IP Library Granted Patent US 6,899,988
Granted Patent B2
US 6,899,988 · App. 10/461,738 · Granted May 31, 2005

Laser thermal metallic donors

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Quick Facts
Patent No.
US 6,899,988
App. No.
10/461,738
Granted
May 31, 2005
Kind
B2
Abstract

A laser-induced thermal imaging system having a multi-layer construction donor element and a receptor element for the preparation of a metallic digital half tone color proof having an improved shiny metallic appearance. The donor element includes a substrate on which is coated at least two layers. The donor element includes a first layer coated on one side of the substrate having at least a first donor binder and a cationic infrared absorbing dye. The donor layer also includes a distinct second layer coated on the first layer. The second layer includes at least a second donor binder, a cationic infrared absorbing dye, a latent crosslinking agent, a fluorocarbon additive, metallic flakes and a dispersible material. The receptor element of the present invention includes a substrate coated with at least a receptor binder and a bleaching agent.

Claims (122)

1. A laser-induced thermal imaging system comprising:

(a) a multi-layer construction donor element comprising a substrate coated with at least:

a first layer coated on one side of the substrate having:

a first donor binder; and

a cationic infrared absorbing dye; and

a distinct second layer covering the first layer having:

a second donor binder;

a cationic infrared absorbing dye;

a second layer crosslinking agent of the formula:

 wherein R 1 is hydrogen, alkyl, cycloalkyl, or aryl and each R 2 and R 3 is independently alkyl or aryl and R 4 is aryl;

a fluorocarbon additive;

metallic flakes; and

a dispersible material;

(b) a receptor element comprising a substrate coated with at least

a receptor binder; and

a bleaching agent.

2. The laser-induced thermal imaging system of claim 1 wherein the first donor binder comprises a hydroxylic polymer.

3. The laser-induced thermal imaging system of claim 1 wherein the first donor binder is polyvinyl butyral.

4. The laser-induced thermal imaging system of claim 1 wherein the first donor binder is present in an amount of about 35 to about 65 wt % based on total weight of the first layer.

5. The laser-induced thermal imaging system of claim 1 wherein the first donor binder does not crosslink when exposed to laser thermal energy.

6. The laser-induced thermal imaging system of claim 1 wherein the cationic infrared absorbing dye in either the first layer or the second layer is a bleachable dye.

7. The laser-induced thermal imaging system of claim 1 wherein the cationic infrared absorbing dye is a tetraarylpolymethine dye, an amine cation radical dye, or mixtures thereof.

8. The laser-induced thermal imaging system of claim 7 wherein the cationic infrared absorbing dye is a tetraarylpolymethine dye.

9. The laser-induced thermal imaging system of claim 8 wherein the tetraarylpolymethine dye is of the formula:

wherein each Ar 1 , Ar 2 , Ar 3 and Ar 4 is aryl and at least one aryl has a cationic amino substituent, and X is an anion.

10. The laser-induced thermal imaging system of claim 8 wherein the tetraarylpolymethine dye is of the formula:

11. The laser-induced thermal imaging system of claim 1 wherein the cationic infrared dye of the first layer is present in an amount of about 3 to about 20 wt % based on total weight of the first layer.

12. The laser-induced thermal imaging system of claim 1 wherein the cationic infrared dye of the second layer is present in an amount of about 5 to about 15 wt % based on total weight of the second layer.

13. The laser-induced thermal imaging system of claim 1 wherein the second donor binder comprises a hydroxylic polymer.

14. The laser-induced thermal imaging system of claim 1 wherein the second donor binder is polyvinyl butyral.

15. The laser-induced thermal imaging system of claim 1 wherein the second donor binder is crosslinked when exposed to laser thermal energy.

16. The laser-induced thermal imaging system of claim 1 wherein the second donor binder is present in an amount of about 10 to about 55 wt % based on total weight of the second layer.

17. The laser-induced thermal imaging system of claim 1 wherein the second donor binder is a blend of one or more crosslinkable hydroxylic polymers with one or more noncrosslinkable polymers selected from the group consisting of polyesters, polyamides, polycarbamates, polyolefins, polystyrenes, polyethers, polyvinyl ethers, polyvinyl esters, polyacrylates, polymethacrylates, polymethyl methacrylates, and combinations thereof.

18. The laser-induced thermal imaging system of claim 1 wherein the second layer crosslinking agent is of the formula:

19. The laser-induced thermal imaging system of claim 1 wherein the second layer crosslinking agent is present in an amount of about 1 to about 5 wt % based on total weight of the second layer.

