Stabilized electrochromic media

• US 7,595,011 B2
• Filed: 06/30/2005
• Issued: 09/29/2009
• Est. Priority Date: 07/12/2004
• Status: Expired due to Fees

• Current Assignee: CIBA Specialty Chemicals
• Original Assignee: CIBA Specialty Chemicals
• Inventors: Lord, Simon, Cliff, Nancy, Kanouni, Mouhcine
• Primary Examiner(s): Kugel; Timothy J.
• Application Number:
  US11/171,176
• Publication Number:
  US 20060007519A1
• Time in Patent Office: 1,552 Days
• Field of Search: 252/583, 252/586, 359/241, 359/245
• US Class Current: 252/583
• CPC Class Codes: C08K 5/34 Heterocyclic compounds having nitrogen in the ring
• 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 1/1533 structural features not otherwise provided for
• CPC Class Codes: G02F 1/167 by electrophoresis
• CPC Class Codes: G02F 2201/086 UV absorbing

Abstract

Disclosed are compositions, which are stabilized against degradation and yellowing during exposure to ultraviolet light by the presence of certain hindered amine additives, a method of stabilizing the compositions by the addition of said additives, to the use of such compositions as media in electroactive devices such as electrochromic and electrophoteric devices, and the electroactive devices comprised of these media.

Claims

1. A composition which is suitable as a medium in an electrochromic device, which composition comprises

a) one or more solvents suitable as a medium in an electrochromic device selected from the group consisting of ketones, cyclic esters, cyclic carbonates and glycidyl ether carbonates, and one or more materials which are a functional element of an electrochromic device,

b) an effective amount of one or more ultraviolet light absorbers selected from the group consisting of hydroxyphenylbenzotriazoles and tris-aryl-s-triazines, and

c) an effective amount of one or more N—

H or N-alkyl hindered amine light stabilizers of formula A′

2. A composition according to claim 1 which comprises an electrolyte as one of the one or more functional elements of an electrochromic device.

3. A composition according to claim 1, wherein at least one of the one or more solvents is selected from the group consisting of ketones and cyclic carbonates.

4. A composition according to claim 1, wherein at least one of the one or more solvents is selected from the group consisting of acetone, methyl ethyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, benzoyl acetone, 4-hydroxy-4-methyl-2-pentanone, acetophenone, beta-propiolactone, 2-acetylbutyrolactone, gamma-butyrolactone, gamma-valerolactone, 4-ethenyl-1,3-dioxalane-2-one, propylene carbonate, ethylene carbonate and 1,2-butylene carbonate.

5. A composition according to claim 1, wherein at least one of the one or more solvents is selected from the group consisting of acetone, methyl ethyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, 4-ethenyl-1,3-dioxalane-2-one, propylene carbonate, ethylene carbonate and 1,2-butylene carbonate.

6. A composition according to claim 1, wherein at least one of the one or more solvents is selected from the group consisting of methyl amyl ketone and propylene carbonate.

7. A composition according to claim 1, wherein at least one of the one or more ultraviolet light absorbers is selected from the group consisting of

2-[2-hydroxy-5-(C₁-C₁₂ alkyl or branched alkyl)phenyl]-2H-benzotriazole,

2-[2-hydroxy-3-(C₁-C₁₂ alkyl or branched alkyl)-5-(C₁-C₁₂ alkyl or branched alkyl)phenyl]-2H-benzotriazole,

2-[2-hydroxy-3,5-di(α

,α

-dimethylbenzyl)phenyl]-2H-benzotriazole,

2-[2-hydroxy-3-(α

,α

-dimethylbenzyl)-5-(C₁-C₁₂alkyl or branched alkyl)]-2H-benzotriazole,

C₁-C₁₈ alkyl or branched alkyl esters of 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydro -cinnamic acid,

2-methoxyethyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,

2-(2-methoxyethoxy)ethyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,

2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydro -cinnamate,

2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy -octa(ethyleneoxy)carbonyl)ethyl]phenyl}-2H-benzotriazofe,

5-chloro-2-[2-hydroxy-5-(C₁-C₁₂ alkyl or branched alkyl)phenyl]-2H-benzotriazole,

