Electrochromic device

• US 6,208,452 B1
• Filed: 10/22/1999
• Issued: 03/27/2001
• Est. Priority Date: 10/22/1998
• Status: Expired due to Fees

• Current Assignee: Nippon Mitsubishi Oil Corporation (ENEOS Holdings, Inc.)
• Original Assignee: Nippon Mitsubishi Oil Corporation (ENEOS Holdings, Inc.)
• Inventors: Sugiura, Izuru, Kobayashi, Masaaki, Nishikitani, Yoshinori, Imafuku, Hiroshi
• Primary Examiner(s): Epps, Georgia
• Assistant Examiner(s): Lester, Evelyn A.
• Application Number:
  US09/425,330
• Time in Patent Office: 522 Days
• Field of Search: 359/265, 359/270, 359/268
• US Class Current: 359/270
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/1516 comprising organic material

Abstract

The electrochromic device which has an ion conductive layer obtained by curing a composition comprising (a) a bipyridinium compound represented by formula (1), (b) a specific amine compound and (c) a precursor component of a polymeric solid 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 an 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 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.

Claims

1. An electrochromic device which has an ion conductive layer obtained by curing a composition comprising (a) a bipyridinium compound represented by formula (1), (b) an amine compound represented by formula (2) and/or (3) and (c) a precursor component of a polymeric solid 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 an halogen anion, CIO₄—

, BF₄—

, PF₆—

, CH₃COO— and

CH₃(C₆H₄)SO₃—

, R¹ is hydrogen or a C₁-C₅ alkyl group, R² is a C₁-C₃₀ divalent hydrocarbon 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 formula (2) being

wherein R⁴ is hydrogen or a C₁-C₅ alkyl group, R⁵ is a C₁-C₁₅ hydrocarbon or oxygen-containing hydrocarbon group, b is an integer of 0 or 1, R⁶ and R⁷ are the same or different and are each independently hydrogen or a C₁-C₂₀ hydrocarbon or oxygen-containing hydrocarbon group, R⁸ is hydrogen or a C₁-C₂₀ hydrocarbon or oxygen-containing hydrocarbon group and Ar¹ is a C₆-C₂₀ divalent aromatic hydrocarbon group; and

said formula (3) being

wherein R⁹ is hydrogen or a C₁-C₅ alkyl group, R¹⁰ is a C₁-C₁₅ hydrocarbon or oxygen-containing hydrocarbon group, c is an integer of 0 or 1, R¹¹ and R¹² are the same or different and are each independently hydrogen or a C₁-C₂₀ hydrocarbon or oxygen-containing hydrocarbon group and R¹³ is hydrogen or a C₁-C₂₀ hydrocarbon or oxygen-containing hydrocarbon group.

2. The electrochromic device according to claim 1 which has said ion conductive layer further containing (d) an ultraviolet absorbing compound having an ethylenic double bond.

3. The electrochromic device according to claim 1 wherein said bipyridinium compound represented by formula (1) wherein R¹ is selected from the group consisting of hydrogen and methyl group, R² is selected from the group consisting of methylene, ethylene, tetramethylene, propylene, m-phenylene, p-phenylene, alkyl-substituted phenylene, biphenylene, naphthylene, oxymethylene and oxypropylene 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, and groups represented by 

CH₂CH₂O

₂ and

said amine compound represented by formula (2) and/or (3) wherein R⁴ and R⁹ are each independently selected from the group consisting of hydrogen or methyl group, R⁵ and R¹⁰ are each independently selected from the group consisting of groups represented by

and —

(C₆H₄)—

CH₂

OCH₂CH₂

₄, R⁶, R⁷, R¹¹ and R¹² are each independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, hexyl, heptyl, octyl, tolyl, ethyphenyl, phenyl, methoxyphenyl and ethoxyphenyl groups, R⁸ and R¹³ are each independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, hexyl, heptyl, octyl, tolyl, ethylphenyl, phenyl, methoxyphenyl and ethoxyphenyl groups, and Ar¹ is selected from the group consisting of o-phenylene, m-phenylene, p-phenylene, alkyl-substituted phenylene, biphenylene and naphthylene groups.

4. The electrochromic device according to claim 1 wherein said precursor component of a polymeric solid electrolyte comprises a polymeric monomer and a supporting electrolyte.

5. The electrochromic device according to claim 1 wherein said polymeric monomer is selected from the group consisting of a monofunctional modified polyalkylene oxide represented by the formula

wherein R⁵⁸, R⁵⁹, R⁶⁰ and R⁶¹ are each independently hydrogen or a C₁-C₅ alkyl group and g′

is an integer of greater than 1;

a difunctional modified polyalkylene oxide represented by the formula

wherein R⁶², R⁶³, R⁶⁴ and R⁶⁵ are each independently hydrogen or a C₁-C₅ alkyl group and h′

is an integer of greater than 1, and a polyfunctional modified polyalkylene oxide represented by the formula

wherein R⁶⁶, R⁶⁷ and R⁶⁸ are each independently hydrogen or a C₁-C₅ alkyl group, i′

is an integer of greater than 1, j′

is an integer of 2 to 4 and L is a connecting group of valence indicated by q.

6. The electrochromic device according to claim 5 wherein said polymeric monomer contains said difunctional polyoxyalkylene oxide and/or said polyfunctional in a total amount of 0.1 to 20 part by weight, of 100 parts by weight of said monofunctional polyoxyalkylene oxide.