Ultraviolet protected electrochemichromic rearview mirror

• US 5,355,245 A
• Filed: 06/25/1993
• Issued: 10/11/1994
• Est. Priority Date: 02/12/1988
• Status: Expired due to Term

• Current Assignee: Donnelly Corporation (Magna International Incorporated)
• Original Assignee: Donnelly Corporation (Magna International Incorporated)
• Inventors: Lynam, Niall R.
• Primary Examiner(s): Sikes, William L.
• Assistant Examiner(s): PARSONS, DAVID
• Application Number:
  US08/082,882
• Time in Patent Office: 473 Days
• Field of Search: 359/602, 359/608, 359/614, 359/870, 359/884, 359/272, 359/265, 359/267, 359/268, 359/270, 359/274, 359/275, 359/361, 359/350
• US Class Current: 359/267
• CPC Class Codes: B32B 17/10005 laminated safety glass or glazing
• CPC Class Codes: B32B 17/10036 comprising two outer glass sheets
• CPC Class Codes: B32B 17/10064 comprising at least two glass sheets, only one of which being an outer layer
• CPC Class Codes: B32B 17/10174 Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
• CPC Class Codes: B32B 17/10302 Edge sealing
• CPC Class Codes: B32B 17/1033 Laminated safety glass or glazing containing temporary protective coatings or layers
• CPC Class Codes: B32B 17/10339 Specific parts of the laminated safety glass or glazing being colored or tinted tinted glass sheet B32B17/1011; tinted interlayer B32B17/10651
• CPC Class Codes: B32B 17/10513 Electrochromic layer
• CPC Class Codes: B32B 17/10761 containing vinyl acetal
• CPC Class Codes: B32B 2367/00 Polyesters, e.g. PET, i.e. polyethylene terephthalate
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B60J 3/04 adjustable in transparency
• CPC Class Codes: B60R 1/088 using a cell of electrically changeable optical characteristic, e.g. liquid-crystal or electrochromic mirrors
• CPC Class Codes: G02F 1/1333 Constructional arrangements; Manufacturing methodsG02F1/135, G02F1/136 take precedence
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
• CPC Class Codes: G02F 1/1533 structural features not otherwise provided for
• CPC Class Codes: G02F 1/157 Structural association of cells with optical devices, e.g. reflectors or illuminating devices
• CPC Class Codes: G02F 2001/1536 additional, e.g. protective, layer inside the cell

Abstract

An ultraviolet protected, electrochemichromic rearview mirror assembly incorporating an electrochemichromic medium with reduced ultraviolet degradation is disclosed which may incorporate tinted means such as a specialized glass, a dye, and/or a polymer layer.

Claims

1. An ultraviolet radiation protected electrochemichromic rearview mirror assembly comprising:

first and second spaced, optically transparent elements, said elements each having front and rear surfaces and defining a space between the rear surface of said first element and the front surface of said second element;

an electrochemichromic medium confined in said space whose light transmittance is variable upon the application of an electric field thereto; and

means for applying an electric field to said electrochemichromic medium to cause variation in the light transmittance of said medium;

said electrochemichromic medium comprising at least 1.2% by weight to volume of one of a) an ultraviolet radiation reducing additive in solution in said electrochemichromic medium and b) a mixture of at least two ultraviolet radiation reducing additives in solution in said electrochemichromic medium, said additive and additives comprising said mixture being selected from the group consisting of benzophenones, cinnamic acid derivatives, esters of benzoin acids, salicylic acid, terephthalic and isophthalic acids with resorcinol and phenols, pentamethyl piperidine derivatives, salicylates, benzotriazoles, cyanoacrylates, benzilidenes, malonates, oxalanilides, nickel chelates and hindered amines, wherein said additive and said mixture of at least two additives does not affect the function of said electrochemichromic medium and does not oxidize or reduce in said electrochemichromic rearview mirror assembly during operation thereof.

2. The electrochemichromic rearview mirror assembly of claim 1 wherein said ultraviolet radiation reducing additive and said mixture of at least two additives includes a benzophenone.

3. The electrochemichromic rearview mirror assembly of claim 1 wherein said ultraviolet radiation reducing additive and said mixture of at least two additives includes a cyanoacrylate.

4. The electrochemichromic rearview mirror assembly of claim 1 wherein said ultraviolet radiation reducing additive and said mixture of at least two additives includes an oxalanilide.

5. The electrochemichromic rearview mirror assembly of claim 1 wherein said electrochemichromic medium comprises at least 12.5% by weight to volume of said ultraviolet radiation reducing additive and said mixture of at least two additives.

