Electrochromic device having improved light stability

• US 6,388,796 B1
• Filed: 02/09/2000
• Issued: 05/14/2002
• Est. Priority Date: 02/18/1999
• Status: Expired due to Fees

• Current Assignee: Bayer AG
• Original Assignee: Bayer AG
• Inventors: Neigl, Ralf, Berneth, Horst
• Primary Examiner(s): Epps, Georgia
• Assistant Examiner(s): THOMPSON, TIMOTHY J
• Application Number:
  US09/501,489
• Time in Patent Office: 825 Days
• Field of Search: 359/265, 359/583, 359/269, 359/270, 359/273, 359/275, 359/267, 252/582, 252/586, 252/583
• US Class Current: 359/265
• CPC Class Codes: C07D 241/38 with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
• CPC Class Codes: C07D 241/46 Phenazines
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions

Abstract

The invention relates to an electrochromic device having

(a) a pair of glass or plastic plates or plastic films wherein at least one such plate or film is provided on one side each with an electrically conductive coating, wherein

(1) at least one such plate or film and its conductive coating is transparent,

(2) the other such plate or film and its conductive coating is optionally mirrored,

(3) the electrically conductive layer of one or both of the two plates or films is optionally divided into separate segments optionally provided with individual contacts, and

(4) the plates or films are joined on the sides of their conductive coating by means of a sealing ring to form a volume; and

(b) the volume formed by the two plates or films and the sealing ring is filled with an electrochromic medium containing certain dihydronaphthazines or dihydrophenazines.

Claims

1. An electrochromic device comprising

(a) a pair of glass or plastic plates or plastic films wherein at least one such plate or film is provided on one side each with an electrically conductive coating, wherein

(1) at least one such plate or film and its conductive coating is transparent,

(2) the other such plate or film and its conductive coating is optionally mirrored,

(3) the electrically conductive layer of one or both of the two plates or films is optionally divided into separate segments optionally provided with individual contacts, and

(4) the plates or films are joined on the sides of their conductive coating by means of a sealing ring to form a volume;

and

(b) the volume formed by the two plates or films and the sealing ring is filled with an electrochromic medium comprising a pair of electrochromic substances OX₂ and RED₁, wherein

(1) OX₂ is a reducible electrochromic substance, and

(2) RED₁ is an oxidizable electrochromic substance represented by at least one of the formulas

 

wherein

R²⁰¹ is aryl,

R²⁰² is alkyl, cycloalkyl, alkenyl, aralkyl, or aryl,

B is a bivalent bridge,

m and n, independently of one another, are integers from 1 to 4, and

R²⁰³ to R²⁰⁶, independently of one another, are hydrogen, halogen, alkyl, alkoxy, cyano or aryl,

with the provisos that when m is at least 2, two adjacent R²⁰³ together also optionally represent a bivalent —

CH═

CH—

CH═

CH—

radical and when n is at least 2, two adjacent R²⁰⁴ together also optionally represent a bivalent —

CH═

CH—

CH═

CH—

radical.

2. An electrochromic device according to claim 1 wherein RED₁ represents one of the formulas (CC), (CCI), (CCII), or (CCIII) wherein

R²⁰¹ is C₆-C₁₀-aryl,

R²⁰² is C₁-C₁₂-alkyl, C₃-C₇-cycloalkyl, C₂-C₁₂-alkenyl, C₇-C₁₆-aralkyl, or C₆-C₁₀-aryl,

B is — (CH₂)_p—

, —

(CH₂)—

(O—

CH₂)_q—

O—

CH₂—

or —

(CH₂)_r—

C₆H₄—

(CH₂)_s—

, where the CH₂ groups may be substituted by methyl,

R²⁰³ to R²⁰⁶, independently of one another, are hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, cyano, or C₆-C₁₀-aryl,

m and n, independently of one another, are integers from 1 to 4,

with the provisos that when m is at least 2, two adjacent R²⁰³ together also optionally represent a bivalent —

CH═

CH—

CH═

CH—

radical and when n is at least 2, two adjacent R²⁰⁴ together also optionally represent a bivalent —

CH═

CH—

CH═

CH—

radical,

p is an integer from 2 to 20, and

q, r, and s, independently of one another, are integers from 0 to 10.

3. An electrochromic device according to claim 1 wherein RED₁ represents one of the formulas (CC), (CCI), (CCII), or (CCIII) wherein

R²⁰¹ is phenyl or phenyl carrying up to three methyl, methoxy, chlorine, bromine, or cyano radicals,

R²⁰² is an optionally branched C₁-C₈-alkyl, cyclopentyl, cyclohexyl, benzyl, phenethyl, phenylpropyl radical wherein each such radical optionally carries up to three methyl, methoxy, chlorine, bromine, or cyano radicals,

B is —

(CH₂)_p—

,

R²⁰³ to R²⁰⁶, independently of one another, are hydrogen, chlorine, bromine, methyl, ethyl, propyl, butyl, methoxy, ethoxy, cyano, or phenyl,

m and n, independently of one another, are integers from 1 to 2,

with the provisos that when m is at least 2, two adjacent R²⁰³ together also optionally represent a bivalent —

CH═

CH—

CH═

CH—

radical and when n is at least 2, two adjacent R²⁰⁴ together also optionally represent a bivalent —

CH═

CH—

CH═

CH—

radical, and

p is an integer from 2 to 10.