5-chloro-2-[2-hydroxy-3-(C₁-C₁₂ alkyl or branched alkyl)-5-(C₁-C₁₂ alkyl or branched alkyl) -phenyl]-2H-benzotriazole,

5-chloro-2-[2-hydroxy-3,5-di(α

,α

-dimethylbenzyl)phenyl]-2H-benzotriazole,

5-chloro-2-[2-hydroxy-3-(α

,α

-dimethylbenzyl)-5-(C₁-C₁₂ alkyl or branched alkyl)]-2H-benzo-triazole,

C₁-C₁₈ alkyl or branched alkyl esters of 3-(5-chloro-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy -hydrocinnamic acid,

2-methoxyethyl 3-(5-chloro-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,

2-(2-methoxyethoxy)ethyl 3-(5-chloro-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,

2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-(5-chloro-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydro -cinnamate,

5-chloro-2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole,

5-trifluoro-2-[2-hydroxy-5-(C₁-C₁₂ alkyl or branched alkyl)phenyl]-2H-benzotriazole,

5-trifluoro-2-[2-hydroxy-3-(C₁-C₁₂ alkyl or branched alkyl)-5-(C₁-C₁₂ alkyl or branched alkyl) -phenyl]-2H-benzotriazole,

5-trifluoro-2-[2-hydroxy-3,5-di(α

,α

-dimethylbenzyl)phenyl]-2H -benzotriazole,

5-trifluoro-2-[2-hydroxy-3-(α

,α

-dimethylbenzyl)-5-(C₁-C₁₂ alkyl or branched alkyl)]-2H-benzo -triazole

C₁-C₁₈ alkyl or branched alkyl esters of 3-(5-trifluoro-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy -hydrocinnamic acid,

2-methoxyethyl 3-(5-trifluoro-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,

2-(2-methoxyethoxy)ethyl 3-(5-trifluoro-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydro -cinnamate,

2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-(5-trifluoro-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy -hydrocinnamate,

5-trifluoro-2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole

2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-(C₁-C₁₂ alkyl or branched alkyl)oxyphenyl)-s -triazine,

2,4-diphenyl-6-(2-hydroxy-4-(C₁-C₁₂ alkyl or branched alkyl)oxyphenyl)-s-triazine,

2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)phenyl]-s-triazine,

2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-5-α

-cumyl -phenyl]-s-triazine,

2-[2-hydroxy-4-(1(C₁-C₁₈ alkyl or branched alkyl)oxycarbonylethoxy)phenyl]-4,6-bis(4-phenylphenyl)-1,3,5-triazine, and

the reaction product of 2,4,6-tris(2,4-dihydroxyphenyl)-s-triazine with octyl α

-haloacetate.

8. A composition according to claim 1, wherein at least one of the one or more ultraviolet light absorbers is selected from the group consisting of

2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,

2-(2-hydroxy-5-tert-octylphenyl-2H-benzotriazole,

2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,

2-(2-hydroxy-3-sec-butyl-5-tert-butylphenyl)-2H-benzotriazole,

2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole,

2-[2-hydroxy-3,5-di(α

,α

-dimethylbenzyl)phenyl]-2H-benzotriazole,

2-[2-hydroxy-3-(α

,α

-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole,

octyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,

butyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,

pentyl 3-(benzotrlazol-2-yl)-5-tert-butyl-4-hydroxyhydroclnnammte,

2-methoxysthyl 3-(benzotriazol2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,

2-(2-methoxyethoxy)ethyl 3-(benzotrlazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,

2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-(benzobmzol-2-yl)-5-tert-butyl-4-hydroxyhydro -cinnamate,

2-{2-hydroxyd-but[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]phenyl}-2H -benzotriazole,

5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotilazol,

5-chloro-2-(2-hydroxy-3,5-dI-tert-butylphenyo-2H-benzotllazole,

octyl 3-(5-chlorobenzotzlazol-2-yl)-5-tert-butyt-4-hydroxyhydrocinnamate,

octyl 3-(5-trifluoromethyt-benzotdazol-2-yl-5-tert-butyl-4-hydroxyhydrocinnamate,

butyl 3-(5-trifluoromethyl-benzotdazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,

pentyl 3-(5-trlfluoromethyl-benzotdazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,

