Electrochromic mirror and electrochromic devices

• US 6,285,486 B1
• Filed: 01/31/2000
• Issued: 09/04/2001
• Est. Priority Date: 07/15/1997
• Status: Expired due to Fees

• Current Assignee: Nippon Mitsubishi Oil Corporation (ENEOS Holdings, Inc.)
• Original Assignee: Nippon Oil Corporation (ENEOS Holdings, Inc.)
• Inventors: Kobayashi, Masaaki, Nishikitani, Yoshinori
• Primary Examiner(s): Epps, Georgia
• Assistant Examiner(s): Thompson, Timothy J
• Application Number:
  US09/495,396
• Time in Patent Office: 582 Days
• Field of Search: 359/265, 359/273, 359/267, 359/268, 359/270, 252/582, 252/583
• 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: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
• CPC Class Codes: G02F 1/1525 characterised by a particular ion transporting layer, e.g. electrolyte
• CPC Class Codes: G02F 1/157 Structural association of cells with optical devices, e.g. reflectors or illuminating devices

Abstract

An electrochromic mirror (10) comprises an reflective electrically conductive substrate and a transparent electrically conductive substrate, a layer of an ion conductive material (14) disposed therebetween and at least one electrochromic chromogenic layer (13) disposed either between the ion conductive material layer and the reflective electrically conductive substrate or between the ion conductive material layer and the transparent electrically conductive substrate, said electrochromic chromogenic layer containing a compound having a viologen structure represented by the formula

wherein X⁻ and Y⁻ may be the same or different and each indicate a counter anion selected from the group consisting of a halogen anion, ClO₄⁻, CH₃COO⁻, and CH₃(C₆H₄)SO₃⁻.

The inventive mirror can be put in a various applications such as an antiglare mirror for an automobile and a decorative mirror for out door use.

Claims

1. An electrochromic mirror comprises an reflective electrically conductive substrate and a transparent electrically conductive substrate, a layer of an ion conductive material disposed therebetween and at least one electrochromic chromogenic layer disposed either between said ion conductive material layer and said reflective electrically conductive substrate or between said ion conductive material layer and said transparent electrically conductive substrate, said electrochromic chromogenic layer containing a compound having a viologen structure represented by the formula

wherein X⁻

and Y⁻

may be the same or different and each indicate a counter anion selected from the group consisting of a halogen anion, ClO₄⁻

, CH₃COO⁻

, and CH₃(C₆H₄)SO₃⁻

.

2. An electrochromic mirror according to claim 1 wherein it is a all-solid type mirror.

3. An electrochromic mirror according to claim 1, wherein said ion conductive material is a solid and said solid ion conductive material is a polymer solid electrolyte derived from the polymerization of a polyethyleneoxide-based compound, an oxyalkyleneacrylate-based compound or a urethaneacrylate-based compound.

4. An electrochromic mirror according to claim 1 wherein said compound having a viologen structure is a polymer or copolymer represented by the formula

wherein m is an integer of more than 1, n is an integer of more than 0, R³³ is a C₁-C₂₀ divalent hydrocarbon residue or merely indicates bond of the viologen group directly to a polymer chain not through the hydrocarbon residue, R³⁴, R³⁵ and R³⁶ each are a C₁-C₂₀ hydrocarbon group and a hetero atom-containing substituent and a halogen atom and X⁻

and Y⁻

indicate the counter anion selected from the group consisting of a halogen anion such as F⁻

, Cl⁻

, Br⁻

and I⁻

, ClO₄⁻

, CH₃COO⁻

, and CH₃(C₆H₄)SO₃⁻

with respect to viologen and may be same or different.

5. An electrochromic mirror according to claim 1 wherein said compound having a viologen structure is a polymer or copolymer represented by the formula

wherein m is an integer of more than 1, n is an integer of more than 0, R³⁷ and R³⁸ may be the same or different and each are a C₁-C₂₀ divalent hydrocarbon residue or merely indicates bond of the viologen group directly to a polymer chain not through the hydrocarbon residue, R³⁸ and R⁴⁰ may be the same or different and each are a C₁-C₂₀ hydrocarbon group and hetero atom-containing substituent and a halogen atom and X⁻

and Y⁻

indicate the counter anion selected from the group consisting of a halogen anion such as F⁻

, Cl⁻

, Br⁻

and I⁻

, ClO₄⁻

, CH₃COO⁻

, and CH₃(C₆H₄)SO₃⁻

with respect to viologen and may be same or different.

