light in the visible spectrum when irradiated with visible light.

19. The method according to claim 1, wherein the at least one image component is reflectively visible.

20. The method according to claim 1, wherein the at least one image component is reflectively invisible.

21. The method according to claim 1, wherein the photoluminescent agent includes a benzoxazole, a benzothiazole or a combination of a benzoxazole and a benzothiazole.

22. The method according to claim 1, wherein the charge control agent is present in a charge control effective amount and the charge control agent in the charge control effective amount is reflectively invisible.

23. The method according to claim 1, wherein the charge control agent includes a calixerene compound that does not emit light in the visible spectrum when irradiated with visible light and does not emit light in the first emission spectral region when irradiated with the first excitation energy.

24. The method according to claim 1, wherein the charge control agent includes a modified layered silicate that does not emit light in the visible spectrum when irradiated with visible light and does not emit light in the first emission spectral region when irradiated with the first excitation energy.

25. The method according to claim 1, wherein the charge control agent includes a hydrophobically modified metal oxide that does not emit light in the visible spectrum when irradiated with visible light and does not emit light in the first emission spectral region when irradiated with the first excitation energy.

26. The method according to claim 1, wherein the at least one toner composition includes an emissively black toner composition, the at least one image component including an emissively black image component printed with the emissively black toner composition, the emission spectra of said emissively black image component when irradiated with said first excitation energy including no dominant emission peaks in the first emission spectral region.

27. The method according to claim 26, wherein said emissively black toner composition comprises:

an emissively black agent that absorbs said first excitation energy and provides no emission of energy in the first emission spectral region when irradiated with said first excitation energy;

a charge control agent; and

one or more additives.

28. The method according to claim 27, wherein the emissively black image component is reflectively visible.

29. The method according to claim 27, wherein the emissively black image component is reflectively invisible.

30. The method according to claim 26, wherein said emissively black toner composition comprises:

a charge control agent having substantially no emission in the first emission spectral region when irradiated with said first excitation energy; and

one or more additives, wherein the emissively black toner composition does not include an emissively black agent or other pigment.

31. The method according to claim 1, wherein the photoluminescent agent is encapsulated with an encapsulant.

32. The method according to claim 31, wherein the encapsulant is selected from the group consisting of:

melamine formaldehyde, epoxy resins, and polyethylene.

33. The method according to claim 1, wherein the photoluminescent agent is present in an amount from about 0.01 weight percent to about 28 weight percent.

34. The method according to claim 1 further comprising:

receiving image data representing the image components; and

converting the image data to a negative form;

wherein the printing step includes printing the at least one image component with a reflective printing system according to the negative form of the image data.

14. A system for full-color emissive image production on a substrate, the image including a plurality of image components representing image indicia, the system comprising:

a plurality of color toner compositions, each of said plurality of color toner compositions including;

a photoluminescent agent that emits light having one or more dominant emission peaks in a first emission spectral region, each of said one or more dominant emission peaks centered at a corresponding emission wavelength, when irradiated with a first excitation energy;

a charge control agent; and

one or more additives,

said photoluminescent agent, charge control agent, and one or more additives being selected and present in an amount in the toner composition such that when the toner composition is printed to produce an image component on a substrate, the emission spectra of the image component for irradiation with said first excitation energy includes only dominant emission peaks in said first emission spectral region corresponding to said one or more dominant emission peaks of said photoluminescent agent; and

a printer for applying the color toner compositions to the substrate.

35. The system according to claim 14, wherein when the plurality of toner compositions are printed to produce the image component on a substrate, the image component has a photoluminescent toner stability factor of about greater than or equal to 25, wherein the photoluminescent toner stability factor is calculated according to the following equation:

PTSF=((1−

ALF-XE)×

ALF-QUV/CP)×

100,

where PTSF is the photoluminescent toner stability factor, ALF-XE is the average loss in photoluminescence of the image component from day 3 to day 7 of a seven day xenon-arc exposure at 0.35 W/m² at 340 nm with the image component distanced from the xenon arc exposure at 10 inches and a temperature of 50 degrees Celcius, ALF-QUV is the average loss in photoluminescence of the image component from day 3 to day 7 of submission of the image component to QUV exposure conditions, and CP is a number of dominant emission peaks in a desired spectral region of an emission spectra for the image component when irradiated with the first excitation energy prior to the xenon-arc exposure and the QUV exposure.

