PRISMATIC RETROREFLECTIVE ARTICLE WITH CROSS-LINKED IMAGE LAYER AND METHOD OF MAKING SAME

• US 20090021831A1
• Filed: 07/16/2007
• Published: 01/22/2009
• Est. Priority Date: 07/16/2007
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Manske, Joy L., Ough, Rodney A., Ray, Bradley R., Bacon, Chester A. JR.
• Granted Patent: US 7,547,105 B2
• Time in Patent Office: Days
• US Class Current: 359/530
• CPC Class Codes: B29D 11/00605 Production of reflex reflectors
• CPC Class Codes: G02B 5/124 plural reflecting elements forming part of a unitary plate or sheet
• CPC Class Codes: Y10T 428/254 Polymeric or resinous material

Abstract

A prismatic retroreflective article and a method for making same. The retroreflective article can include a transparent polymeric body portion, an optical layer coupled to the body portion, and an image layer coupled to the body portion opposite the optical layer. The image layer can define imaged portions and non-imaged portions of the prismatic retroreflective article. The image layer can include cross-links formed between a polymer resin having hydroxyl functional groups and a cross-linking agent having isocyanate functional groups. The image layer can have a percent elongation of at least 80 percent and less than 200 percent. The method can include printing or coating an image layer onto to the body portion of the retroreflective sheeting opposite the optical layer, and cross-linking the image layer to form cross-links between the hydroxyl functional groups of the polymer resin and the isocyanate functional groups of the cross-linking agent.

Claims

1. A prismatic retroreflective article comprising:

a transparent polymeric body portion having an elastic modulus less than 13×

10⁸ Pa (1.3 GPa);

an optical layer comprising internally reflecting cube-corner optical elements, the optical layer having an elastic modulus greater than 14×

10⁸ Pa (1.4 GPa) and being coupled to the body portion; and

an image layer coupled to the body portion opposite the optical layer, the image layer defining an image having imaged portions and non-imaged portions, wherein the image layer forms an exterior layer of the prismatic retroreflective article in the imaged portions, the image layer including cross-links formed between a polymer resin having hydroxyl functional groups and a cross-linking agent having isocyanate functional groups, the polymer resin comprising at least one of a polyester and a vinyl copolymer.

2. The prismatic retroreflective article of claim 1, wherein the prismatic retroreflective article has a retroreflectivity of at least 330 cd/(lux·

m²) as measured according to ASTM E-810 test method or CIE 54.2;

2001 test method at 0.2 degree observation angle and +5 degree entrance angle, at 0 degrees and 90 degrees orientation angles.

3. The prismatic retroreflective article of claim 1, wherein the polymer resin comprises a vinyl copolymer.

4. The prismatic retroreflective article of claim 1, wherein the polymer resin comprises a vinyl copolymer, and wherein the polymer resin further comprises an acrylic resin.

5. The prismatic retroreflective article of claim 1, wherein the cross-linking agent comprises at least one of aliphatic isocyanates, aliphatic polyfunctional isocyanates, cycloaliphatic polyfunctional isocyanates, and combinations thereof.

6. The prismatic retroreflective article of claim 1, wherein the cross-linking agent comprises at least one of 1,6-hexamethylene diisocyanate (HDI), 1,4-tetramethylene diisocyanate, and combinations thereof.

7. The prismatic retroreflective article of claim 1, wherein the image layer has a percent elongation of at least 80 percent.

8. The prismatic retroreflective article of claim 1, wherein the image layer has a percent elongation of less than 200 percent.

9. The prismatic retroreflective article of claim 1, wherein the image layer has a percent elongation of at least 100 percent and less than 150 percent.

10. The prismatic retroreflective article of claim 1, wherein the vinyl copolymer comprises a vinyl acetate-vinyl alcohol-vinyl chloride copolymer.

11. The prismatic retroreflective article of claim 1, further comprising a barrier layer disposed between the image layer and the body portion, such that the barrier layer forms an exterior layer of the prismatic retroreflective article in the non-imaged portions.

12. The prismatic retroreflective article of claim 11, wherein the barrier layer comprises at least one of polyurethanes, polyurethane acrylates, and polyacrylates.

