Variable reflectance motor vehicle mirror

• US 5,128,799 A
• Filed: 09/17/1991
• Issued: 07/07/1992
• Est. Priority Date: 03/31/1986
• Status: Expired due to Term

• Current Assignee: Gentex Corporation
• Original Assignee: Gentex Corporation
• Inventors: Byker, Harlan J.
• Primary Examiner(s): LaRoche, Eugene R.
• Assistant Examiner(s): Lester, Evelyn A.
• Application Number:
  US07/762,732
• Time in Patent Office: 294 Days
• Field of Search: 350/357, 350/601, 359/265, 359/270, 359/272, 359/274, 359/275, 359/267, 359/839
• US Class Current: 359/265
• CPC Class Codes: B60R 1/088 using a cell of electrically changeable optical characteristic, e.g. liquid-crystal or electrochromic mirrors
• CPC Class Codes: C07D 498/04 Ortho-condensed systems
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G01R 13/40 using modulation of a light beam otherwise than by mechanical displacement, e.g. by Kerr effect visual indication of correct tuning H03J3/14
• 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 2001/1502 complementary cell
• CPC Class Codes: G02F 2001/15145 the electrochromic layer comprises a mixture of anodic and cathodic compounds

Abstract

The present invention provides variable reflectance motor vehicle mirrors wherein the component of variable transmittance is a single-compartment, self-erasing, solution-phase electrochromic device.

Claims

1. A variable reflectance mirror for a motor vehicle comprising as the variable transmittance component a single-compartment, self-erasing, solution-phase electrochromic device wherein the sheet resistance of a transparent electrode layer of the electrochromic device is 1-40 ohms per square.

2. A mirror according to claim 1 which has a range of reflectance from greater than 70% to less than 10%.

3. A mirror according to claim 2 wherein the electrochromic device is gray-scale controllable over a range of reflectance by applying potential differences between the electrode layers o the device of 0.2 volts to 1.5 volts.

4. A mirror according to claim 3 wherein the electrochromic device comprises two planar parallel, spaced-apart electrode layers, to which DC current is provided through leads connected to a DC power source, said device oriented so that the lead connecting the electrode layer, which is the anode, to the power source is higher in elevation than the lead connecting the electrode, which is the cathode, to the power source.

5. A mirror according to claim 2 wherein reflectance is capable of being reduced from greater than 70% difference of less than 1.4 volts between the electrode layers of the electrochromic device.

6. A mirror according to claim 2 wherein the electrochromic device comprises two planar, parallel, spaced-apart electrode layers, to which DC current is provided through leads connected to a DC power source, said device oriented so that the lead connecting the electrode layer, which is the anode, to the power source is higher in elevation than the lead connecting the electrode, which is the cathode, to the power source.

7. A mirror according to claim 1 wherein the electrochromic device is gray-scale controllable over a range of reflectance by applying potential differences between the electrode layers of the device of 0.2 volts to 1.5 volts.

8. A mirror according to claim 1 wherein the electrochromic device comprises two planar, parallel, spaced-apart electrode layers, to which DC current is provided through leads connected to a DC power source, said device oriented so that the lead connecting the electrode layer, which is the anode, to the power source is higher in elevation than the lead connecting the electrode, which is the cathode, to the power source.

9. A mirror according to claim 1 wherein the electrochromic device comprises, as the medium of reversibly variable transmittance to light reflected by the mirror, a solution which comprises:

(A) a solvent;

(B) at least one cathodic electrochromic compound which, in a voltammogram done in the solvent at room temperature, displays at least two chemically reversible reduction waves, with the first of said reductions accompanied by an increase in molar extinction coefficient at at least one wavelength in the visible range;

(C) at least one anodic electrochromic compound which, in a voltammogram done in the solvent at room temperature, displays at least two chemically reversible oxidation waves, with the first of said oxidations accompanied by an increase in molar extinction coefficient at at least one wavelength in the visible range; and

(D) if all cathodic and anodic compounds in their zero-potential equilibrium states in the solution are not ionic, an inert current carrying electrolyte.