20. The laser-induced thermal imaging system of claim 1 wherein the fluorocarbon additive comprises a sulfonamido compound.

21. The laser-induced thermal imaging system of claim 1 wherein the fluorocarbon additive comprises (C 8 F 17 )SO 2 NH(CH 2 CH 3 ).

22. The laser-induced thermal imaging system of claim 1 wherein the fluorocarbon additive is present in an amount of about 0.5 to about 5.0 wt % based on total weight of the second layer.

23. The laser-induced thermal imaging system of claim 1 wherein the metallic flakes are aluminum, mica, or mixtures thereof.

24. The laser-induced thermal imaging system of claim 1 wherein the metallic flakes of are aluminum.

25. The metallic flakes of claim 1 wherein the metallic flakes have a particle size from about 7 to 24 microns.

26. The laser-induced thermal imaging system of claim 1 wherein the metallic flakes are present in an amount of about 20 to about 50 wt % based on the total weight of the second layer.

27. The laser-induced thermal imaging system of claim 1 wherein the dispersible material is a pigment, a crystalline nonsublimable dye, a color enhancing additive, a texturizing material, or mixtures thereof.

28. The laser-induced thermal imaging system of claim 27 wherein the dispersible material comprises a pigment.

29. The laser-induced thermal imaging system of claim 27 wherein the dispersible material comprises texturizing particles.

30. The laser-induced thermal imaging system of claim 1 wherein the first layer further comprises optional additives selected from the group consisting of coating aids, dispersing agents, optical brighteners, UV absorbers, fillers, surfactants and combinations thereof.

31. The laser-induced thermal imaging system of claim 1 wherein the second layer further comprises optional additives selected from the group consisting of coating aids, dispersing agents, optical brighteners, UV absorbers, fillers, surfactants and combinations thereof.

32. The laser-induced thermal imaging system of claim 1 wherein the receptor binder comprises a hydroxylic polymer.

33. The laser-induced thermal imaging system of claim 1 wherein the receptor binder is polyvinyl butyral.

34. The laser-induced thermal imaging system of claim 1 wherein the receptor binder is a polyvinyl pyrrolidone/vinyl acetate copolymer binder, a styrene-butadiene copolymer, a phenoxy resin, or combinations thereof.

35. The laser-induced thermal imaging system of claim 1 wherein the bleaching agent is an amine, a salt that decomposes thermally to release an amine, a reducing agent or combinations thereof.

36. The laser-induced thermal imaging system of claim 1 wherein the bleaching agent comprises a guanidine of the formula:

wherein each R 1 and R 2 is independently hydrogen or an organic group.

37. The laser-induced thermal imaging system of claim 36 wherein each R 1 and R 2 is independently hydrogen or alkyl.

38. The laser-induced thermal imaging system of claim 1 wherein the bleaching agent comprises a 1,4-dihydropyridine.

39. The laser-induced thermal imaging system of claim 1 wherein the receptor element further comprises optional additives selected from the group consisting of particulate material, surfactants, antioxidants and combinations thereof.

40. The laser-induced thermal imaging system of claim 1 wherein the receptor element comprises a substrate having a textured receiving layer surface comprising a plurality of protrusions projecting above the outer surface of the substrate by an average distance of about 1 μm to about 8 μm.

41. The laser-induced thermal imaging system of claim 40 , wherein the protrusions are formed from particulate material.

42. The laser-induced thermal imaging system of claim 41 , wherein the particulate material comprises polymeric beads.

43. The laser-induced thermal imaging system of claim 42 wherein the polymeric beads are polymethylmethacrylate beads, polystearyl methacrylate beads, or mixtures thereof.

44. The laser-induced thermal imaging system of claim 1 wherein the substrate of the receptor element is coated paper, metals, films or plates composed of various film-forming synthetic or high molecular weight polymers including addition polymers, wherein the addition polymers are selected from the group consisting of poly(vinylidene chloride), poly(vinyl chloride), poly(vinyl acetate), polystyrene, polyisobutylene polymers and copolymers, linear condensation polymers (e.g., poly(ethylene terephthalate), poly(hexamethylene adipate), poly(hexamethylene adipamide/adipate), and combinations thereof.

45. The laser induced thermal imaging system of claim 1 wherein the substrate of the receptor element is paper or plastic film coated with a thermoplastic receiving layer.

46. The laser-induced thermal imaging system of claim 1 which produces a transferred image having a resolution of at least about 300 dots per inch.

47. The laser-induced thermal imaging system of claim 1 which produces a transferred image having a resolution of at least about 1000 dots per inch.