4. An electrochromic device according to claim 1 wherein RED₁ represents the formula (CC) wherein

R²⁰¹ is phenyl,

R²⁰² is methyl, ethyl, propyl, butyl, phenylpropyl, or phenyl,

R²⁰³ and R²⁰⁴ are hydrogen, and

m and n are 1.

5. An electrochromic device according to claim 4 wherein R²⁰¹ and R²⁰² are phenyl.

6. An electrochromic device according to claim 1 wherein RED₁ represents the formula (CCII) wherein

R²⁰² is phenyl,

B is —

(CH₂)_p—

,

R²⁰³ and R²⁰⁴ are hydrogen,

m and n are 1, and

p is an integer from 2 to 6.

7. An electrochromic device according to claim 6 wherein p is 3 to 5.

8. An electrochromic device according to claim 1 wherein OX₂ comprises a compound selected from the formulas

wherein

R² to R⁵, R⁸, R⁹, R¹⁶ to R¹⁹, independently of one another, are C₁-C₁₈-alkl, C₂-C₁₂-alkenyl, C₄-C₇-cycloalkyl, C₇-C₁₅-aralkyl, or C₆-C₁₀-aryl, or

R⁴;

R⁵ or R⁸;

R⁹ together can form a —

(CH₂)₂—

or —

(CH₂)₃—

bridge,

R⁶, R⁷ and R²² to R²⁵, independently of one another, are hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, cyano, nitro, or C₁-C₄-alkoxycarbonyl, or

R²²;

R²³ and/or R²⁴;

R²⁵ can form a —

CH═

CH—

CH═

CH—

bridge,

R¹⁰;

R¹¹, R¹⁰;

R¹³, R¹²;

R¹³ and R¹⁴;

R¹⁵, independently of one another, are hydrogen or in pairs are a —

(CH₂)₂—

, —

(CH₂)₃—

, or —

CH═

CH—

bridge,

R²⁰ and R²¹, independently of one another, are O, N—

CN, C(CN)₂, or N—

C₆-C₁₀-aryl,

R²⁶ and R²⁷ are hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, cyano, nitro, C₁-C₄-alkoxycarbonyl, or C₆-C₁₀-aryl,

R⁶⁹ to R⁷⁴, R⁸⁰ and R⁸¹, independently of one another, are hydrogen or C₁-C₆-alkyl, or

R⁶⁹;

R¹², R⁷⁰;

R¹³, R⁷³;

R⁸⁰ and/or R⁷⁴;

R⁸¹ together form a —

CH═

CH—

CH═

CH—

bridge,

E¹ and E², independently of one another, are O, S, NR¹, or C(CH₃)₂, or

E¹ and E² together form an —

N—

(CH₂)₂—

N—

bridge,

R¹ is C₁-C₁₈-alkyl, C₂-C₁₂-alkenyl, C₄-C₇-cycloalkyl, C₇-C₁₅-aralkyl, or C₆-C₁₀-aryl,

Z¹ is a direct bond or —

CH═

CH—

, —

C(CH₃)═

CH—

, —

C(CN)═

CH—

, —

CCl═

CCl—

, —

C(OH)═

CH—

, —

CCl═

CH—

, —

C≡

C—

, —

CH═

N—

N═

CH—

, —

C(CH₃)═

N—

N═

C(CH₃)—

, or —

CCl═

N—

N═

CCl—

,

Z² is —

(CH₂)_r—

or —

CH₂-C₆H₄-CH₂—

,

r is an integer from 1 to 10,

R⁹⁴ and R⁹⁵, independently of one another, are hydrogen or cyano,

R¹⁰¹ to R¹⁰⁵, independently of one another, are C₆-C₁₀-aryl or an optionally benzo-fused aromatic or quasi-aromatic, five- or six-membered heterocyclic ring,

R¹⁰⁷, R¹⁰⁹, R¹¹³ and R¹¹⁴, independently of one another, are a radical of the formulas (CV) to (CVII)

R¹⁰⁸, R¹¹⁵ and R¹¹⁶, independently of one another, are C₆-C₁₀-aryl or a radical of the formula (CV),

R¹¹⁰ to R¹¹², R¹¹⁷ and R¹¹⁸, independently of one another, are hydrogen, C₁- to C₄-alkyl, halogen, or cyano,

E¹⁰¹ and E¹⁰², independently of one another, are O, S, or N—

R¹¹⁹,

R¹¹⁹ and R¹²², independently of one another, are C₁-C₁₈-alkyl, C₂-C₈-alkenyl, C₄-C₇-cycloalkyl, C₇-C₁₅-aralkyl, or C₆-C₁₀-aryl,

R¹⁰⁶, R¹²⁰, R¹²¹, R¹²³ and R¹²⁴, independently of one another, are hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, cyano, nitro, or C₁-C₄-alkoxycarbonyl, or

R¹²⁰, R¹²¹ or R¹²³, R¹²⁴ together form a —

CH═

CH—

CH═

CH—

bridge,

A¹, A² and A³, independently of one another, are O or C(CN)₂,

R⁹⁶ is hydrogen, phenyl, or tert-butyl, and

X⁻

is an anion which is redox-inert under the conditions.

9. A window, separating screen, sight protection screen, glazing, roof glazing, light filter, mirror, or display device comprising an electrochromic device according to claim 1.