10. A mirror according to claim 9 wherein, in the solution of reversibly variable transmittance,

(A) the solvent is liquid at room temperature and selected from propylene carbonate gamma-butyrolactone, gamma-valerolactone, and any homogeneous mixture that is liquid at room temperature of any two or more of said solvents or any one or more of said solvents with ethylene carbonate;

(B) the cathodic compounds are selected from

(i) compounds of Formula II ##STR13## wherein R₂₁ and R₂₂ are the same or different and are each selected from alkyl to 1 to 10 carbon atoms, phenyl optionally substituted at any one position with chloride, bromide, iodide, cyano, or an alkyl group of 1 to 4 carbon atoms, and benzyl, wherein the phenyl group of the benzyl group is optionally substituted at any one position with chloride, bromide, iodide, cyano, or an alkyl group of 1 to 4 carbon atoms; and

wherein X₂₃ ^- and X₂₄ ^- are the same or different and are each selected from chloride, bromide, iodide, BF₄^-,PF₆^-, AsF₆ -, ClO₄^- and NO₃^-;

and

(ii) compounds of Formula III ##STR14## wherein R₂₁ and R₂₂ are the same or different and are defined as above for the compound of Formula II, R₃₁ is alkylene of 1 to 10 carbon atoms, and X₃₁^-, X₃₂^-, X₃₃^-, X₃₄^-, are the same or different and are each selected from chloride, bromide, iodide, BF₄^-, PF₆^-, AsF₆^-, ClO₄^- and NO₃^- ;

(C) the anodic compounds are selected from

(i) compounds of Formula IV ##STR15## wherein R₄₁, R₄₂, R₄₃ and R₄₄ are the same or different and are each selected from hydrogen, alkyl of 1 to 10 carbon atoms, phenyl optionally substituted at any one position with chloride, bromide, iodide, cyano, or an alkyl group of 1 to 4 carbon atoms, and benzyl, wherein the phenyl moiety of the benzyl group is optionally substituted at any one position with chloride, bromide, iodide, cyano, or an alkyl group of 1 to 4 carbon atoms.

(ii) compounds of Formula V ##STR16## wherein R₅₃ is the same as or different from R₅₅ and both R₅₃ and R₅₅ are selected from alkyl of 1 to 10 carbon atoms, phenyl optionally substituted at any one position with chloride, bromide, iodide, cyano, or alkyl of 1 to 4 carbon atoms, or benzyl, optionally substituted at any one position of the phenyl group with chloride, bromide, iodide, cyano, or alkyl of 1 to 4 carbon atoms;

(iii) compounds of Formula VI ##STR17## wherein R₆₁, R6₆₂ R₆₃ and R₆₄ are the same or different and are each selected form alkyl of 1 to 10 carbon atoms or phenyl; and

R₆₅ and R₆₆ are the same or different and are each selected from hydrogen or alkyl of 1 to 10 carbon atoms, provided that both R₆₅ and R₆₆ are hydrogen or both are alkyl, and if R₆₅ and R₆₆ are both hydrogen, not more than one of R₆₁ and R₆₂ is hydrogen and not more than one of R₆₃ and R₆₄ is hydrogen;

(iv) compounds of Formula VII ##STR18## wherein R₇₁ is oxygen or sulfur, R₇₅ is hydrogen or dialkylamino, wherein the alkyl groups are the same or different and are each selected from alkyl of 1 to 6 carbon atoms, and R₇₂, R₇₃ and R₇₄ are the same or different and are each selected from hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, optionally substituted at any one position with an alkyl group of 1 to 6 carbon atoms, and benzyl, optionally substituted at any one position of the phenyl group with an alkyl group of 1 to 6 carbon atoms; and