48. The laser-induced thermal imaging system of claim 1 which produces a transferred image at a sensitivity of no greater than about 0.5 Joule/cm 2 .

49. A laser-induced thermal imaging system comprising:

(a) a multi-layer construction donor element comprising a substrate coated with at least:

a first layer coated on one side of the substrate having:

a first donor binder;

a cationic infrared absorbing dye; and

optional additives; and

a distinct second layer covering the first layer having:

a second donor binder;

a cationic infrared absorbing dye;

a second layer crosslinking agent of the formula:

 wherein R 1 is hydrogen, alkyl, cycloalkyl, or aryl and each R 2 and R 3 is independently alkyl or aryl, and R 4 is aryl;

a fluorocarbon additive;

metallic flakes;

a dispersible material; and

optional additives; and

(b) a receptor element comprising a substrate coated with at least

a receptor binder;

a bleaching agent; and

optional additives.

50. A laser-induced thermal imaging system comprising:

a multi-layer construction donor element comprising a substrate coated with at least:

a first layer coated on one side of the substrate having:

a first donor binder; and

a cationic infrared absorbing dye; and

a distinct second layer covering the first layer having:

a second donor binder;

a cationic infrared absorbing dye;

a second layer crosslinking agent of the formula:

 wherein R 1 is hydrogen, alkyl, cycloalkyl, or aryl and each R 2 and R 3 is independently alkyl or aryl, and R 4 is aryl;

a fluorocarbon additive;

metallic flakes; and

a dispersible material.

51. A method of imaging comprising:

(a) providing a multi-layer construction donor element comprising a substrate coated with at least:

a first layer coated on one side of the substrate having:

a first donor binder, and

a cationic infrared absorbing dye; and

a distinct second layer covering the first layer having:

a second donor binder;

a cationic infrared absorbing dye;

a second layer crosslinking agent of the formula:

 wherein R 1 is hydrogen, alkyl, cycloalkyl, or aryl and each R 2 and R 3 is independently alkyl or aryl, and R 4 is aryl;

a fluorocarbon additive;

metallic flakes; and

a dispersible material;

(b) providing a receptor element comprising a substrate coated with at least

a receptor binder; and

a bleaching agent;

(c) assembling the donor element in contact with the receptor element and exposing the assembly to laser radiation of a wavelength absorbed by the cationic infrared absorbing dye, said laser radiation being modulated in accordance with digitally stored image information, thereby transferring portions of the second layer from the donor element to the receptor element;

(d) separating the donor element and receptor element, leaving an image residing on the receptor element; and

(c) subjecting the receptor and image residing thereon to heat treatment.

52. The method of imaging of claim 51 wherein the first donor binder and the cationic infrared absorbing dye of the first layer are dispersed with an organic solvent and coated on top of one side of the substrate of the donor element.

53. The method of imaging of claim 52 wherein the organic solvent of the first layer is methyl ethyl ketone, methyl isobutyl ketone, ethanol or mixtures thereof.

54. The method of imaging of claim 51 wherein the second donor binder, the cationic infrared absorbing agent, the latent crosslinking agent, the fluorocarbon, the metallic flakes, and the dispersible materials are dissolved with an organic solvent and coated on top of the first layer of the donor element.

55. The method of imaging of claim 54 wherein the organic solvent of the second layer is methyl ethyl ketone, methyl isobutyl ketone, or ethanol.

56. The method of imaging of claim 51 wherein steps (1)-(3) form a cycle which is repeated, wherein a different donor element comprising a different colorant is used for each cycle, but the same receptor element is used for each cycle.

57. The method of imaging of claim 56 wherein the image residing on the receptor after all the repetitions of steps (1)-(3) is transferred to another receptor as a final step.

