Electrochromic device having improved light stability

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 ist 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.

What is claimed is:  
     
         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 ist 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 OX 2  and RED 1 , wherein 
 (1) OX 2  is a reducible electrochromic substance, and  
 (2) RED 1  is an oxidizable electrochromic substance represented by at least one of the formulas  
                     
 wherein  
 R 201  is aryl,  
 R 200  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  
 R 203  to R 206 , independently of one another, are hydrogen, halogen, alkyl, alkoxy, cyano or aryl,  
   with the provisos that when m is at least 2, two adjacent R 203  together also optionally represent a bivalent —CH═CH—CH═CH— radical and when n is at least 2, two adjacent R 204  together also optionally represent a bivalent —CH═CH—CH═CH— radical.    
     
     
         2 . An electrochromic device according to  claim 1  wherein RED, represents one of the formulas (CC), (CCI), (CCII), or (CCIII) wherein 
 R 201  is C 6 -C 10 -aryl,  
 R 202  is C 1 -C 12 -alkyl, C 3 -C 7 -cycloalkyl, C 2 -C 12 -alkenyl, C 7 -C 16 -aralkyl, or C 6 -C 10 -aryl,  
 B is —(CH 2 ) p —, —(CH 2 )—(O—CH 2 ) q  O—CH 2 — or —(CH 2 ) r —C 6 H 4 —(CH 2 ) s —, where the CH 2  groups may be substituted by methyl,  
 R 203  to R 206 , independently of one another, are hydrogen, halogen, C 1 -C 4 -alkyl, C 1 -C,-alkoxy, cyano, or C 6 -C 10 -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 R 203  together also optionally represent a bivalent —CH═CH—CH═CH— radical and when n is at least 2, two adjacent R 204  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 RED, represents one of the formulas (CC), (CCI), (CCII), or (CCIII) wherein R 201  is phenyl or phenyl carrying up to three methyl, methoxy, chlorine, bromine, or cyano radicals, R 202  is an optionally branched C 1 -C 8 -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 —(CH 2 ) p —, 
 R 203  to R 206 , 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 R 203  together also optionally represent a bivalent —CH═CH—CH═CH— radical and when n is at least 2, two adjacent R 204  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 RED, represents the formula (CC) wherein 
 R 201  is phenyl,  
 R 202  is methyl, ethyl, propyl, butyl, phenylpropyl, or phenyl,  
 R 203  and R 204  are hydrogen, and  
 m and n are 1.  
 
     
     
         5 . An electrochromic device according to  claim 4  wherein R 201  and R 202  are phenyl.  
     
     
         6 . An electrochromic device according to  claim 1  wherein RED, represents the formula (CCII) wherein 
 R 202  is phenyl,  
 B is —(CH 2 ) p —,  
 R 203  and R 204  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 OX 2  comprises a compound selected from the formulas  
       
         
           
           
               
               
           
         
         wherein  
         R 2  to R 5 , R 8 , R 9 , R 16  to R 19 , independently of one another, are C 1 -C 18 -alkyl, C 2 -C 12 -alkenyl, C 4 -C 7 -cycloalkyl, C 7 -C 15 -aralkyl, or C 6 -C 10 -aryl, or  
         R 4 ; R 5  or R 8 ; R 9  together can form a —(CH 2 ) 2 — or — (CH 2 ) 3 — bridge,  
         R 6 , R 7  and R 22  to R 25 , independently of one another, are hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, halogen, cyano, nitro, or C 1 -C 4 -alkoxycarbonyl, or  
         R 22 ; R 23  and/or R 24 ; R 25  can form a —CH═CH—CH═CH— bridge,  
         R 10 ; R 11 , R 10 ; R 13 , R 12 ; R 13  and R 14 ; R 15 , independently of one another, are hydrogen or in pairs are a —(CH 2 ) 2 —, —(CH 2 ) 3 —, or —CH═CH— bridge,  
         R 20  and R 21 , independently of one another, are O, N—CN, C(CN) 2 , or N—C 6- C 10 -aryl,  
         R 26  and R 27  are hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, halogen, cyano, nitro, C 1 -C 4 -alkoxycarbonyl, or C 6 -C 10 -aryl,  
         R 69  to R 74 , R 80  and R 81 , independently of one another, are hydrogen or C 1 -C 6 -alkyl, or  
         R 69 ; R 12 , R 70 ; R 13 , R 73 , R 80  and/or R 74 ; R 81  together form a —CH═CH—CH═CH— bridge,  
         E 1  and E 2 , independently of one another, are O, S, NR 1 , or C(CH 3 ) 2 , or  
         E 1  and E 2  together form an —N—(CH 2 ) 2 -N— bridge,  
         R 1  is C 1 -C 18 -alkyl, C 2 -C 12 -alkenyl, C 4 -C 7 -cycloalkyl, C 7 -C 15 -aralkyl, or C 6 -C 10 -aryl,  
         Z 1  is a direct bond or —CH═CH—, —C(CH 3 )═CH—, —C(CN)═CH—, —CCl═CCl—, —C(OH)═CH—, —CCl═CH—, —C≡C—, —CH═N—N═CH—, —C(CH 3 )═N—N═C(CH 3 )—, or —CCl—N—N═CCl—,  
         Z 2  is —(CH 2 ) r — or —CH 2 —C 6 H 4 —CH 2 —,  
         r is an integer from 1 to 10,  
         R 94  and R 95 , independently of one another, are hydrogen or cyano,  
         R 101  to R 105 , independently of one another, are C 6 -C 10 -aryl or an optionally benzo-fused aromatic or quasi-aromatic, five- or six-membered heterocyclic ring,  
         R 107 , R 109 , R 113  and R 114 , independently of one another, are a radical of the formulas (CV) to (CVII)  
         