6. The electrochemichromic rearview mirror assembly of claim 5 wherein said ultraviolet radiation reducing additive and said mixture of at least two additives includes a benzophenone.

7. The electrochemichromic rearview mirror assembly of claim 5 wherein said ultraviolet radiation reducing additive and said mixture of at least two additives includes a cyanoacrylate.

8. The electrochemichromic rearview mirror assembly of claim 5 wherein said ultraviolet radiation reducing additive and said mixture of at least two additives includes an oxalanilide.

9. The electrochemichromic rearview mirror assembly of claim 1 wherein said electrochemichromic medium comprises at least one electrochemichromic compound selected from the group consisting of viologens and phenylenediamines.

10. The electrochemichromic rearview mirror assembly of claim 9 wherein said electrochemichromic compound is a viologen.

11. The electrochemichromic rearview mirror assembly of claim 10 wherein said viologen is selected from the group consisting of methylviologen, ethylviologen, benzylviologen and heptylviologen.

12. The electrochemichromic rearview mirror assembly of claim 11 wherein said viologen is heptylviologen.

13. The electrochemichromic rearview mirror assembly of claim 9 wherein said electrochemichromic compound is a phenylenediamine.

14. The electrochemichromic rearview mirror assembly of claim 13 wherein said phenylenediamine is N,N,N'"'"',N'"'"'-tetramethylphenylenediamine.

15. The electrochemichromic rearview mirror assembly of claim 1 wherein said electrochemichromic medium comprises at least one electrochemichromic compound which is a phenazine.

16. The electrochemichromic rearview mirror assembly of claim 15 wherein said phenazine is 5,10-dimethyl-5,10-dihydrophenazine.

17. The electrochemichromic rearview mirror assembly of claim 1 wherein said ultraviolet radiation reducing additive and said mixture of at least two additives is dissolved in a solvent comprising propylene carbonate.

18. The electrochemichromic rearview mirror assembly of claim 1 wherein said means for applying an electric field includes a substantially transparent conductive coating consisting of indium tin oxide on at least one of said rear surface of said first element and said front surface of said second element.

19. The electrochemichromic rearview mirror assembly of claim 1 wherein said means for applying an electric field includes a substantially transparent conductive coating consisting of doped tin oxide on at least one of said rear surface of said first element and said front surface of said second element.

20. The electrochemichromic rearview mirror assembly of claim 1 wherein said means for applying an electric field includes a substantially transparent conductive coating consisting of doped zinc oxide on at least one of said rear surface of said first element and said front surface of said second element.

21. The electrochemichromic rearview mirror assembly of claim 1 wherein at least one of said optically transparent elements is formed from a specialized glass selected from the group consisting of glass having a higher iron oxide content than conventional soda lime window glass, said iron oxide content being at least 0.2% to 0.9% by weight, and glass having a higher cerium oxide content than conventional soda lime window glass, said cerium oxide content being at least 0.2% to 0.9% by weight.

22. The electrochemichromic rearview mirror assembly of claim 1 further comprising spectrally selective absorbing means for absorbing more light in those regions of the visible spectrum from about 560 nanometers to about 780 nanometers than is absorbed in those regions of the visible spectrum from about 400 nanometers to about 560 nanometers.

23. The electrochemichromic rearview mirror assembly of claim 1 wherein at least one of said elements is formed from specialized glass which absorbs substantially more visible light in wavelengths higher than about 560 nanometers than in other regions of the visible spectrum and has a blue tint.

24. The electrochemichromic rearview mirror assembly of claim 23 wherein said rearview mirror assembly is an outside mirror on a vehicle.

25. The electrochemichromic rearview mirror assembly of claim 1 wherein at least one of said elements is formed from specialized glass which absorbs substantially more visible light in wavelengths higher than about 560 nanometers than in other regions of the visible spectrum and has a green tint.

26. The electrochemichromic rearview mirror assembly of claim 25 wherein said rearview mirror assembly is an outside mirror on a vehicle.

27. The electrochemichromic rearview mirror assembly of claim 1 wherein said electrochemichromic medium comprises a blue, electrochemically inert dye.

28. The electrochemichromic rearview mirror assembly of claim 1 wherein said assembly further includes ultraviolet radiation reducing means for transmitting less ultraviolet radiation than conventional soda lime window glass of thickness about 2 millimeters coated with indium tin oxide of a thickness of about 1500 angstroms.

29. The electrochemichromic rearview mirror assembly of claim 28 wherein said ultraviolet radiation reducing means includes an ultraviolet radiation reducing coating selected from the group consisting of paint coatings, lacquer coatings, and thin film coatings.