(v) compounds of Formula VIII ##STR19##

11. A mirror according to claim 10 wherein, in the solution of reversibly variable transmittance,

(A) the solvent is propylene carbonate;

(B) the solution includes one or two different cathodic compounds, each at a concentration of 0.01 M to 0.1 M in the solution at 25°

C. at zero-potential equilibrium, and

(C) the solution includes one or two different anodic compounds, each at a concentration of 0.01 M to 0.1 M in the solution at 25°

C. at zero-potential equilibrium.

12. A mirror according to claim 11 wherein, in the solution of reversibly variable transmittance,

(A) the cathodic compounds are selected from compounds of Formula X ##STR20## wherein R₁₀₁ is n-heptyl, phenyl or benzyl and X₁₀₁^- is BF₄^- or ClO₄^- ;

and the compounds of formula XI ##STR21## wherein X_112- is BF₄^- or PF₆^- ; and

(B) the anodic compounds are selected from the compounds of Formula XII ##STR22## wherein R₁₂₁ is methyl or phenyl; and

the compounds of Formula XIII ##STR23## wherein R₁₃₁ is methyl or phenyl.

13. A mirror according to claim 12 wherein, in the solution of reversibly variable transmittance, the cathodic compounds are selected from 1,1'"'"'-dibenzyl-4,4'"'"'-bipyridinium difluoroborate and tetramethylene bis tetra(hexafluorophosphate), the anodic compounds are selected from 5,10-dihydro-5,10-dimethylphenazine and N,N,N'"'"',N'"'"'-tetramethyl-1,4-phenylenediamine, the total concentration of the cathodic compounds is 0.01 M to 0.05 M at 25°

C., and the total concentration of the anodic compounds is 0.01 M to 0.05 M at 25°

C.

14. A mirror according to claim 11 wherein, in the solution of reversibly variable transmittance, the anodic compound is 5,10-dihydro-5,10-dimethylphenazine.

15. A mirror according to claim 12 wherein, in the solution of reversibly variable transmittance, the anodic compound is 5,10-dihydro-5,10-dimethylphenazine.

16. A mirror according to claim 13 wherein, in the solution of reversibly variable transmittance, the anodic compound is 5,10-dihydro-5,10-dimethylphenazine.

17. A mirror according to claim 16 wherein, in the solution of reversibly variable transmittance, the cathodic compound is 1,1'"'"'-dibenzyl-4,4'"'"'-bipyridinium difluoroborate.

18. A mirror according to any of claims 9, 10, 11, 12, 13, 14, 15, 16, and 17 wherein, in the electrochromic device, the solution of reversibly variable transmittance is between and in contact with two planar, parallel, spaced-apart walls, at least one of which is transparent and each of which, on the side in contact with said solution, is coated with an electrode layer of electrically conductive material, provided that, if one of said walls is not transparent, it comprises a reflecting layer of high reflectance material which reflects, through said solution and the transparent wall, light which reaches said reflecting layer after entering the solution through the transparent wall.

19. A mirror according to claim 18 wherein, in the electrochromic device, DC current is provided to the electrode layers through leads connected to a DC power source, and wherein the electrochromic device is oriented so that the lead connecting the electrode layer, which is the anode, to the power source is higher in elevation than the lead connecting the electrode, which is the cathode, to the power source.

20. A mirror according to any of claims 9, 10, 11, 12, 13, 14, 15, 16 and 17 wherein, in the electrochromic device, DC current is provided to the electrode layers through leads connected to a DC power source, and wherein the electrochromic device is oriented so that the lead connecting the electrode layer, which is the anode, to the power source is higher in elevation than the lead connecting the electrode, which is the cathode, to the power source.

21. A mirror according to any of claims 11, 12, 13, 14, 15, 16, and 17 wherein the solution of reversibly variable transmittance is thickened with 3% (w/w) to 25% (w/w) of acrylic sheet material thickener.

