Fluorescent polymeric articles having screening layer formed from U.V. light absorbing polymer

• US 6,514,594 B1
• Filed: 11/09/2000
• Issued: 02/04/2003
• Est. Priority Date: 11/09/2000
• Status: Expired due to Term

• Current Assignee: General Electric Company
• Original Assignee: Avery Dennison Corporation
• Inventors: Dockus, Kimberly A., Buoni, Drew J., Wei, Guang-Xue
• Primary Examiner(s): Truong, Duc
• Application Number:
  US09/710,560
• Time in Patent Office: 817 Days
• Field of Search: 428/141, 428/40.7, 428/690, 428/917, 430/56, 430/60, 430/68, 430/75, 525/92.E, 525/89, 525/451, 525/461, 525/462, 525/466
• US Class Current: 428/141
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/18 characterised by the use of special additives
• CPC Class Codes: B32B 27/36 comprising polyesters
• CPC Class Codes: C08J 2367/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds; C08J2367/06 takes precedence
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: C08K 5/0041 Optical brightening agents, organic pigments
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 2666/18 Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
• CPC Class Codes: C08L 51/08 grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 67/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds C08L67/06 takes precedence
• CPC Class Codes: C08L 67/03 the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
• CPC Class Codes: C08L 69/00 Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• CPC Class Codes: G02B 5/124 plural reflecting elements forming part of a unitary plate or sheet
• CPC Class Codes: Y10S 428/917 Electroluminescent
• CPC Class Codes: Y10T 428/1429 Fluorine
• CPC Class Codes: Y10T 428/24355 Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]

Abstract

A fluorescent article is disclosed in which a U.V. light screening layer comprising a polymer having in its backbone repeating units of a U.V. light absorbing moiety, or a moiety capable of being transformed by Photo-Fries rearrangement into a U.V. light absorbing moiety, is disposed in operative screening relation to a layer containing a fluorescent colorant. The U.V. light screening layer affords surprisingly improved fluorescence protection as compared to prior U.V. light screening layers having only U.V. light absorbing additives.

Claims

1. An article comprising;

(a) a fluorescent polymeric layer comprising a fluorescent dye; and

(b) an ultraviolet light screening layer comprising a polymeric resin, said polymeric resin comprising at least one polymer, or a mixture thereof, selected from the group consisting of;

(i) polymers having a polymeric backbone comprising the following repeating moiety A;

 

wherein R is a non-interfering substitutent and P is the remainder of the polymer; and

whereby the polymers are able to absorb ultraviolet light; and

(ii) polymers having a polymeric backbone comprising the following repeating moiety B;

 

wherein R is a non-interfering substituent and P is the remainder of the polymer;

said moiety B being transformable to said moiety A by photo-Fries rearrangement, whereby said polymer comprising moiety B can be transformed to an ultraviolet light absorbing polymer comprising moiety A.

2. The article of claim 1 wherein the ultraviolet light screening layer comprises a polyarylate resin.

3. The article of claim 2 wherein the polyarylate resin comprises at least one polymer selected from the group consisting of polyarylate polymers comprising one or both of the following repeating structures I and II:

4. The article of claim 1 wherein the polymeric resin of the U.V. screening layer comprises a blend of polyarylate and at least one additional polymer.

5. The article of claim 4 wherein said additional polymer is selected from the group consisting of polycarbonate, poly(cyclohexanedimethanol terephthalate), poly(cyclohexanedimethenol-co-ethylene terephthalate), poly(ethylene terephthalate), and blends thereof.

6. The article of claim 4 wherein said additional polymer in the ultraviolet light screening layer comprises polycarbonate.

7. The article of claim 1 wherein said at least one polymer in the ultraviolet light screening layer is a block copolyestercarbonate having arylate blocks and carbonate blocks.

8. The article of claim 7 wherein the block copolymer has a polymeric backbone comprising one or both of the following repeating structures:

wherein each R¹ is independently H or C₁-C₁₂ alkyl, p is 0-3, each R² is independently a divalent organic radical;

m is about 2-200; and

n is about 30-150.

9. The article of claim 1 in the form of a retroreflective sheeting material.

10. The article of claim 1 wherein the fluorescent layer further comprises a non-fluorescent colorant.

11. The article of claim 1 wherein the fluorescent dye is selected from the group consisting of perylene dyes, perylene ester dyes, perylene imide dyes, thioxanthone dyes, thioindigoid dyes, thioxanthene dyes, benzoxanthene dyes, benzothiazine dyes, naphthalimide dyes, coumarin dyes, and mixtures thereof.