           
             
             
                 
                 
             
           
         
         R 108 , R 115  and R 116 , independently of one another, are C 6 -C 10 -aryl or a radical of the formula (CV),  
         R 110  to R 112 , R 117  and R 118 , independently of one another, are hydrogen, C 1 - to C 4 -alkyl, halogen, or cyano,  
         E 101  and E 102 , independently of one another, are 0, S, or N—R 119 ,  
         R 119  and R 122 , independently of one another, are C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 4 -C 7 -cycloalkyl, C 7 -C 15 -aralkyl, or C 6 -C 10 -aryl,  
         R 106 , R 120 , R 121 , R 123  and R 124 , independently of one another, are hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, halogen, cyano, nitro, or C 1 -C 4 -alkoxy-carbonyl, or  
         R 120 , R 121  or R 123 , R 124  together form a —CH═CH—CH═CH— bridge,  
         A 1 , A 2  and A 3 , independently of one another, are O or C(CN) 2 ,  
         R 96  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 .  
     
     
         10 . A dihydrophenazine of the formula (CC)  
       
         
           
           
               
               
           
         
         wherein  
         R 201  is C 6 -C 10 -aryl,  
         R 202  is C 1 -C 12 -alkyl, C 3 -C 7 -cycloalkyl, C 2 -C 12 -alkenyl, C 7 -C 16 -aralkyl, or C 6 -C 10 -aryl,  
         R 203  anci R 204 , independently of one another, are hydrogen, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, cyano, or C 6 -C 10 -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 R 203  together also optionally represent a bivalent —CH═CH—CH═CH— radical and when n is at least 2, two adjacent R 204  together also optionally represent a bivalent —CH═CH—CH═CH— radical.  
       
     
     
         11 . A dihydrophenazine of the formula (CCII)  
       
         
           
           
               
               
           
         
         wherein  
         R 202  is C 1 -C 12 -alkyl, C 3 -C 7 -cycloalkyl, C 2 -C 12 -alkenyl, C 7 -C 16 -aralkyl, or C 6 -C 10 -aryl,  
         B is —(CH 2 )—, —(CH 2 )—(O—CH 2 ) q —O—CH 2 — or —(CH 2 ) r —C 6 H 4 —(CH 2 ) s —, where the CH 2  groups are optionally substituted by methyl,  
         R 203  and R 204 , independently of one another, are hydrogen, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, cyano, or C 6 -C 10 -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 R 203  together also optionally represent a bivalent —CH═CH—CH═CH— radical and when n is at least 2, two adjacent R 204  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.  
       
     
     
         12 . An electrochromic medium comprising a pair of electrochromic substances OX 2  and RED 1 , wherein 
 (1) OX 2  is a reducible electrochromic substance, and    (2) RED 1  is an oxidizable electrochromic'substance represented by at least one of the formulas                          wherein    R 201  is aryl,    R 202  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    R 203  to R 206 , independently of one another, are hydrogen, halogen, alkyl, alkoxy, cyano or aryl,    with the provisos at least 2, two adjacent R 203  together also optionally represent a bivalent —CH═CH—CH═CH— radical and    when n is at least 2, two adjacent R 204  together also optionally represent a bivalent —CH-═CH—CH═CH— radical.