Electrochromic device

• US 6,115,171 A
• Filed: 06/01/1999
• Issued: 09/05/2000
• Est. Priority Date: 01/23/1997
• Status: Expired due to Fees

• Current Assignee: Nippon Mitsubishi Oil Corporation (ENEOS Holdings, Inc.)
• Original Assignee: Nippon Mitsubishi Oil Corporation (ENEOS Holdings, Inc.)
• Inventors: Minami, Masaki, Asano, Tsuyoshi, Nishikitani, Yoshinori, Takaesu, Noboru
• Primary Examiner(s): Sugarman, Scott J.
• Assistant Examiner(s): Lucas, Michael A
• Application Number:
  US09/323,445
• Time in Patent Office: 462 Days
• Field of Search: 359/285, 359/265, 359/237
• US Class Current: 359/285
• CPC Class Codes: G02F 1/1533 structural features not otherwise provided for
• CPC Class Codes: G02F 2001/1536 additional, e.g. protective, layer inside the cell

Abstract

An electrochromic device comprising a pair of electrically conductive substrates disposed facing each other and each having at least on its inner surface an electrode at least one of said electrically conductive substrates comprising a transparent substrate and a transparent electrode, an ion conductive material inserted between said pair of electrically conductive substrates, an electrochromic material-containing layer disposed between either one of said electrodes and said ion conductive material and an ultraviolet absorptive layer disposed between either at least one of said transparent substrates and the electrode disposed thereover or on the surface of said transparent substrate opposite to the transparent electrode disposed thereover, said ultraviolet absorptive layer being formed by coating and curing on the surface at said transparent substrate a reaction product of (A) an aminosilane compound of the formula (I) or the derivative thereof and (B) an ultraviolet absorptive material having in its molecules a carboxyl group,

said formula (I) being represented by ##STR1## wherein R¹ is a C₁ -C₁₀ alkylene group or a divalent group of the formula --(CH₂)_m --NH--m in which m is an integer of 1-4, the groups R² are the same or different and each selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom, a C₁ -C₁₀ alkyl group and a C₁ -C₁₀ alkyl group provided that at least one of the groups R² is an alkoxy group or a hydroxyl group and n is an integer of 0 or greater;

said reaction product having amide bonds derived from said aminosilane compound or the derivative thereof.

Claims

1. An electrochromic device comprising a pair of electrically conductive substrates disposed facing each other and each having at least on its inner surface an electrode at least one of said electrically conductive substrates comprising a transparent substrate and a transparent electrode, an ion conductive material inserted between said pair of electrically conductive substrates, an electrochromic material-containing layer disposed between either one of said electrodes and said ion conductive material and an ultraviolet absorptive layer disposed between either at least one of said transparent substrates and the electrode disposed thereover or on the surface of said transparent substrate opposite to the transparent electrode disposed thereover, said ultraviolet absorptive layer being formed by coating and curing on the surface of said transparent substrate a reaction product of (A) an aminosilane compound of the formula (I) or the derivative thereof, (B) an ultraviolet absorptive material having in its molecules a carboxyl group and (D) an epoxysilane compound, a ring opening polymerization product thereof, or combinations thereof,

said formula(l) being represented by ##STR21## wherein R¹ is a C₁ -C₁₀ alkylene group or a divalent group of the formula --(CH₂)_m --NH-- in which m is an integer of 1-4, the groups R² are the same or different and each selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom, a C₁ -C₁₀ alkyl group, a C₁ -C₁₀ alkoxy group and a C₆ -C₁₀ aryl group provided that at least one of the groups R² is an alkoxy group or a hydroxyl group and n is an integer of 0 or greater;

said reaction product having amide bonds derived from said aminosilane compound or the derivative thereof.

2. An electrochromic device according to claim 1 further comprising an intermediate layer disposed between said transparent substrate and said ultraviolet absorptive layer.

3. An electrochromic device according to claim 1 further comprising an overcoat layer disposed over said ultraviolet absorptive layer.

4. An electrochromic device according to claim 1 wherein said electrode has a thickness of ranging from 100 to 5,000 angstroms and resistance ranging from 0.5 to 500 Ω

/cm².

5. An electrochromic device according to claim 1 wherein said ion conductive material has an ion conductivity of 1×

10^-7 S/cm.

6. An electrochromic device according to claim 1 wherein said ion conductive material is selected from the group consisting of polyethyleneoxide, polymer of oxyethylenemethacrylate, nafion, polystyrene sulfonate, Li₃ N, Na-β

-Al₂ O₃ and Sn(HPO₄)₂ ·

H₂ O.