22. A mirror according to claim 21 wherein, in the electrochromic device, the solution of reversibly variable transmittance is between and in contact with two planar, parallel, spaced-apart walls, at least one of which is transparent and each of which, on the side in contact with said solution, is coated with an electrode layer of electrically conductive material, provided that, if one of said walls is not transparent, it comprises a reflecting layer of high reflectance material which reflects, through said solution and the transparent wall, light which reaches said reflecting layer after entering the solution through the transparent wall.

23. A mirror according to claim 22 wherein, in the electrochromic device, DC current is provided to the electrode layers through leads connected to a DC power source, and wherein the electrochromic device is oriented so that the lead connecting the electrode layer, which is the anode, to the power source is higher in elevation than the lead connecting the electrode, which is the cathode, to the power source.

24. A mirror according to claim 21 wherein the solution of reversibly variable transmittance includes an inert, current-carrying electrolyte, at a concentration of 0.01 M to 1.0 M in the solution at 25°

C., selected from an alkali metal salt of Formula M₃₁⁺ X₃₅^-, a tetraalkylammonium salt of Formula M₃₂⁺ X₃₅^-, aluminum chloride, aluminum bromide and any combination of the foregoing salts, wherein M₃₁⁺ is potassium, sodium or lithium, M₃₂⁺ is tetraalkylammonium wherein the alkyl groups are the same or different and are each selected from alkyl of 1 to 10 carbon atoms, and X₃₅ ^- is chloride, bromide, BF₄^-, PF₆^-, AsF₆^-, ClO₄^- or NO_3-.

25. A mirror according to any of claims 11, 12, 13, 14, 15, 16, and 17 wherein the solution of reversibly variable transmittance includes an inert, current-carrying electrolyte, at a concentration of 0.01 M to 1.0 M in the solution at 25°

C., selected from an alkali metal salt of Formula M₃₁⁺ X₃₅^-, a tetraalkylammonium salt of Formula M₃₂⁺ X₃₅^-, aluminum chloride, aluminum bromide and any combination of the foregoing salts, wherein M₃₁⁺ is potassium, sodium or lithium, M₃₂⁺ is tetraalkylammonium wherein the alkyl groups are the same or different and are each selected from alkyl of 1 to 10 carbon atoms, and X₃₅^- is chloride, bromide, BF₄^-, PF₆^-, AsF₆^-, ClO₄^- or NO₃^-.

26. A variable reflectance mirror for a motor vehicle which comprises as the variable transmittance component a single-compartment, self-erasing, solution-phase electrochromic device and which has a range of reflectance from greater than 70% to less than 10%.

27. A mirror according to claim 26 wherein the electrochromic device is gray-scale controllable over a range of reflectance by applying potential differences between the electrode layers of the device of 0.2 volts to 1.5 volts.

28. A mirror according to claim 27 wherein the reflectance is capable of being reduced from greater than 70% to less than 20% in less than 10 seconds with a potential difference of less than 1.4 volts between the electrode layers of the electrochromic device.

29. A variable reflectance mirror according to claim 26 wherein the reflectance is reduced from greater than 70% to less than 10% in less than 10 seconds with a potential difference of less than 1.4 volts between the electrode layers.

30. A variable reflectance mirror for a motor vehicle comprising a single-compartment, self-erasing, solution-phase electrochromic device which is gray-scale controllable over a range of reflectance by applying potential differences between the electrode layers of the device of 0.2 volts to 1.5 volts.

31. A variable reflectance mirror for a motor vehicle which comprises as the variable transmittance component a single-compartment, self-erasing, solution-phase electrochromic device which comprises two planar, parallel, spaced-apart electrode layers, to which DC current is provided through leads connected to a DC power source, said device oriented so that the lead connected the electrode layer which is the anode, to the power source is higher in elevation than the lead connecting the electrode, which is the cathode, to the power source.