12. The article of claim 11 wherein the fluorescent dye comprises a thioxanthene dye.

13. The article of claim 12 wherein the thioxanthene dye comprises Solvent Yellow 98.

14. The article of claim 11 wherein the fluorescent dye comprises a perylene imide or perylene ester dye.

15. The article of claim 14 wherein the fluorescent dye comprises any one or more of Lumogen F Yellow 083, Lumogen F Orange 240, and Lumogen F Red 300.

16. The article of claim 11 wherein the fluorescent dye comprises a benzoxanthene dye.

17. The article of claim 11 wherein the fluorescent dye comprises a benzothiazine dye.

18. The article of claim 1 wherein the fluorescent layer comprises a polymeric resin selected from the group consisting of polycarbonate, poly(ethylene terephthalate), poly(cyclohexanedimethanol-co-ethylene terephthalate), poly(cyclohexanedimethanol terephthalate), polyarylate, copolyestercarbonate block copolymers containing arylate and carbonate blocks, polyurethanes, polystyrenes, acrylic polymers, polyvinyl chloride, and blends thereof.

19. The article of claim 18 wherein the fluorescent layer comprises polyarylate.

20. The article of claim 19 wherein the polyarylate has a polymeric backbone comprising one or both of the following repeating structures:

21. The article of claim 1 in the form of a fluorescent retroreflective sheeting material comprising:

a fluorescent layer comprising said polymeric matrix comprising a polyarylate and a fluorescent dye admixed therein; and

a plurality of retroreflective elements.

22. The article of claim 18 wherein the fluorescent layer comprises a polymeric resin selected from the group consisting of poly(ethylene terephthalate), poly(cyclohexanedimethanol-co-ethylene terephthalate), and mixtures thereof.

23. The article of claim 19 wherein the fluorescent layer comprises a blend of polyarylate and at least one additional resin selected from the group consisting of polycarbonate, poly(ethylene terephthalate), poly(cyclohexanedimethanol terephthalate), and poly (cyclohexanedimethanol-co-ethylene terephthalate).

24. The article of claim 23 wherein the fluorescent layer comprises a blend of polyarylate and polycarbonate.

25. The article of claim 23 wherein the fluorescent layer comprises a blend of polyarylate and poly(ethylene terephthalate).

26. The article of claim 1 wherein the fluorescent layer comprises one or more additives selected from the group consisting of U.V. absorbing additives and hindered amine light stabilizing additives, wherein said one or more additives is present as an admixture with the polymeric resin in said layer.

27. The article of claim 1 further comprising a plurality of retroreflective elements selected from the group consisting of microprismatic cube comers and glass microspheres.

28. The article of claim 27 wherein said retroreflective elements are microprismatic cube corners.

29. The article of claim 28 wherein said cube comers are formed on a surface of said fluorescent layer.

30. The article of claim 28 comprising a third polymeric layer, said fluorescent layer being disposed between said screening layer and said third polymeric layer, said cube corners being disposed on the surface of said third polymeric layer opposite said fluorescent layer.

31. The article of claim 30 comprising a fourth layer disposed in laminar configuration over said screening layer.

32. The article of claim 27 wherein the retroreflective elements are microspheres in an enclosed lens configuration.

33. The article of claim 32 wherein said at least one polymer is a polyarylate.

34. A retroreflective sheeting material comprising:

(a) a fluorescent polymeric layer comprising a fluorescent dye; and

(b) an ultraviolet light screening layer comprising a polymeric resin, said polymeric resin comprising at least one polymer, or mixture thereof, selected from the group consisting of;

(i) polymers having a polymeric backbone comprising the following repeating moiety A;

 

wherein R is a non-interfering substitutent and P is the remainder of the polymer; and

whereby the polymers are able to absorb ultraviolet light; and

(ii) polymers having a polymeric backbone comprising the following repeating moiety B;

 

wherein R is a non-interfering substituent and P is the remainder of the polymer;

said moiety B being transformable to said moiety A by photo-Fries rearrangement in the presence of ultraviolet light, whereby said polymer comprising moiety B can be transformed to an ultraviolet light absorbing polymer comprising moiety A.

35. The retroreflective sheeting material of claim 34 wherein said at least one polymer in the ultraviolet screening layer comprises a polyarylate having a polymeric backbone comprising one or both of the following repeating units (I) and (II):

36. The retroreflective sheeting material of claim 35 wherein the fluorescent layer comprises a polymeric resin selected from the group consisting of polycarbonate, poly(ethylene terephthalate), poly(cyclohexanedimethanol-co-ethylene terephthalate), poly(cyclohexanedimethanol terephthalate), polyarylate, copolyestercarbonate, block copolymers containing arylate and carbonate blocks, polyurethanes, polystyrenes, acrylic polymers, polyvinyl chloride, and blends thereof.