30. The electrochemichromic rearview mirror assembly of claim 29 wherein said ultraviolet radiation reducing coating exhibits a cut-off in the transmission of ultraviolet radiation at a wavelength above about 295 nanometers.

31. The electrochemichromic rearview mirror assembly of claim 1 wherein said electrochemichromic medium is introduced into said assembly by means of vacuum backfilling.

32. The electrochemichromic rearview mirror assembly of claim 1 further comprising safety means incorporated in said assembly for preventing fragment scattering, lacerative injuries and contact with said electrochemichromic medium should one of said elements break or crack.

33. An ultraviolet radiation protected electrochemichromic rearview mirror assembly comprising:

first and second spaced, optically transparent elements, said elements each having front and rear surfaces and defining a space between the rear surface of said first element and the front surface of said second element;

an electrochemichromic solution confined in said space whose light transmittance is variable upon the application of an electric field thereto;

said electrochemichromic solution comprising (i) a solvent;

(ii) at least one electrochemichromic compound in solution in said solvent; and

(iii) a cyanoacrylate compound in solution in said solvent effective to reduce ultraviolet radiation passing through said solution; and

means for applying an electric field to said electrochemichromic solution to cause variation in the light transmittance of said solution.

34. An ultraviolet radiation protected electrochemichromic rearview mirror assembly comprising:

first and second spaced, optically transparent elements, said elements each having front and rear surfaces and defining a space between the rear surface of said first element and the front surface of said second element;

an electrochemichromic solution confined in said space whose light transmittance is variable upon the application of an electric field thereto;

said electrochemichromic solution comprising (i) a solvent;

(ii) at least one electrochemichromic compound in solution in said solvent; and

(iii) a benzophenone compound in solution in said solvent effective to reduce ultraviolet radiation passing through said solution; and

means for applying an electric field to said electrochemichromic solution to cause variation in the light transmittance of said solution.

35. An ultraviolet radiation protected electrochemichromic rearview mirror assembly comprising:

first and second spaced, optically transparent elements, said elements each having front and rear surfaces and defining a space between the rear surface of said first element and the front surface of said second element;

an electrochemichromic solution confined in said space whose light transmittance is variable upon the application of an electric field thereto;

said electrochemichromic solution comprising (i) a solvent;

(ii) at least one electrochemichromic compound in solution in said-solvent; and

(iii) an oxalanilide compound in solution in said solvent effective to reduce ultraviolet radiation passing through said solution; and

means for applying an electric field to said electrochemichromic solution to cause variation in the light transmittance of said solution.

36. A reduced ultraviolet radiation transmitting, electrochemichromic rearview mirror assembly comprising:

first and second spaced, optically transparent elements mounted in a mirror case, said elements each having front and rear surfaces and defining a space between the rear surface of said first element and the front surface of said second element;

an electrochemichromic medium confined in said space whose light transmittance is variable upon the application of an electric field thereto;

means for applying an electric field to said electrochemichromic medium to cause variation in the light reflectance of said mirror assembly from a high reflectance state to a dimmed reflectance state;

a reflective coating on one surface of said second element adapted to reflect light incident thereon through said first element and said electrochemichromic medium; and

ultraviolet reducing means incorporated in said assembly for reducing ultraviolet radiation degradation of said electrochemichromic medium in said assembly;

said assembly including tinted means for causing said high reflectance state to have a blue tint in the visible light which is reflected;

said tinted means comprising at least one of said elements being a panel formed from specialized glass which absorbs more light in those regions of the visible spectrum from about 560 nanometers to about 780 nanometers than is absorbed in those regions of the visible spectrum from about 400 nanometers to about 560 nanometers.

37. The mirror assembly of claim 36 wherein said specialized glass absorbs more visible light in wavelengths higher than about 560 nanometers than in other regions of the visible spectrum and has a blue tint.

38. The mirror assembly of claim 36 wherein said panel is a blue tinted float glass incorporating added iron content.

39. The mirror assembly of claim 36 wherein said ultraviolet radiation reducing means comprises at least one ultraviolet radiation reducing additive in solution with said electrochemichromic medium, said additive stabilizing said medium against degradation from ultraviolet radiation and selected from the group consisting of benozophenones, cinnamic acid derivatives, esters of benzoin acids, salicylic acid, terephthalic and isophthalic acids with resorcinol and phenols, pentamethyl piperidine derivatives, salicylates, benzotriazoles, cyanoacrylates, benzilidenes, malonates and oxalanilides, nickel chelates and hindered amines.

40. The mirror assembly of claim 39 wherein said ultraviolet reducing additive is in solution with said electrochemichromic medium to a concentration greater than 12.5% by weight to volume.

