Electrochromic device

• US 6,538,792 B1
• Filed: 06/19/2000
• Issued: 03/25/2003
• Est. Priority Date: 12/19/1997
• 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
• Primary Examiner(s): Jones, Deborah
• Assistant Examiner(s): XU, LING X
• Application Number:
  US09/596,324
• Time in Patent Office: 1,009 Days
• Field of Search: 359/265, 359/270, 359/273, 359/272, 428/411.1, 428/500, 428/515, 428/702, 428/704, 428/689, 252/582, 252/586
• US Class Current: 359/265
• 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 1/1516 comprising organic material
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31909 Next to second addition polymer from unsaturated monomers

Abstract

An electrochromic element composed of an ionically conductive substance layer containing a specified electrochromic substance sandwiched between two electrically conductive substrates at least one of which is transparent.

Claims

1. An electrochromic device comprising two electrically conductive substrates, at least one of which is transparent, and an ion conductive substance layer disposed therebetween and comprising a mixture obtained by dispersing an electrochromic substance represented by formula (1) below into a composition containing a monofunctional acryloyl-modified polyalkylene oxide represented by formula (17) and a polyfunctional acryloyl-modified polyalkylene oxide represented by formula (18) or (19), a polar solvent and a supporting electrolyte;

formula (1) being represented by

wherein X⁻

and Y⁻

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

, BF₄⁻

, PF₄⁻

, CH₃COO⁻

and CH₃(C₆H₄)SO₃⁻

and R¹ and R² are the same or different and are each a hydrocarbon group having from 1 to 20 carbon atoms;

formula (17) being represented by

wherein R²⁷, R²⁸, and R²⁹ are each selected from the group consisting of hydrogen and an alkyl group having 1 to 5 carbon atoms, R³⁰ is an alkyl group having 1 to 5 carbon atoms, and j is an integer of 2 to 30;

formula (18) being represented by

wherein R³¹, R³², R³³, and R³⁴ are each selected from the group consisting of hydrogen and an alkyl group having 1 to 5 carbon atoms, and k is an integer of 2 to 30; and

formula (19) being represented by

wherein R³⁵, R³⁶, and R³⁷ are each selected from the group consisting of hydrogen and an alkyl group having 1 to 5 carbon atoms, l is an integer of 2 to 30, m is an integer of 2 to 4 and L is a connecting group having a valence corresponding to m.

2. The electrochromic device according to claim 1 wherein the electrochromic substance of formula (1) is selected from the group consisting of N,N′

-diheptylbipyridiniumdibromide,

N,N′

-diheptylbipyridiniumdichloride,

N,N′

-diheptylbipyridiniumdiperchlorate,

N,N′

-diheptylbipyridiniumtetrafluoroborate,

N,N′

-diheptylbipyridiniumhexafluorophosphate,

N,N -dihexylbipyridiniumdibromide, N,N′

-dihexylbipyridiniumdichloride,

N,N′

-dihexylbipyridiniumdiperchlorate,

N,N′

-dihexylbipyridiniumtetrafluoroborate,

N,N′

-dihexylbipyridiniumdihexafluorophosphate,

N,N′

-dipropylbipyridiniumdibromide, N,N′

-dipropylbipyridiniumdichloride,

N,N′

-dipropylbipyridiniumdiperchlorate,

N,N′

-dipropylbipyridiniumtetrafluoroborate,

N,N′

-dipropylbipyridiniumdihexafluorophosphate,

N,N′

-dibenzylbipyridiniumdibromide,

N,N′

-dibenzylbipyridiniumperchlorate,

N,N′

-dibenzylbipyridiniumtetrafluoroborate,

N,N′

-dibenzylbipyridiniumdihexafluorophosphate,

N-heptyl-N′

-benzylbipyridiniumdiperchlorate,

N-heptyl-N′

-benzylbipyridiniumditetrafluoroborate,

N-heptyl-N′

-benzylbipyridiniumdibromide,

N-heptyl-N′

-benzylbipyridiniumdichloride,

N-heptyl-N′

-methylpyridiniumdibromide and

N-heptyl-N′

-methylpyridiniumdlchloride.

3. By The electrochromic device according to claim 1 wherein the polar solvent is an organic polar solvent selected from the group consisting of methanol, ethanol, propylene carbonate, ethylene carbonate, dimethylsulfoxide, dimethoxyethane, acetonitrile, γ

-butyrolactone, γ

-valerolactone, sulforan, dimethylformamide, dimethoxyethane, tetrahydrofuran, propionitrile, glutaronitrile, adiponitrile. methoxyacetonitrile, dimethylacetoamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, trimethylphosphate, and polyethylene glycol.

4. The electrochromic device according to claim 1 wherein the supporting electrolyte is selected from the group consisting of alkali metal salts, alkaline earth metal salts, quaternary ammonium salts and cyclic quaternary ammonium salts.

5. The electrochromic device according to claim 1 wherein an amount of the polar solvent contained in the layer is in a range of 100 to 800 weight % based on a total amount of the monofunctional acryloyl-modified polyalkylene oxide and the polyfunctional acryloyl-modified polyalkylene oxide.

6. An electrochromic device comprising two conductive substrates, at least one of which is transparent, and an ion conductive substance layer disposed therebetween and containing an electrochromic substance represented by the formula (1)

wherein X⁻

and Y⁻

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

, BF₄⁻

, PF₄⁻

, CH₃COO⁻

and CH₃(C₈H₄)SO₃⁻

and R¹ and R² are the same or different and are each a hydrocarbon group having from 1 to 20 carbon atoms and wherein the ion conductive substance comprises a mixture obtained by dispersing the electrochromic substance into a composition containing an urethaneacrylate represented by formula (2) below, a polar solvent and a supporting electrolyte;

formula (2) being represented by the formula

wherein R⁶ and R⁷ are the same or different and are each a group of formula (3), (4) or (5) below, R⁸ and R⁹ are the same or different and are each a C₁-C₂₀, preferably C₂-C₁₂ divalent hydrocarbon residue, Y is selected from a polyether unit, a polyester unit, a polycarbonate unit and mixed units thereof and b is an integer from 1 to 100, preferably 1 to 50 and more preferably 1 to 20;

formulae (3), (4) and (5) being represented by the formulae

wherein R¹⁰, R¹¹ and R¹² are the same or different and are each a hydrogen atom or a C₁-C₃ alkyl group and R¹³ is a C₁-C₂₀, preferably C₂-C₈ organic residue of divalent through quatervalent.