13. The prismatic retroreflective article of claim 1, wherein the amount of cross-linking agent is at least 3% and no more than 45%, based on the weight of the image layer.

14. The prismatic retroreflective article of claim 1, wherein the amount of cross-linking agent is at least 15% and no more than 30%, based on the weight of the image layer.

15. A method of making a prismatic retroreflective article, the method comprising:

providing retroreflective sheeting, the retroreflective sheeting including

a body portion having an elastic modulus of less than 13×

10⁸ Pa, and

an optical layer comprising internally reflecting cube-corner optical elements, the optical layer having an elastic modulus of greater than 14×

10⁸ Pa and being coupled to the body portion;

printing or coating an image layer onto to the body portion of the retroreflective sheeting opposite the optical layer, the image layer comprising

a polymer resin comprising at least one of a polyester and a vinyl copolymer, the polymer resin having hydroxyl functional groups, and

a cross-linking agent having isocyanate functional groups; and

cross-linking the image layer to form cross-links between the hydroxyl functional groups of the polymer resin and the isocyanate functional groups of the cross-linking agent.

16. The method of claim 15, further comprising drying the image layer via oven drying.

17. The method of claim 15, further comprising drying the image layer via air drying.

18. The method of claim 15, wherein the prismatic retroreflective article has a retroreflectivity of at least 330 cd/(lux·

m²) as measured according to ASTM E-810 test method or CIE 54.2;

2001 test method at 0.2 degree observation angle and +5 degree entrance angle, at 0 degrees and 90 degrees orientation angles.

19. The method of claim 15, wherein the polymer resin comprises a vinyl copolymer.

20. The method of claim 15, wherein the polymer resin comprises a vinyl copolymer, and the polymer resin further comprises an acrylic resin.

21. The method of claim 15, wherein cross-linking the image layer includes cross-linking the image layer to form an image layer having a percent elongation of at least 80 percent.

22. The method of claim 15, wherein cross-linking the image layer includes cross-linking the image layer to form an image layer having a percent elongation of less than 200 percent.

23. The method of claim 15, wherein cross-linking the image layer includes cross-linking the image layer to form an image layer having a percent elongation of at least 100 percent and less than 150 percent.

24. The method of claim 15, wherein printing or coating the image layer includes forming an image having imaged portions and non-imaged portions, and wherein the image layer forms an exterior layer of the prismatic retroreflective article in the imaged portions.

25. The method of claim 15, wherein the retroreflective sheeting further comprises a barrier layer coupled to the body portion opposite the optical layer, and wherein printing or coating the image layer includes forming an image having imaged portions and non-imaged portions, such that the image layer forms the exterior layer of the prismatic retroreflective article in the imaged portions and the barrier layer forms the exterior layer of the prismatic retroreflective article in the non-imaged portions.

26. The method of claim 15, wherein the retroreflective sheeting further comprises a barrier layer comprising cross-linked polyurethane chemistries coupled to the body portion opposite the optical layer.

27. The method of claim 15, wherein printing or coating an image layer includes printing or coating an ink system that comprises at least 2 parts cross-linking agent per 100 parts ink system, and no more than 15 parts cross-linking agent per 100 parts ink system.

28. The method of claim 15, wherein printing or coating an image layer includes printing or coating an image layer that comprises at least 3% cross-linking agent solids to image layer solids, and no more than 45% cross-linking agent solids to image layer solids.

29. The method of claim 15, wherein cross-linking the image layer comprises chemically cross-linking the image layer.

30. A prismatic retroreflective article comprising:

a transparent polymeric body portion having an elastic modulus less than 13×

10⁸ Pa (1.3 GPa);

an optical layer comprising internally reflecting cube-corner optical elements, the optical layer having an elastic modulus greater than 14×

10⁸ Pa (1.4 GPa) and being coupled to the body portion; and

an image layer coupled to the body portion opposite the optical layer, the image layer having a percent elongation of at least 80 percent and less than 200 percent, the image layer including cross-links formed between a polymer resin having hydroxyl functional groups and a cross-linking agent having isocyanate functional groups, the polymer resin comprising at least one of a polyester and a vinyl copolymer.