6. An electrochromic mirror according to claim 1 wherein said compound having a viologen structure is a polymer or copolymer represented by the formula

wherein m is an integer of more than 1, n is an integer of more than zero, R⁴¹ is a C₁-C₂₀ divalent hydrocarbon residue or merely indicates bond of the viologen group directly to a polymer chain not through the hydrocarbon residue, R⁴², R⁴³ and R⁴⁴ may be the same or different and each are a C₁-C₂₀ hydrocarbon group and hetero atom-containing substituent and a halogen atom and X⁻

and Y⁻

indicate the counter anion selected from the group consisting of a halogen anion such as F⁻

, Cl⁻

, Br⁻

and I⁻

, ClO₄⁻

, CH₃COO⁻

, and CH₃(C⁶H⁴)SO₃⁻

with respect to viologen and may be same or different.

7. An electrochromic mirror according to claim 1 wherein said compound having a viologen structure is a copolymer represented by the formula

wherein p is an integer of more than 0, q is an integer of between 1 and 1,000, R is a C₁ -C₂₀ divalent hydrocarbon residue or merely indicates bond of the viologen group directly to a polymer chain not through the hydrocarbon residue, X⁻

and Y⁻

indicate the counter anion selected from the group consisting of a halogen anion such as F⁻

, Cl⁻

, Br⁻

and I⁻

, ClO₄⁻

, CH₃COO⁻

, and CH₃(C₆H₄)SO₃⁻

with respect to viologen and may be same or different.

8. An electrochromic mirror according to claim 1 wherein said compound having a viologen structure is a polymer or copolymer represented by the formula

wherein r is an integer of more than 1, R⁴⁶ is a C₁-C₂₀ divalent hydrocarbon residue or merely indicates bond of the viologen group directly to a polymer chain not through the hydrocarbon residue, R⁻

is a C₁-C₂₀ hydrocarbon group and hetero atom-containing substituent and a halogen atom and X⁻

and Y⁻

indicate the counter anion selected from the group consisting of a halogen anion such as F⁻

, Cl⁻

, Br⁻

and I⁻

, ClO₄⁻

, CH₃COO⁻

, and CH³(C⁶H⁴)SO₃⁻

with respect to viologen and may be same or different.

9. An all-solid type electrochromic device comprising two electrically conductive substrates, at least one of which is transparent, a layer of an ion conductive material, said solid ion conductive material disposed between said two electrically conductive substrates, and at least one electrochromic chromogenic layer disposed between said ion conductive material and either of said two electrically conductive substrates, wherein said ion conductive material comprises a polymer solid electrolyte derived from the polymerization of a compound selected from polyethyleneoxide-based compounds, oxyaldleneacrylate-based compounds and urethaneacrylate-based compounds, and wherein said electrochromic chromogenic layer contains a compounds having a viologen structure selected from polymers and copolymers represented by the formula

wherein X⁻

and Y⁻

may be the same or different and each indicate a counter anion selected from the group consisting of a halogen anion, ClO₄⁻

, CH³COO⁻

, CH₃(C⁶H⁴)SO₃⁻

and BF₄⁻

.

10. An all-solid type electrochromic device according to claim 9 comprising two electrically conductive substrates, at least one of which is transparent, a layer of a solid ion conductive material, said solid ion conductive material disposed between said two electrically conductive substrates, and at least one electrochromic chromogenic layer disposed between said ion conductive material and either of said two electrically conductive substrates, wherein said ion conductive material comprises a polymer solid electrolyte derived from the polymerization of a compound selected from polyethyleneoxide-based compounds, oxyalkyleneacrylate-based compounds and urethaneacrylate-based compounds, and wherein said electrochromic chromogenic layer contains a compound having a viologen structure selected from polymers and copolymers represented by the formula

wherein m is an integer of more than 1, n is an integer of more than 0, R³³ is a C₁-C₂₀ divalent hydrocarbon residue, R³⁴, R³⁵ and R³⁶ are each independently a C₁-C₂₀ hydrocarbon group, a hetero atom-containing substituent, or a halogen atom, and X⁻