36. The system according to claim 14, wherein the first emission spectral region is a spectral region selected from the group consisting of a visible spectral region, an infrared spectral region, an ultraviolet spectral region, and any combinations thereof.

37. The system according to claim 14, wherein the one or more dominant emission peaks include only a single dominant emission peak.

38. The system according to claim 14, wherein the photoluminescent agent does not emit light in the visible spectrum when irradiated with visible light.

39. The system according to claim 14, wherein the photoluminescent agent, charge control agent, and one or more additives are selected and present in an amount in the toner composition such that when the toner composition is printed to produce an image component on a substrate, the image component is reflectively visible.

40. The system according to claim 14, wherein the photoluminescent agent, charge control agent, and one or more additives are selected and present in an amount in the toner composition such that when the toner composition is printed to produce an image component on a substrate, the image component is reflectively invisible.

41. The system according to claim 14, wherein the photoluminescent agent includes a benzoxazole, a benzothiazole or a combination of a benzoxazole and a benzothiazole.

42. The system according to claim 14, wherein the charge control agent is present in a charge control effective amount and the charge control agent in the charge control effective amount is reflectively invisible.

43. The system according to claim 14, wherein the charge control agent includes a calixerene compound that does not emit light in the visible spectrum when irradiated with visible light and does not emit light in the first emission spectral region when irradiated with the first excitation energy.

44. The system according to claim 14, wherein the charge control agent includes a modified layered silicate that does not emit light in the visible spectrum when irradiated with visible light and does not emit light in the first emission spectral region when irradiated with the first excitation energy.

45. The system according to claim 14, wherein the charge control agent includes a hydrophobically modified metal oxide that does not emit light in the visible spectrum when irradiated with visible light and does not emit light in the first emission spectral region when irradiated with the first excitation energy.

15. A system for full-color emissive image production on a substrate, the system comprising:

a first color toner having a first invisibly emissive effective amount of a first photoluminescent agent that does not emit light in the visible spectrum when irradiated with visible light and emits light having one or more emission peaks when irradiated with a first non-visible excitation wavelength of light and a first emissively invisible charge control agent;

a second color toner having a second invisibly emissive effective amount of a second photoluminescent agent that does not emit light in the visible spectrum when irradiated with visible light and emits light having one or more emission peaks when irradiated with a second non-visible excitation wavelength of light and a second emissively invisible charge control agent; and

a third color toner having a third invisibly emissive effective amount of a third photoluminescent agent that does not emit light in the visible spectrum when irradiated with visible light and emits light having one or more emission peaks when irradiated with a third non-visible excitation wavelength of light and a third emissively invisible charge control agent,

the first, second, and third toner each producing an image component of the full-color image when printed on the substrate, an emission spectrum corresponding to the image component of said first toner when irradiated with said first non-visible excitation wavelength including only dominant emission peaks corresponding to the one or more emission peaks of the first photoluminescent agent, an emission spectrum corresponding to the image component of said second toner when irradiated with said second non-visible excitation wavelength including only dominant emission peaks corresponding to the one or more emission peaks of the second photoluminescent agent, an emission spectrum corresponding to the image component of said third toner for irradiation with said third non-visible excitation wavelength including only dominant emission peaks corresponding to the one or more emission peaks of the third photoluminescent agent; and

a printer for applying the first, second, and third color toners to the substrate.