5-triflouromethyl-2{2-hydroxy-3-tert-butyl-5[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl) -ethyl]pheny}-2H-benzotrimzole,

2-(2-methoxyethoxy)ethyl 3-(5-trifluoromethylbenzotrizol-2-yl-5-tert-butyl-4-hydroxyhydro -cinnamate,

2-[2-(2-methoxyethoxy)ethoxy]ethyl3-(5-trifluoromethylbenzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,

2,4-bis(2,4-dimethylphenyl-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine,

2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)phenyl]-s -triazine,

2-[2-hydroxy-4-(1-octyoxycarbonylethoxy)phenyl]-4,6-bis(4-phenylphenyl)-1 ,3,5-tiiazlne and

the reaction product of 2,4,6-tris(2,4-dlhydroxyphenyl)-s-triazine with octyl α

-haloacetate.

9. The composition according to claim 1, wherein at least one of the one or more N—

H or N-alkyl hindered amine light stabilizers is selected from the group consisting of

4-hydroxy-2,2,8,6-tetramethylpiperidine,

4-hydroxy-1,2,2,6,6-pentamethylpiperidine,

1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,

1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,

2,2,6,6-tetramethyl-4-piperidyl or 1,2,2,6,6-pentamethyl-4-piperidyl esters of C2-C24 carboxylic acids or said carboxylic acids substituted by one or more hydroxy, C1-C8alkoxy, C2-C8acyloxy, carbonyl, carboxy or C2-C8 alkoxy carbonyl;

2,2,6,6-tetramethyl-4-piperidyl or 1,2,2,6,6-pentamethyl-4-piperidyl bis esters of C2-C10 di -carboxylic acids.

10. A composition according to claim 1 where at least one of the one or more the N—

H or N-alkyl hindered amine light stabilizer selected from the group consisting of

4-hydroxy-2,2,6,6-tetramethylpiperidine,

4-hydroxy-1 2,2,6,6-pentamethylpiperidine,

bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,

bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate,

bis(1,2,2,6,6-pentamethylpiperidin-4-yl) succinate and

4-stearyloxy-2,2,6,6-tetramethylpiperidine.

11. The composition according to claim 1, wherein at least one of the one or more N—

H or N-alkyl hindered amine light stabilizers is a N-methyl HALS.

12. A composition according to claim 1 where ultraviolet light absorbers and hindered amine stabilizers, in total, are present from about 0.05% to about 30% by weight, based on the weight of the solvent.

13. A composition according to claim 1 where ultraviolet light absorbers and hindered amine stabilizers, in total, are present from about 0.1% to about 15% by weight, based on the weight of the solvent.

14. The composition according to claim 1 wherein m is 1 or m is 2, E is hydrogen or C₁-C₁₈ alkyl, when m is 1, R₂ is hydrogen, C₁-C₁₈alkyl or said alkyl optionally interrupted by one or more oxygen atoms, C₇-C₁₈aralkyl, glycidyl, a monovalent acyl radical of a C₂-C₁₈ aliphatic carboxylic acid, said aliphatic monovalent acyl radical of a C₂-C₁₈ aliphatic carboxylic acid substituted by one or more hydroxy, C₁-C₈ alkoxy, C₂-C₈ acyloxy, C₂-C₈ alkoxy carbonyl and when m is 2, R₂ is C₁-C₁₂alkylene or a divalent acyl radical of an aliphatic dicarboxylic acid having 2-18 C atoms.

15. A method of preparing a stablized medium useful in electrochromic devices, which method comprises adding to a composition comprising:

i) one or more solvents suitable as a medium in an electroactive device selected from the group consisting of ketones cyclic esters, cyclic carbonates and glycidyl ether carbonates and one or more more materials which are a functional element of an electrochromic device, and

ii) an effective amount of one or ultraviolet light absorbers selected from the group consisting of hydroxyphenylbenzotriazoles, and tris-aryl-s-triazines

an effective amount of one or more N—

H and N-alkyl hindered amine light stabilizers of formula A′