37. The retroreflective sheeting material of claim 36 wherein the fluorescent layer comprises polyarylate.

38. The retroreflective sheeting material of claim 37 wherein the fluorescent dye comprises a dye selected from the group consisting of thioxanthene dyes.

39. The retroreflective sheeting material of claim 38 wherein said thioxanthene dye comprises Solvent Yellow 98.

40. The retroreflective sheeting material of claim 36 wherein the fluorescent layer comprises polycarbonate.

41. The retroreflective sheeting material of claim 40 wherein the fluorescent dye comprises a dye selected from the group consisting of benzothiazine, benzoxanthene, and thioxanthene dyes.

42. The sheeting material of claim 41 wherein the fluorescent dye comprises Solvent Yellow 98.

43. The retroreflective sheeting material of claim 36 wherein the fluorescent layer comprises poly (cyclohexanedimethanol-co-ethylene terephthalate).

44. The retroreflective sheeting material of claim 43 wherein the fluorescent dye comprises a dye selected from the group consisting of thioxanthene, perylene, perylene imide, perylene ester, and benzoxanthene dyes.

45. The sheeting material of claim 44 wherein the fluorescent dye comprises any one or more of Solvent Yellow 98, Lumo en F Yellow 083, Lumogen F Orange 240, and Lumogen F Red 300.

46. The retroreflective sheeting material of claim 36 wherein the fluorescent layer comprises a blend of polyarylate and polycarbonate.

47. The retroreflective sheeting material of claim 46 wherein the fluorescent dye comprises a dye selected from the group consisting of thioxanthene dyes.

48. The retroreflective sheeting material of claim 47 wherein said thioxanthene dye comprises Solvent Yellow 98.

49. The retroreflective sheeting material of claim 36 wherein the fluorescent layer comprises a blend of polyarylate and poly(ethylene terephthalate).

50. The retroreflective sheeting material of claim 49 wherein the fluorescent dye comprises a dye selected from the group consisting of thioxanthene dyes.

51. The sheeting material of claim 50 wherein the thioxanthene dye comprises Solvent Yellow 98.

52. The retroreflective sheeting material of claim 34 wherein said ultraviolet light screening layer and said fluorescent layer are disposed in laminar configuration, and said retroreflective elements are disposed on a surface of said fluorescent layer opposite said screening layer.

53. The retroreflective sheeting material of claim 34 further comprising a tie layer or adhesive between said ultraviolet light screening layer and said fluorescent layer.

54. The retroreflective sheeting material of claim 34 further comprising an adhesive between said ultraviolet light screening layer and said fluorescent layer.

55. The retroreflective sheeting material of claim 34 further comprising a third polymeric layer disposed over said ultraviolet light screening layer.

56. The retroreflective sheeting material of claim 34 further comprising a third polymeric layer disposed behind said fluorescent layer, and said retroreflective elements are disposed on the surface of the third polymeric layer opposite said fluorescent layer.

57. The retroreflective sheeting material of claim 56 further comprising a fourth polymeric layer disposed over said ultraviolet light screening layer.

58. The retroreflective sheeting material of claim 56 further comprising a tie layer or adhesive between said fluorescent layer and said ultraviolet light screening layer.

59. The retroreflective sheeting material of claim 34 wherein said ultraviolet light screening layer absorbs substantial amounts of light between wavelengths about 375-410 nanometers.

60. The retroreflective sheeting material of claim 34 wherein said ultraviolet light screening layer absorbs substantial amounts of light at wavelengths below about 375 nanometers.

61. An article comprising

(a) a fluorescent polymeric layer comprising a fluorescent dye;

and

(b) an ultraviolet light screening layer comprising a polymeric resin, said polymeric resin comprising at least one polymer, or a mixture thereof, which either is, or is capable of undergoing rearrangement into a U.V. light absorbing polymer material.

62. The article of claim 61 wherein said polymer is or is capable of undergoing transformation into, a polymer that absorbs substantial amounts of light in a portion of the light spectrum between about 375-410 nm.

63. The article of claim 61 wherein said polymer is or is capable of undergoing transformation into, a polymer that absorbs substantial amounts of light in a portion of the light spectrum between about 290-375 nm.

64. The article of claim 61 wherein said polymer comprises a polyarylate.