Assignments (11)
RELEASE OF SECURITY INTEREST Recorded Jan 24, 2020
From: BARCLAYS BANK PLC
To: EASTMAN KODAK COMPANY; FAR EAST DEVELOPMENT LTD.; FPC INC.; KODAK (NEAR EAST) INC.; KODAK AMERICAS LTD.; KODAK REALTY INC.; LASER PACIFIC MEDIA CORPORATION; QUALEX INC.; KODAK PHILIPPINES LTD.; NPEC INC.
Reel/Frame 052773/0001 →
RELEASE OF SECURITY INTEREST Recorded Jul 22, 2019
From: JP MORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
To: EASTMAN KODAK COMPANY; FAR EAST DEVELOPMENT LTD.; FPC, INC.; KODAK (NEAR EAST), INC.; KODAK AMERICAS, LTD.; KODAK IMAGING NETWORK, INC.; KODAK PORTUGUESA LIMITED; KODAK REALTY, INC.; LASER PACIFIC MEDIA CORPORATION; PAKON, INC.; QUALEX, INC.; KODAK PHILIPPINES, LTD.; NPEC, INC.; CREO MANUFACTURING AMERICA LLC; KODAK AVIATION LEASING LLC
Reel/Frame 049814/0001 →
INTELLECTUAL PROPERTY SECURITY AGREEMENT (ABL) Recorded Sep 5, 2013
From: EASTMAN KODAK COMPANY; FAR EAST DEVELOPMENT LTD.; FPC INC.; KODAK (NEAR EAST), INC.; KODAK AMERICAS, LTD.; KODAK IMAGING NETWORK, INC.; KODAK PORTUGUESA LIMITED; KODAK REALTY, INC.; LASER-PACIFIC MEDIA CORPORATION; PAKON, INC.; QUALEX INC.; KODAK PHILIPPINES, LTD.; NPEC INC.; CREO MANUFACTURING AMERICA LLC; KODAK AVIATION LEASING LLC
To: BANK OF AMERICA N.A., AS AGENT
Reel/Frame 031162/0117 →
RELEASE OF SECURITY INTEREST IN PATENTS Recorded Sep 5, 2013
From: CITICORP NORTH AMERICA, INC., AS SENIOR DIP AGENT; WILMINGTON TRUST, NATIONAL ASSOCIATION, AS JUNIOR DIP AGENT
To: EASTMAN KODAK COMPANY; PAKON, INC.
Reel/Frame 031157/0451 →
INTELLECTUAL PROPERTY SECURITY AGREEMENT (FIRST LIEN) Recorded Sep 5, 2013
From: EASTMAN KODAK COMPANY; FAR EAST DEVELOPMENT LTD.; FPC INC.; KODAK (NEAR EAST), INC.; KODAK IMAGING NETWORK, INC.; KODAK PORTUGUESA LIMITED; KODAK REALTY, INC.; LASER-PACIFIC MEDIA CORPORATION; PAKON, INC.; QUALEX INC.; KODAK PHILIPPINES, LTD.; NPEC INC.; CREO MANUFACTURING AMERICA LLC; KODAK AVIATION LEASING LLC; KODAK AMERICAS, LTD.
To: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE
Reel/Frame 031158/0001 →
INTELLECTUAL PROPERTY SECURITY AGREEMENT (SECOND LIEN) Recorded Sep 5, 2013
From: EASTMAN KODAK COMPANY; FAR EAST DEVELOPMENT LTD.; FPC INC.; KODAK (NEAR EAST), INC.; KODAK AMERICAS, LTD.; KODAK IMAGING NETWORK, INC.; KODAK PORTUGUESA LIMITED; KODAK REALTY, INC.; LASER-PACIFIC MEDIA CORPORATION; PAKON, INC.; QUALEX INC.; KODAK PHILIPPINES, LTD.; NPEC INC.; CREO MANUFACTURING AMERICA LLC; KODAK AVIATION LEASING LLC
To: BARCLAYS BANK PLC, AS ADMINISTRATIVE AGENT
Reel/Frame 031159/0001 →
PATENT SECURITY AGREEMENT Recorded Apr 1, 2013
From: EASTMAN KODAK COMPANY; PAKON, INC.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION, AS AGENT
Reel/Frame 030122/0235 →
SECURITY INTEREST Recorded Feb 21, 2012
From: EASTMAN KODAK COMPANY; PAKON, INC.
To: CITICORP NORTH AMERICA, INC., AS AGENT
Reel/Frame 028201/0420 →
MERGER Recorded Aug 18, 2006
From: KPG HOLDING COMPANY, INC. (FORMERLY KODAK POLYCHROME GRAPHICS LLC)
To: EASTMAN KODAK COMPANY
Reel/Frame 018132/0373 →
RE-RECORD TO CORRECT THE THIRD ASSIGNOR ON AN ASSIGNMENT RECORDED ON REEL 014183 FRAME 0303 Recorded Jan 12, 2004
From: KIDNIE, KEVIN M.; FOHRENKAMM, ELSIE A.; ZWADLO, GREGORY L.
To: KODAK POLYCHROME GRAPHICS LLC
Reel/Frame 014872/0535 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 13, 2003
From: KIDNIE, KEVIN M.; FOHRENKAMM, ELSIE A.; ZWALDO, GREGORY L.
To: KODAK POLYCHROME GRAPHICS, LLC
Reel/Frame 014183/0303 →