Variable reflectance mirror

• US 5,282,077 A
• Filed: 04/19/1993
• Issued: 01/25/1994
• 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): Arnold, Bruce Y.
• Assistant Examiner(s): Lester, Evelyn A.
• Application Number:
  US08/049,615
• Time in Patent Office: 281 Days
• Field of Search: 359/265, 359/270, 359/267, 359/272, 359/275, 359/839
• US Class Current: 359/272
• 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 mirrors wherein the component of variable transmittance is a single-compartment, self-erasing, solution-phase electrochromic device.

Claims

1. A variable reflectance mirror which comprises a single-compartment, self-erasing, solution-phase electrochromic device which 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.

2. A mirror according to claim 1 wherein, in the solution of reversibly variable transmittance,

(A) the solvent is liquid at room temperature and selected from propylene carbonate, gamma-butyrolactorne, 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 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 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^-, PH₆^-, 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 are the same 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;

##STR17## wherein R₆₁, R₆₂, 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 are 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. 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 VII ##STR19##

3. A mirror according to claim 2 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 0.1M to 0.1M 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 0.01M to 0.1M in the solution at 25°

C. at zero-potential equilibrium.

4. A mirror according to claim 3 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 the 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.

5. A mirror according to claim 4 wherein, in the solution of reversibly variable transmittance, the cathodic compounds are selected from 1,1'"'"'-dibenzyl-4,4'"'"'-bipyridinium difluoroborate and tetramethylene bis[4(1benzylpyridine-4'"'"'-yl)pyridinium]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 0.01M to 0.05M at 25°

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

C.

6. A mirror according to claim 3 wherein, in the solution of reversibly variable transmittance, the anodic compound is 5,10-dihydro-5,10-dimethylphenazine.

7. A mirror according to claim 4 wherein, in the solution of reversibly variable transmittance, the anodic compound is 5,10-dihydro-5,10-dimethylphenazine.

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

9. A mirror according to claim 8 wherein, in the solution of reversibly variable transmittance, the cathodic compound is 1,1'"'"'-dibenzyl-4,4'"'"'-bipyridinium difluoroborate.

10. A mirror according to any of claim 3, 4, 5, 6, 7, 8 and 9 wherein the solution of reversibly variable transmittance is thickened with 3% (w/w) to 25% (w/w) or acrylic sheet material thickener.

11. A mirror according to any of claim 3, 4, 5, 6, 7, 8 and 9 wherein the solution of reversibly variable transmittance includes an inert, current-carrying electrolyte, at a concentration of 0.01M to 1.0M 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^- and NO₃^-.

12. A mirror according to claim 10, wherein the solution of reversibly variable transmittance includes an inert, current-carrying electrolyte, at a concentration of 0.01M to 1.0M 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^- and NO₃^-.

13. A mirror according to claim 1, 3, 2, 4, 5, 6, 7, 8, and 9 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 ar 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.

14. A mirror according to claim 10 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 ar 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.