Electrochromic device

• US 6,657,768 B2
• Filed: 05/03/2002
• Issued: 12/02/2003
• Est. Priority Date: 12/14/1998
• Status: Expired due to Fees

• Current Assignee: Nippon Mitsubishi Oil Corporation (ENEOS Holdings, Inc.)
• Original Assignee: Nippon Mitsubishi Oil Corporation (ENEOS Holdings, Inc.)
• Inventors: Kobayashi, Masaaki, Nishikitani, Yoshinori, Imafuku, Hiroshi
• Primary Examiner(s): Jones, Deborah
• Assistant Examiner(s): XU, LING X
• Application Number:
  US10/138,661
• Publication Number:
  US 20020136898A1
• Time in Patent Office: 578 Days
• Field of Search: 359/265, 359/270, 359/273, 428/457, 428/704, 428/702, 428/425.9, 428/411.1, 428/469, 428/689, 428/500, 252/582, 252/583, 252/586
• US Class Current: 359/265
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/1516 comprising organic material
• CPC Class Codes: G02F 2203/02 reflective
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31515 As intermediate layer
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31609 Particulate metal or metal compound-containing
• CPC Class Codes: Y10T 428/31678 Of metal
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers

Abstract

The electrochromic devices have an ion conductive layer formed by curing a composition comprising a bipyridinium compound represented by the formula

a specific metallocene compound and a precursor of a polymeric solid electrolyte, between two electrically conductive substrates, at least one of which is transparent.

Claims

1. An electrochromic device comprising an ion conductive layer obtained by curing a composition containing (A) a bipyridinium compound represented by formula (1), (B) a metallocene compound represented by formula (2) or (2′

) and (C) a precursor of a polymeric solid electrolyte comprising a monofunctional modified polyalkylene oxide represented by formula (12), a polymeric monomer selected from the group consisting of a difunctional modified polyalkylene oxide represented by formula (13) and a polyfunctional modified polyalkylene oxide represented by formula (14), and a supporting electrolyte, disposed between two electrically conductive substrates at least one of which is transparent, said formula (1) being

wherein X- and Y- are the same or different and are each independently a counter anion selected from the group consisting of au halogen anion, ClO₄⁻

, BF₄⁻

, PF₆⁻

, CH₃COO⁻

and CH₃(C₆H₄)SO₃⁻

, R¹ is hydrogen or a C₁-C₅ alkyl group, R² is a C₁-C₃₀ divalent hydrocarbon group or oxygen-containing hydrocarbon group, R³ is a C₁-C₂₀ hydrocarbon or oxygen-containing hydrocarbon group and a is an integer of 0 or 1;

said formulae (2) and (2′

) being

wherein R⁴ and R⁵ are each independently a hydrocarbon group selected from the group consisting of alkenyl and aryl groups, if R⁴ or R⁵ is an aryl group, the aromatic ring may form a condensation ring by bonding to a cyclopentadienyl ring, n¹ is an integer of 0≦

n¹≦

4, n² is an integer of 0≦

n²≦

5, but at least one of n₁ and n₂ is ≧

1, A and A′

are the same or different and are each independently a monovalent group, in is 0 or 1, M is selected from the group consisting of Cr, Go, Fe, Mg, Ni, Os, Ru and V, M′

is selected from the group consisting of Hf, Mo, Nb, Ti, V and Zr and Q and Q′

are the same or different and each are independently selected from the group consisting of hydrogen, halogen and a C₁-C₁₂ alkyl group;

said formula (A) being

wherein R⁶ is hydrogen or a methyl group, R⁷ is hydrogen or at methyl group, b is 0 or 1 and provided that R⁷ is hydrogen if b is 0;

said formula (12) being

wherein R³³, R³⁴, R³⁵ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, R³⁶ is an alkyl group having 1 to 5 carbon atoms, and g′

is an integer of 1 or greater;

said formula (13) being

wherein R³⁷, R³⁸, R³⁹ and R⁴⁰ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms and h′

is an integer of 1 or greater; and

said formula (14) being

wherein R⁴¹, R⁴² and R⁴³ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, i′

is an integer of 1 or greater than 1, j′

is an integer of 2 to 4 and L is a connecting group of valence of “

j′

”

.

2. The electrochromic device according to claim 1 wherein the ion conductive layer further comprises (D) an ultraviolet absorbing compound having an ethylenic double bond.

3. The electrochromic device according to claim 1 wherein the bipyridinium compound is represented by formula (1) wherein R¹ is selected from the group consisting of hydrogen and a methyl group, R² is selected from the group consisting of methylene, m-phenylene and p-phenylene groups, R³ is selected from the group consisting of methyl, ethyl, i-propyl, n-propyl, n-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, benzyl and vinylbenzyl groups and groups represented by

4. The electrochromic device according to claim 1 wherein the metallocene compound is represented by formula (2) or (2′

) wherein M represents Fe and M′

represents Ti or Zr.

5. The electrochromic device according to claim 4 wherein the bipyridinium compound is represented by formula (1) wherein R¹ is selected from the group consisting of hydrogen and a methyl group, R² is selected from the group consisting of methylene, m-phenylene and p-phenylene groups, R³ is selected from the group consisting of methyl, ethyl, i-propyl, n-propyl, n-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, benzyl and vinylbenzyl groups and groups represented by

6. The electrochromic device according to claim 5 wherein the bipyridinium compound is N-n-propyl-N′

-vinylbenzylbipyridinium bromide chloride.

7. The electrochromic device according to claim 5 wherein the bipyridinium compound is N,N′

-di-vinylbenzylbipyridinium chloride.

8. The electrochromic device according to claim 1 wherein the metallocene compound is represented by formula (2) wherein M represents Fe.

9. The electrochromic device according to claim 1 wherein the precursor of a polymeric solid electrolyte further comprises a solvent.

10. The electrochromic device according to claim 9 wherein the solvent is an organic polar solvent.