7. An electrochromic device according to claim 1 wherein said electrochromic material is selected from the group consisting of Mo₂ O₃, Ir₂ O₃, NiO, V₂ O₅, Wo₃, biologen, polythiophen, polyaniline, polypyrrole and metal phthalocyanine.

8. An electrochromic device according to claim 1 wherein said aminosilane compound is selected from the group consisting of 3-aminopropyltriethoxysilane, 3-aminopropyldiisopropylethoxysilane, ³ -aminopropylmethyidiethoxysilane, 3-aminopropyltrichrolosilane, 3-aminopropylpolydimethylsiloxane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and 3-aminopropyltris(methoxyethoxy)silane.

9. An electrochromic device according to claim 1 wherein said ultraviolet absorptive layer is added with an optional compound selected from the group consisting of silicone resins, epoxysilanes, polyether-modified polysiloxane and inorganic fine particle dispersions.

10. An electrochromic device according to claim 1 wherein said ultraviolet absorptive layer is 0.5 to 50 μ

m in thickness.

11. An electrochromic device according to claim 1 wherein said epoxysilane compound is a compound of the formulae selected from the group consisting of the formulae (XIX) and (XX),

said formula (XIX) being represented by ##STR22## said formula (XX) being represented by ##STR23## wherein R⁹ is a C₁ -C₁₀ alkylene group or a divalent group represented by the formula --R--O--R¹ wherein R and R¹ each are an alkylene group, the groups R¹ may be the same or different and each are a hydrogen atom, a hydroxyl group, a halogen atom, a C₁ -C₁₀ alkyl or alkoxy group and a C₆ -C₁₀ aryl group provided that at least one of the groups Re is an alkoxy group or a hydroxyl group and n is an integer between 0 and 3.

12. An electrochromic device according to claim 1 wherein said epoxysilane compound is selected from the group consisting of 3-glycidoxypropyntrimethoxysilane, dimethoxy-3-glycidoxypropylmethylsilane, 2-(3,4-epoxycyclohexylethyl)trimethoxysilane, 2-(3,4-epoxycyclohexylethyl)triethoxysilane and dimethylethoxy-3-glycidoxypropylsilane.

13. An electrochromic device according to claim 1 wherein said Component (B) is used in an amount of 5-90 mass percent, based on total mass of Components (A) and (B).

14. An electrochromic device according to claim 1 wherein said Component (D) is used in an amount of 10-500 mass percent, based on total mass of Components (A) and (B).

15. An electrochromic device according to claim 1 wherein said reaction product is obtained in the presence of a silicone resin having a functional group which can be reacted with the alkoxysilyl group of said Component (A).

16. An electrochromic device according to claim 15 wherein said silicone resin is used in amount of 5-300 mass percent, based on total mass of Components (A) and (B).

17. An electrochromic device according to claim 1 wherein said reaction product is derived in the presence of a compound represented by the formula ##STR24## wherein R¹², R¹³ and R¹⁴ may be the same or different and are a C₁ -C₁₀ alkylene group, the groups R¹⁵ may be the same or different and each are selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom, a C₁ -C₁₀ alkyl and alkoxy group and a C₆ -C₁₀ aryl group, provided that at least one of the groups R¹⁵ is a C₁ -C₁₀ alkoxy group, and m, n and p are each an integer of greater than 0.

18. An electrochromic device according to claim 17 wherein said compound of the formula (XXI) is selected from the group consisting of tetraethyleneglycol- bis(triethoxysilylethyl)ether, polyethyleneglycol-bis(triethoxysilylethyl)ether and polypropyleneglycol-bis(triethoxysilylethyl)ether.

19. An electrochromic device according to claim 1 7 wherein said compound of the formula (XXI) is used in an amount of 10-50 mass percent, based on total mass of Components (A) and (B).

20. An electrochromic device according to claim 1 wherein said reaction product is further added with an inorganic fine particle dispersion.

21. An electrochromic device according to claim 20 wherein said inorganic fine particle dispersion is used in an amount of 5-400 mass percent, based on total mass of Components (A) and (B).

22. An electrochromic device according to claim 1 wherein said reaction product is obtained under the condition that 50 mol percent or more of the aminosilane of said Component (A) form an amide bond.

23. An electrochromic device according to claim 1 wherein said reaction product is obtained in the presence of a solvent at a reaction temperature of 60-350°

C. for a reaction period of time of 5 minutes-50 hours.

24. An electrochromic device according to claim 23 wherein said solvent is selected from the group consisting of an aromatic solvent and a ketone-based solvent.