Electrochromic display device and compositions useful in making such devices

1. A display device comprising at least two electrodes, and positioned between those two electrodes in such a manner to be visible a composition comprising:

(a) a non-aqueous compound that undergoes a reversible electron transfer reaction with a subsequent change in its protic state resulting in a pH gradient in the device,

(b) at least one indicator dye, and

(c) a charge transport material.

2. A display device comprising at least two electrodes, one being anodic and one being cathodic, and positioned between those two electrodes in such a manner to be visible a composition comprising:

(a) a compound that undergoes a reversible electron transfer reaction with a subsequent change in its protic state resulting in a pH gradient in the device,

(b) at least one indicator dye, and

(c) a charge transport material

wherein components (a), (b) and (c) are different from one another and component (a) preferentially undergoes the electron transfer reaction at the electrode surface.

3. The device of claim 2 wherein the preferential electron transfer reaction occurs at an electrode surface.

4. The device of claim 2 wherein the electrode potential of component (a) is less than the electrode potential for the other components of identical sign in a half cell reaction.

5. The device of claim 2 characterized in that component (a) is present in an amount from 0.01 to 15 weight percent by weight, component (b) is present in an amount from 0.01 to 15 percent by weight, component (c) is present in an amount from 5 to 99.98 percent by weight and further comprising a matrix material component (d) present in an amount from 0 to 90 percent by weight, an opacifier component (e) present in an a amount from 0 to 40 percent by weight, and component (f) a secondary redox couple present in an amount from 0 to 15 weight percent by weight.

6. The device of claim 2 wherein component (a) is selected from the group consisting of iodates, bromates, sulfates, metal hydroxides, phosphates, ketones, aldehydes, quinones, quinolines, sulfur compounds, hydroxybenzenes, carboxylic acids and amines.

7. The device of claim 2 wherein component (b) comprises one or more indicator dyes or their derivatives selected from the group consisting of phenylthalein, bromocrescol purple, phenol red, ethyl red, quinaldine red, thymolthalein, thymol blue, malachite green, crystal violet, methyl violet 2B, xylenol blue, cresol red, phyloxine B, congo red, methyl orange, bromochlorophenol blue, alizarin red, chlorophenol red, 4-nitrophenol, nile blue A, aniline blue, indigo carmine, and bromothymol blue.

8. The device of claim 2 wherein component (c) comprises a salt and a solvent selected from the group consisting of propylene carbonate, dimethyl formamide, N-methyl pyrrolidinone, acetonitrile, dimethylsulfozide, alcohols, pyridine and 1,4-dioxane, ethylene glycol, propylene glycol or polyethylene glycol.

9. The device of claim 2 wherein component (c) is a solid electrolyte.

10. The device of claim 2 wherein the anodic electrode and the cathodic electrode are located on separate substrates and form electrode substrate composites and at least one of the electrode substrate composites is transparent.

11. The device of claim 2 wherein at least one of the electrodes or the composition is patterned to form an image when a voltage is passed across the composition.

12. The device of claim 5 wherein the matrix component (d) comprises a polymer or other viscosity modifier and the matrix is blended with the other components of the composition.

13. The device of claim 5 wherein the opacifier is selected from the group consisting of titanium dioxide, latexes, and barium titanate.

14. A display device comprising at least two electrodes, one being anodic and one being cathodic, and positioned between those two electrodes in such a manner to be visible a composition comprising:

(a) a compound that undergoes a reversible redox reaction to generate a pH gradient between the two electrodes,

(b) at least one indicator dye, and

(c) a charge transport material wherein components (a), (b) and (c) are different from one another and the standard reduction potential of component (a) is less than the standard reduction potential for the other components.

15. The device of claim 14 characterized in that component (a) is present in an amount from 0.01 to 15 weight percent by weight, component (b) is present in an amount from 0.01 to 15 percent by weight, component (c) is present in an amount from 5 to 99.98 percent by weight and further comprising a matrix material component (d) present in an amount from 0 to 90 percent by weight, an opacifier component (e) present in an amount from 0 to 40 percent by weight, and a secondary redox couple component (f) present in an amount from 0 to 15 weight percent by weight.

16. The device of claim 14 wherein component (a) is selected from the group consisting of iodates, bromates, sulfates, metal hydroxides, phosphates, ketones, aldehydes, quinones, quinolines, sulfur compounds, hydroxybenzenes, carboxylic acids and amines.

17. The device of claim 14 wherein component (b) comprises one or more indicator dyes or their derivatives selected from the group consisting of phenylthalein, bromocrescol purple, phenol red, ethyl red, quinaldine red, thymolthalein, thymol blue, malachite green, crystal violet, methyl violet 2B, xylenol blue, cresol red, phyloxine B, congo red, methyl orange, bromochlorophenol blue, alizarin red, chlorophenol red, 4-nitrophenol, nile blue A, aniline blue, indigo carmine, and bromothymol blue.

18. The device of claim 14 wherein component (c) is a solid electrolyte.

19. The device of claim 14 wherein the anodic electrode and the cathodic electrode are each located on separate substrates and form electrode substrate composites and at least one of the electrode substrate composites is transparent.

20. The device of claim 14 wherein at least one of the electrodes or the composition is patterned to form an image when a voltage is passed across the composition.