41. The mirror assembly of claim 37 wherein said tinted means further comprises a blue electrochemically inert dye in solution with said electrochemichromic medium.

42. The mirror assembly of claim 41 wherein said blue dye is a phthalocyanine dye.

43. The mirror assembly of claim 36 wherein said specialized glass has a thickness of at least 2.3 mm.

44. The mirror assembly of claim 36 wherein said rearview mirror assembly is an outside mirror on a vehicle.

45. The mirror assembly of claim 36 wherein said high reflectance state is achieved when said electric field is at a zero potential.

46. The mirror assembly of claim 36 wherein said reflective coating is silver.

53. The mirror assembly of claim 46 wherein said rearview mirror assembly is an outside mirror on a vehicle.

47. An ultraviolet radiation protected electrochemichromic rearview mirror assembly comprising:

first and second spaced, optically transparent elements, said elements each having front and rear surfaces and defining a space between the rear surface of said first element and the front surface of said second element;

an electrochemichromic solution confined in said space whose light transmittance is variable upon the application of an electric field thereto;

reflective coating on one surface of said second element adapted to reflect light incident thereon through said first element and said electrochemichromic solution;

said electrochemichromic solution comprising (i) a solvent;

(ii) at least one electrochemichromic compound in solution in said solvent; and

(iii) an ultraviolet radiation reducing additive in solution in said solvent effective to reduce ultraviolet radiation passing through said solution;

means for applying an electric field to said electrochemichromic solution to cause variation in the light reflectance of said mirror assembly from a high reflectance state to a dimmed reflectance state; and

said assembly including tinted means for causing said high reflectance state to have a blue tint in the visible light which is reflected.

48. The mirror assembly of claim 47 wherein said tinted means includes a blue glass member.

49. The mirror assembly of claim 47 wherein said tinted means includes a blue tinted polymer layer.

50. The mirror assembly of claim 47 wherein said tinted means includes a blue electrochemically inert dye in solution in said solvent.

51. The mirror assembly of claim 47 wherein said high reflectance state is achieved when said electric field is at a zero potential.

52. The mirror assembly of claim 47 wherein said reflective coating is silver.

54. A reduced ultraviolet radiation transmitting, electrochemichromic rearview mirror assembly comprising:

first and second spaced, optically transparent elements mounted in a mirror case, said elements each having front and rear surfaces and defining a space between the rear surface of said first element and the front surface of said second element;

an electrochemichromic medium confined in said space whose light transmittance is variable upon the application of an electric field thereto;

means for applying an electric field to said electrochemichromic medium to cause variation in the light reflectance of said mirror assembly from a high reflectance state to a dimmed reflectance state;

a reflective coating on one surface of said second element adapted to reflect light incident thereon through said first element and said electrochemichromic medium; and

ultraviolet radiation reducing means incorporated in said assembly for reducing ultraviolet radiation degradation of said electrochemichromic medium in said assembly;

said assembly including tinted means for causing said high reflectance state to have a blue tint in the visible light which is reflected;

said ultraviolet radiation reducing means selected from the group consisting of (i) an ultraviolet radiation reducing additive in solution with said electrochemichromic medium and (ii) a specialized glass selected from the group consisting of glass having a higher iron oxide content than conventional soda lime window glass, said iron oxide content being at least 0.2% to 0.9% by weight, and glass having a higher cerium oxide content than conventional soda lime window glass, said cerium oxide content being at least 0.2% to 0.9% by weight.

55. The mirror assembly of claim 54 wherein said tinted means includes a blue glass member.

56. The mirror assembly of claim 54 wherein said tinted means includes a blue tinted polymer layer.

57. The mirror assembly of claim 54 wherein said tinted means includes a blue electrochemically inert dye in solution with said electrochemichromic medium.

58. The mirror assembly of claim 54 wherein said reflective coating is silver.

59. The mirror assembly of claim 54 wherein said specialized glass exhibits a cut off in the transmission of ultraviolet radiation at a wavelength above about 330 nanometers.

60. The mirror assembly of claim 54 wherein said rearview mirror assembly is an outside mirror on a vehicle.

61. The mirror assembly of claim 54 wherein said ultraviolet radiation reducing additive is selected from the group consisting of benozophenones, cinnamic acid derivatives, esters of benzoin acids, salicylic acid, terephthalic and isophthalic acids with resorcinol and phenols, pentamethyl piperidine derivatives, salicylates, benzotriazoles, cyanoacrylates, benzilidenes, malonates and oxalanilides, nickel chelates and hindered amines.

62. The mirror assembly of claim 54 wherein said high reflectance state is achieved when said electric field is at a zero potential.