Electrochromic composition

• US 9,841,652 B2
• Filed: 09/16/2014
• Issued: 12/12/2017
• Est. Priority Date: 09/17/2013
• Status: Active Grant

• Current Assignee: Essilor International SA
• Original Assignee: Essilor International SA
• Inventors: Biver, Claudine, Archambeau, Samuel, Berit-Debat, Fabien
• Primary Examiner(s): Jones, James
• Application Number:
  US15/022,821
• Publication Number:
  US 20160231636A1
• Time in Patent Office: 1,183 Days
• Field of Search: 359275
• CPC Class Codes: C09K 2211/1007 Non-condensed systems
• CPC Class Codes: C09K 2211/1011 Condensed systems
• CPC Class Codes: C09K 2211/1029 containing one nitrogen atom as the heteroatom
• CPC Class Codes: C09K 2211/1044 containing two nitrogen atoms as heteroatoms
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02C 7/101 having an electro-optical light valve electro-optical elements per se G02F
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
• CPC Class Codes: G02F 1/15165 Polymers
• CPC Class Codes: G02F 2001/1502 complementary cell

Abstract

The present invention relates to an electrochromic composition comprising at least one reducing compound, at least one oxidizing compound which is selected from specific viologen derivatives, and at least one dye. Said composition can be used as a variable transmittance medium for the manufacture of an optical article, such as an ophthalmic lens.

Claims

1. An electrochromic composition comprising:

at least one reducing compound;

at least one dye;

at least one electrochromic oxidizing compound selected from viologen derivatives of formula (I)

2. The electrochromic composition according to claim 1, wherein Z is selected from C₁-C₁₂ alkylene, aryl substituted C₁-C₁₂ alkylene, phenylene, naphthylene, (C₁-C₄ alkylene)-phenylene-(C₁-C₄ alkylene), (C₁-C₄ alkylene)-naphthylene-(C₁-C₄ alkylene), quinoxaline-2,3-diyl, (C₁-C₄ alkylene)-quinoxaline-2,3-diyl-(C₁-C₄ alkylene), phenylene-phenylene, (C₁-C₄ alkylene)-phenylene-phenylene-(C₁-C₄ alkylene) and phenylene-fluorenylene-phenylene, preferably Z is selected from —

CH₂—

, —

(CH₂)₂—

, —

(CH₂)₃—

, —

(CH₂)₄—

, —

(CH₂)₅—

, —

CH₂—

CH(CH₃)—

CH₂—

, —

CH₂—

CH(CH₂Phenyl)-CH₂—

, —

(CH₂)₂—

CH(CH₃)—

CH₂—

, —

(CH₂)₃—

CH(CH₃)—

CH₂—

, —

(CH₂)₂—

CH(CH₃)—

(CH₂)₂—

,

3. The electrochromic composition according to claim 1, wherein R³, R⁴, R⁵ and R⁶ are each independently selected from C₁-C₄ alkyl, C₁-C₄ alkoxycarbonyl, alkanoyl, aroyl, aryl and heteroaryl, wherein the aryl and heteroaryl may be substituted by one or more substituents selected from C₁-C₄ alkyl and C₁-C₄ haloalkyl, preferably, R³, R⁴, R⁵ and R⁶ are each independently selected from methyl, ethoxycarbonyl, phenyl, p-methylphenyl and p-trifluoromethylphenyl.

4. The electrochromic composition according to claim 1, wherein the counterion X⁻

is selected from halide, tetrafluoroborate, tetraphenylborate, hexafluorophosphate, nitrate, methanesulfonate, trifluoromethane sulfonate, toluene sulfonate, hexachloroantimonate, bis(trifluoromethanesulfonyl)imide, perchlorate, acetate and sulfate.

5. The electrochromic composition according to claim 1, wherein at least one of the viologen derivatives is selected from compounds of formula (III):

6. The electrochromic composition according to claim 1, wherein at least one of the viologen derivatives is selected from compounds of formula (IV):

7. The electrochromic composition according to claim 1, wherein said viologen derivatives are selected from compounds I-1 to 1-50, III-1 to 111-18 and IV-1 and IV-14:

8. The electrochromic composition according to claim 1, wherein the reducing compound is selected from ferrocene and their derivatives such as ethyl ferrocene, t-butyl ferrocene;

phenoxazine and their derivatives, such as N-benzylphenoxazine;

phenazine and their derivatives, such as 5,10-dihydrophenazine, N,N,N′

,N′

-tetramethyl-p-phenylenediamine;

phenothiazine and their derivatives, such as 10-methylphenothiazine and isopropylphenothiazine;

thioanthrene; and

tetrathiafulvalene.

9. The electrochromic composition according to claim 8, wherein said composition comprises a fluid, mesomorphous or gel host medium preferably selected from the group consisting of organic solvents, liquid crystals, polymers, liquid crystal polymers and mixtures thereof.

10. The electrochromic composition according to claim 1, wherein the dye is selected from the group consisting of:

organic or inorganic photochromic and/or dichroic substances;

electrochromic substances distinct from the first constituent of this invention and which may be selected among the above compounds of Formulas (I) and/or (II) or among different electrochromic compounds;

organic and inorganic pigments, especially in the form of nanoparticles;

organic dyes;

optical brighteners;

or mixtures thereof.

11. An electrochromic device comprising the composition as defined in claim 1.

12. The electrochromic device according to claim 11, wherein said electrochromic device comprises a mechanism for holding the composition in a mechanically stable environment.

13. The electrochromic device according to claim 11, wherein said electrochromic device comprises at least one transparent electrochromic cell comprising a pair of opposed substrates facing each other and forming a gap, and the gap is filled with the electrochromic composition as defined in claim 1.

14. The electrochromic device according to claim 11, wherein said electrochromic device is an optical article.

15. The electrochromic device according to claim 14, wherein the optical article is an optical lens or optical filter, window, visor, mirror or displays.

16. The electrochromic device according to claim 15, wherein the optical article is an optical lens.

17. The electrochromic device according to claim 15, wherein the optical article is an ophthalmic lens.