46. An article of manufacture, comprising:

a substrate; and

at least one image component that includes;

a photoluminescent agent that emits light having one or more emission peaks in a first emission spectral region, each of the one or more emission peaks centered at a corresponding respective emission wavelength, when irradiated with a first excitation energy;

a charge control agent; and

one or more additives,

wherein the at least one image component has an emission spectra when irradiated with the first excitation energy that includes only dominant emission peaks in a first emission spectral region corresponding to the one or more emission peaks of the photoluminescent agent.

47. The article of manufacture according to claim 46, wherein the article of manufacture is a security identification document, or a label or package for process control, counterfeit control, or authentication of an article.

48. The article of manufacture according to claim 46, wherein the at least one image component has a photoluminescent toner stability factor of about greater than or equal to 25, wherein the photoluminescent toner stability factor is calculated according to the following equation:

PTSF=((1−

ALF-XE)×

ALF-QUV/CP)×

100,

where PTSF is the photoluminescent toner stability factor, ALF-XE is the average loss in photoluminescence of the image component from day 3 to day 7 of a seven day xenon-arc exposure at 0.35 W/m² at 340 nm with the image component distanced from the xenon arc exposure at 10 inches and a temperature of 50 degrees Celcius, ALF-QUV is the average loss in photoluminescence of the image component from day 3 to day 7 of submission of the image component to QUV exposure conditions, and CP is a number of dominant emission peaks in a desired spectral region of an emission spectra for the image component when irradiated with the first excitation energy prior to the xenon-arc exposure and the QUV exposure.

49. The article of manufacture according to claim 46, wherein the one or more emission peaks include only a single emission peak.

50. The article of manufacture according to claim 46, wherein the photoluminescent agent does not emit light in the visible spectrum when irradiated with visible light.

51. The article of manufacture according to claim 46, wherein the at least one image component includes a reflectively visible image component.

52. The article of manufacture according to claim 46, wherein the at least one image component includes a reflectively invisible image component.

53. The article of manufacture according to claim 46, wherein the photoluminescent agent includes a benzoxazole, a benzothiazole or a combination of a benzoxazole and a benzothiazole.

54. The article of manufacture according to claim 46, wherein the charge control agent is present in a charge control effective amount and the charge control agent in the charge control effective amount is reflectively invisible.

55. The article of manufacture according to claim 46, wherein the charge control agent includes a calixerene compound that does not emit light in the visible spectrum when irradiated with visible light and does not emit light in the first emission spectral region when irradiated with the first excitation energy.

56. The article of manufacture according to claim 46, wherein the charge control agent includes a modified layered silicate that does not emit light in the visible spectrum when irradiated with visible light and does not emit light in the first emission spectral region when irradiated with the first excitation energy.

57. The article of manufacture according to claim 46, wherein the charge control agent includes a hydrophobically modified metal oxide that does not emit light in the visible spectrum when irradiated with visible light and does not emit light in the first emission spectral region when irradiated with the first excitation energy.

58. The article of manufacture according to claim 46, wherein the at least one image component includes an emissively black image component having an emissively black photoluminescent agent, the emission spectra of said emissively black image component when irradiated with said first excitation energy including no dominant emission peaks in the first emission spectral region.

59. The article of manufacture according to claim 58, wherein said emissively black photoluminescent agent absorbs said first excitation energy and provides no emission of energy in the first emission spectral region when irradiated with said first excitation energy.

60. The article of manufacture according to claim 58, wherein the emissively black image component is reflectively visible.

61. The article of manufacture according to claim 58, wherein the emissively black image component is reflectively invisible.

62. The article of manufacture according to claim 46, wherein the at least one image component includes an emissively black image component including a charge control agent having substantially no emission in the first emission spectral region when irradiated with said first excitation energy, further wherein the emissively black image component does not include an emissively black agent or other pigment.

63. The article of manufacture according to claim 46, wherein the photoluminescent agent is encapsulated with an encapsulant.

64. The article of manufacture according to claim 63, wherein the encapsulant selected from the group consisting of:

melamine formaldehyde, epoxy resins, and polyethylene.