Stabilized electrochromic media

• US 20060007519A1
• Filed: 06/30/2005
• Published: 01/12/2006
• Est. Priority Date: 07/12/2004
• Status: Active Grant

• Current Assignee: CIBA Specialty Chemicals
• Original Assignee: CIBA Specialty Chemicals
• Inventors: Cliff, Nancy, Lord, Simon, Kanouni, Mouchine
• Granted Patent: US 7,595,011 B2
• Time in Patent Office: Days
• US Class Current: 359/265
• 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 electroactive devices, which composition comprises

a) one or more solvents suitable as a medium in an electroactive device,

b) an effective amount of one or more additive compounds selected from the group consisting of ultraviolet light absorbers, and

c) an effective amount of one or more additive compounds selected from the group consisting of N—

H and N-alkyl hindered amine light stabilizers.

2. A composition according to claim 1, wherein the electroactive device is 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 sulfones, amides, sulfoxides, ethers, polyethers, alcohols, polyols, nitriles, ketones, aldehydes, carboxylic acids, cyclic esters, cyclic carbonates, glycidyl ether carbonates and silicon/polyol co-polymers.

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

5. A composition according to claim 1, wherein at least one of the one or more solvents is selected from the group consisting of 3-methylsulfolane, tetramethylene sulfone, N,N-dimethylformamide, dimethyl sulfoxide, tetraglyme, methanol, ethanol, ethoxyethanol, acetonitrile, glutaronitrile, 3-hydroxypropionitrile, methoxypropionitrile, 3-ethoxypropionitrile 2-methylglutaronitrile, cyanoethyl sucrose, acetone, methyl ethyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, benzoyl acetone, 4-hydroxy-4-methyl-2-pentanone, acetophenone, acetic acid, beta-propiolactone, 2-acetylbutyrolactone, gamma-butyrolactone, gamma-valerolactone, 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 3-methylsulfolane, tetramethylene sulfone, tetraglyme, acetonitrile, glutaronitrile, 3-hydroxypropionitrile, methoxypropionitrile, 3-ethoxypropionitrile 2-methylglutaronitrile, 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.

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

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 hydroxyphenylbenzotriazoles, benzophenones, oxanilides, tris-aryl-s-triazines, cyanoacrylates, benzoxazinones, cinnamates, malonates, benzoates, terephthalic or isophthalic acid esters with a resorcinol or phenol, benzylidenes and salicylates.

9. 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 hydroxyphenylbenzotriazoles, benzophenones, and tris-aryl-s-triazines.

10. 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-hydroxybenzophenone substituted in the 4-position by hydroxy, C₁-C₁₂ alkoxy, C₁-C₁₂ branched alkoxy or said alkoxy or branched alkoxy substituted by one or more hydroxy and/or interupted by one or more oxygen atoms,

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-C₁₂ alkyl or branched alkyl)]-2H-benzotriazole,

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

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

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-benzotriazole,

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

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

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-benzotriazole,

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

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

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

C₁-C₁₈ alkyl or branched alkyl esters of p-methoxycinnamic acid,

C₁-C₁₈ alkyl or branched alkyl esters of p-methoxybenzylidenemalonic acid,

C₁-C₁₈ alkyl or branched alkyl esters of 2-cyano-3,3-diphenylacrylic acid,

di-(1,2,2,6,6-pentamethylpiperidin-4-yl) p-methoxybenzylidenemalonate,

2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-(C₁-C₁₂ alkyl or branched alkyl)oxy-phenyl)-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

-cumylphenyl]-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.

11. 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

4-methoxy-2-hydroxybenzophenone,

4-octyloxy-2-hydroxybenzophenone,

4-dodecyloxy-2-hydroxybenzophenone,

4-(2-ethylhexyloxy)-2-hydroxybenzophenone,

2,4-dihydroxybenzophenone,

4-methoxy-2,2′

-dihydroxybenzophenone,

4,4′

-dimethoxy-2,2′

-dihydroxybenzophenone,

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

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-hydroxyhydrocinnamate,

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

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

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

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

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

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

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

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

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

2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-(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-hydroxy-propoxy)phenyl]-s-triazine,

2-[2-hydroxy-4-(1-octyoxycarbonylethoxy)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.

12. 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 compound of formula A′

, B′

or O′

13. 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-2,2,6,6-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-C8 alkoxy, C2-C8 acyloxy, 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,

1,1′

-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),

bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl) malonate,

3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,

2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane,

the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane and epichlorohydrin,

4-benzoyl-2,2,6,6-tetramethylpiperidine,

tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate,

tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate,

N,N′

,N″

,N′

″

-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,

octamethylene bis(2,2,6,6-tetramethylpiperidin-4-carboxylate),

N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,

N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide,

1,5-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,5-diaza-4-oxopropane,

1,3,5-tris[3-(2,2,6,6-tetramethylpiperidin-4-ylamino)-2-hydroxy-propyl) isocyanurate,

2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5,1,11,2]heneicosane,

C₁₂-C₁₄alkyl 3-(2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5,1,11,2]-heneicosane-20-yl)propionate,

1,3-di(2,2,6,6-tetramethylpiperidin-4-yl) 2,4-ditridecyl butanetetracarboxylate,

1,3-di(1,2,2,6,6-pentamethylpiperidin-4-yl) 2,4-ditridecyl butanetetracarboxylate,

1,4-bis(2,2,6,6-tetramethylpiperidin-4-yl)-2,2-dimethyl-1,4-diaza-4-oxopropane,

di-(1,2,2,6,6-pentamethylpiperidin-4-yl) p-methoxybenzylidenemalonate,

dodecyl 3-(2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5,1,11,2]heneicosane-20-yl)propionate,

the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4′

-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),

the polycondensation product of dimethyl succinate and 4-hydroxy-2,2,6,6-tetra-methyl-1-piperidine ethanol,

the polycondensation product of 2,4-dichloro-6-[N-butyl-N-(2,2,6,6-tetramethyl-piperidin-4-yl)amino]-s-triazine and 1,10-diamino-4,7-diazadecane,

polymeric hindered amine light stabilizers and oligomeric hindered amine light stabilizers.

14. 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,

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

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

16. 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.

17. 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.

18. 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.

19. A composition according to claim 1 where the electroactive device is an electrophoteric device.

20. A composition according to claim 1 where at least one of the one or more solvents is selected from the group consisting of esters, epoxides, vinyl ethers, aromatic hydrocarbons, halogenated organic solvents, saturated linear or branched hydrocarbons, silicone oils, and low molecular weight halogen-containing polymers.

21. A method of preparing a stablized medium useful in electrochromic devices, which method comprises adding an effective amount of one or more additive compounds selected from the group consisting of N—

H and N-alkyl hindered amine light stabilizers to a composition comprising;

i) one or more solvents suitable as a medium in an electroactive device, and

ii) an effective amount of one or more additive compounds selected from the group consisting of ultraviolet light absorbers.

22. An electroactive device comprising a composition which comprises

a) one or more solvent suitable as a medium in an electroactive device,

b) one or more additive compounds selected from the group consisting of ultraviolet light absorbers and

c) one or more additive compounds selected from the group consisting of N—

H and N-alkyl hindered amine light stabilizers.