21. The device of claim 14 wherein the matrix component (d) comprises a polymer or other viscosity modifier and the matrix is blended with the other components of the composition.

22. The device of claim 14 wherein the opacifier is selected from the group consisting of titanium dioxide, latexes, and barium titanate.

23. A composition comprising:

(a) a compound that undergoes a electron transfer reaction with subsequent change in its protic state

(b) at least one indicator dye which changes color when a change in pH occurs, and

(c) an ionically conductive material and optionally component (d), a matrix material, wherein components (a), (b), (c) and (d) are different from one another and component (a) preferentially undergoes the electron transfer reaction when a charge is applied to the composition and provided that if (c) is a fluid the composition further comprises the matrix material (d).

24. The composition of claim 23 characterized in that component (a) is present in an amount from 0.01 to 15 weight percent, component (b) is present in an amount from 0.01 to 15 weight percent, component (c) is present in an amount from 5 to 99.98 weight percent, component (d) is present in an amount from 0 to 90 weight percent, an opacifier component (e) is present in an amount from 0 to 75 weight percent based on total weight of the composition and component (f) a secondary redox couple present in an amount of 0 to 15 weight percent.

25. The composition of claim 23 wherein component (a) is selected from the group consisting of iodates, bromates, sulfates, metal hydroxides, phosphates, ketones, aldehydes, quinones, quinolines, sulfur compounds, hydroxybenzenes, carboxylic acids, and amines.

26. The composition of claim 23 wherein component (b) comprises one or more indicator dyes selected from but not limited to the group consisting of phenylthalein, bromocrescol purple, phenol red, ethyl red, quinaldine red, thymolthalein, thymol blue, malachite green, crystal violet, methyl violet 2B, xylenol blue, cresol red, phyloxine B, congo red, methyl orange, bromochlorophenol blue, alizarin red, chlorophenol red, 4-nitrophenol, nile blue A, aniline blue, indigo carmine, and bromothymol blue.

27. The composition of claim 23 wherein component (c) is a solid electrolyte.

28. The composition of claim 23 wherein the matrix (d) comprises a polymer or other viscosity modifier and the matrix is blended with the other components of the composition.

29. The composition of claim 23 wherein component (e) one opacifier is selected from the group consisting of titanium dioxide, latexes, and barium titanate.

30. The composition of claim 23 wherein the component (f) the secondary redox couple is selected from the group consisting of iodates, bromates, sulfates, metal hydroxides, phosphates, ketones, aldehydes, quinones, quinolines, sulfur compounds, hydroxybenzenes, carboxylic acids, polyoxometallates, and amines.

31. A composition comprising:

(a) a compound that undergoes a reversible redox reaction to generate a pH gradient,

(b) at least one indicator dye,

(c) a charge transport material, and

(d) optionally, a matrix material wherein components (a), (b), (c) and (d) are different from one another, the standard reduction potential of component (a) is less than the standard reduction potential for the other components and provided that if (c) is a fluid the composition further comprises the matrix material (d).

32. The composition of claim 31 characterized in that component (a) is present in an amount from 0.01 to 15 weight percent, component (b) is present in an amount from 0.01 to 15 weight percent, component (c) is present in an amount from 5 to 99.98 weight percent, component (d) is present in an amount from 0 to 90 weight percent, an opacifier component (e) is present in an amount from 0 to 75 weight percent based on total weight of the composition and component (f) a secondary redox couple present in an amount of 0 to 15 weight percent.

33. The composition of claim 31 wherein component (a) is selected from the group consisting of iodates, bromates, sulfates, metal hydroxides, phosphates, ketones, aldehydes, quinones, quinolines, sulfur compounds, hydroxybenzenes, carboxylic acids, and amines.

34. The composition of claim 31 wherein component (b) comprises one or more indicator dyes selected from but not limited to the group consisting of phenylthalein, bromocrescol purple, phenol red, ethyl red, quinaldine red, thymolthalein, thymol blue, malachite green, crystal violet, methyl violet 2B, xylenol blue, cresol red, phyloxine B, congo red, methyl orange, bromochlorophenol blue, alizarin red, chlorophenol red, 4-nitrophenol, nile blue A, aniline blue, indigo carmine, and bromothymol blue.

35. The composition of claim 31 wherein component (c) is a solid electrolyte.

36. The composition of claim 31 wherein the matrix (d) comprises a polymer or other viscosity modifier and the matrix is blended with the other components of the composition.

37. The composition of claim 31 wherein component (e), the opacifier is selected from the group consisting of titanium dioxide, latexes, and barium titanate.

38. The composition of claim 31 wherein component (f) the secondary redox couple is selected from the group consisting of iodates, bromates, sulfates, metal hydroxides, phosphates, ketones, aldehydes, quinones, quinolines, sulfur compounds, hydroxybenzenes, carboxylic acids, polyoxometallates, and amines.

39. An article comprising a film further comprising the composition of claim 23 located on a substrate.

40. The article of claim 39 comprising a second substrate on the side of the film opposite the first substrate wherein at least one of the substrates is a release layer.

41. The article of claim 40 wherein the film thickness is from 25-100 um.

42. An article comprising a film further comprising the composition of claim 31 located on a substrate.

43. The article of claim 42 comprising a second substrate on the side of the film opposite the first substrate wherein at least one of the substrates is a release layer.

44. The article of claim 42 wherein the film thickness is from 25-100 um.