and Y⁻

represent counter anions selected from the group consisting of F⁻

, Cl⁻

, Br⁻

, I⁻

, ClO₄⁻

, CH₃COO⁻

, and CH₃(C₆H₄)SO₃⁻

and BF₄⁻

, with respect to viologen and may be the same or different;

or the formula

wherein m is an integer of more than 1, n is an integer of more than 0, R³⁷ and R³⁸ are each independently a C₁-C₂₀ divalent hydrocarbon residue, R³⁹ and R⁴⁰ are each independently a C₁-C₂₀ hydrocarbon group, a hetero atom-containing substituent, or a halogen atom, and X⁻

and Y⁻

represent counter anions selected from the group consisting of F⁻

, Cl⁻

, Br⁻

, I⁻

, ClO₄⁻

, CH₃COO⁻

, and CH₃(C₆H₄)SO₃⁻

and BF₄⁻

, with respect to viologen and may be the same or different.

11. An all-solid type electrochromic device according to claim 10 wherein said solid ion conductive material is a polymeric electrolyte obtained by solidifying a composition of an organic polar solvent, a supporting electrolyte and a urethane acrylate of the formula

wherein R¹ and R² may be the same or different and each comprises an α

,β

-unsaturated ester moiety;

R³ and R⁴ may be the same or different and each is a C₁-C₂₀ divalent hydrocarbon residue, Y is selected from the group consisting of polyether units, polyester units, polycarbonate units and mixtures thereof; and

n is an integer of from 1 to 100.

12. An all-solid type electrochromic device according to claim 10 wherein said solid ion conductive material is a polymeric electrolyte obtained by solidifying a compound comprising an organic polar solvent, a supporting electrolyte, and a poly-functional acryloyl-modified polyalkylene oxide and a mono-poly-functional acryloyl polyalkylene oxide represented by the formula

wherein R²², R²³, R²⁴ and R²⁵ may be the same or different and each is a hydrogen atom or an alkyl group having from 1 to 5 carbon atoms, and wherein n is an integer of greater than 1.

13. An all-solid type electrochromic device according to claim 9 wherein both of said two electrically conductive substrates are transparent.

14. An all-solid type electrochromic device according to claim 13 wherein said transparent electrically conductive substrates are each a laminate comprising a transparent substrate and a transparent electrode layer formed thereon.

15. An all-solid type electrochromic device according to claim 9 wherein one of said two electrically conductive substrates is transparent and the other is reflective.

16. An all-solid type electrochromic device according to claim 9 wherein said reflective electrically conductive substrate is a laminate including a transparent or opaque substrate having a reflective electrode layer formed thereon, a laminate including a transparent substrate having on one surface a transparent electrode layer and on the other surface a reflective layer, a laminate including a transparent substrate having a reflective layer formed and a transparent layer formed on after another or a plate-like substrate which functions as a reflective layer and an electrode.

17. An all-solid type electrochromic device according to claim 16 wherein said transparent substrate is selected from the group consisting of polyethylene terephthalate, polyamide, polysulfone, polyether sulfone, polyether etherketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate and polystyrene.

18. An all-solid type electrochromic device according to claim 17 wherein said transparent substrate is selected from the group consisting of polyethylene terephthalate, polyamide, polysulfone, polyether sulfone, polyether etherketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate and polystyrene.

19. An all-solid type electrochromic device according to claim 16 wherein said transparent electrode layer is an electrically conductive film formed from a material selected from the group consisting of gold, silver, chrome, copper, tungsten, ITO (In₂O₃—

SnO₂), tin oxide, silver oxide, zinc oxide and vanadium oxide.

20. An electrochromic mirror according to claim 17 wherein said transparent electrode layer is an electrically conductive film formed from a material selected from the group consisting of gold, silver, chrome, copper, tungsten, ITO (In₂O₃—

SnO₂), tin oxide, silver oxide, zinc oxide and vanadium oxide.

21. An electrochromic mirror according to claim 17 wherein said reflective electrode layer is a film of a material selected from the group consisting of gold, platinum, tungsten, tantalum, rhenium, osmium, iridium, silver, nickel and palladium and an alloy of platinum-palladium, platinum-rhodium and stainless steel.

22. An electrochromic mirror according to claim 9 wherein said ion conductive material is liquid, gel or solid.