Black electrochromic compound, and electrolyte-integrated radiation curable electrochromic composition and electrochromic device which contain same

Patent metadata

Field	Value
Publication number	US-11592721-B2
Application number	US-201716481026-A
Country	US
Kind code	B2
Filing date	May 15, 2017
Priority date	Jan 26, 2017
Publication date	Feb 28, 2023
Grant date	Feb 28, 2023

Abstract

The present invention relates to an electrochromic compound, and an electrochromic composition and an electrochromic device, including the same. The electrochromic compound according to the present invention may achieve excellent black coloring effects and excellent curing characteristics, and thus may be used advantageously in an electrochromic device.

First claim

The invention claimed is:

1. A compound having the following Chemical Formula 1:

where, R is each independently selected from the group consisting of hydrogen, a halogen, a C 1 -C 20 alkyl, a halogenated C 1 -C 20 alkyl, an aryl group, an alkyl group linked to oxygen and nitrogen, a C 6 -C 40 aryl group linked to oxygen and nitrogen, and a compound of the following Chemical Formula 2,
with a proviso that at least three R's represent a substituent of the following Chemical Formula 2:

where, X−represents a counter-anion,
A is not present or is selected from the group consisting of a C 1 -C 10 alkylene; a halogenated C 1 -C 10 alkylene; a C 2 -C 10 alkenylene; a halogenated C 2 -C 10 alkenylene; a C 2 -C 10 alkynylene; a halogenated C 2 -C 10 alkynylene; and a heteroatom selected from N, P, O, and S, and
Z is independently selected from the group consisting of a C 1 -C 20 alkyl; a C 1 -C 20 alkyl substituted with CN; a C 1 -C 20 alkoxy; CN; a C 2-20 alkenyl; a C 2-20 alkynyl; a 3- to 10-membered ring cycloalkyl; a 3- to 10-membered ring heterocycloalkyl comprising a heteroatom selected from N, P, O, and S; a C 6-40 aryl; a C 6-40 aryl substituted with one or more substitution groups selected from a C 1 -C 20 alkyl, a C 1 -C 20 alkoxy, a C 1 -C 20 aryloxy, a halogen, a hydroxyl, and CN; and a C 6-40 heteroaryl comprising a heteroatom selected from N, P, O, and S,
with the proviso that the at least one R group that is of the Chemical Formula 2 has Z independently selected from the group consisting of a C 1 -C 20 alkyl; a C 1 -C 20 alkyl substituted with CN; a C 1 -C 20 alkoxy; CN; a C 2-20 alkenyl; a C 2-20 alkynyl; a 3- to 10-membered ring cycloalkyl; and a 3- to 10-membered ring heterocycloalkyl including a heteroatom selected from N, P, O, and S, and
with the proviso that the at least one R group that is of the Chemical Formula 2 has Z independently selected from the group consisting of a C 6-40 aryl; a C 6-40 aryl substituted with one or more substitution groups selected from a C 1 -C 20 alkyl, a C 1 -C 20 alkoxy, a C 1 -C 20 aryloxy, a halogen, a hydroxyl, and CN; and a C 6-40 heteroaryl including a heteroatom selected from N, P, O, and S.

2. The compound of claim 1 , wherein the three R's at the number 1, 3, 5 positions of Chemical Formula 1 are each independently the compound of Chemical Formula 2, and the remaining R's are independently hydrogen or a C 1 -C 20 alkyl.

3. The compound of claim 1 , wherein the A is a C 1 —C 10 alkylene.

4. The compound of claim 1 , wherein the three R's at the number 1, 3, 5 positions of Chemical Formula 1 are each independently the compound of Chemical Formula 2, and among the three R's, one R or two R's is or are selected wherein Z is independently selected from the group consisting of a C 1 -C 20 alkyl; a C 1 -C 20 alkyl substituted with CN; a C 1 -C 20 alkoxy; CN; a C 2-20 alkenyl; a C 2-20 alkynyl; a 3- to 10-membered ring cycloalkyl; and a 3- to 10-membered ring heterocycloalkyl comprising a heteroatom selected from N, P, O, and S, in Chemical Formula 2, and the remaining two R's or one R are selected wherein Z is independently selected from the group consisting of a C 6-40 aryl; a C 6-40 aryl substituted with one or more substitution groups selected from a C 1 -C 20 alkyl, a C 1 -C 20 alkoxy, a C 1 -C 20 aryloxy, a halogen, a hydroxyl, and CN; and a C 6-40 heteroaryl comprising a heteroatom selected from N, P, O, and S, in Chemical Formula 2.

5. The compound of claim 4 , wherein the C 6-40 aryl has any one of the following structures:

where, R1 is each independently selected from the group consisting of hydrogen, a halogen, a C 1 -C 10 alkyl, CN, a hydroxyl, and a C 1 -C 10 alkoxy.

6. The compound of claim 1 , wherein the compound is represented by the following chemical formula:

where X and Z are each independently the same as those defined in claim 1 .

7. The compound of claim 1 , wherein Z does not comprise an anchoring group.

8. The compound of claim 1 , wherein X is selected from the group consisting of Cl − , Br − , I − , F − , C1O 4 − , BF 4 − , PF 6 − , and TFSi − .

9. The compound of claim 1 , wherein the compound exhibits electrochromic characteristics.

10. An electrochromic composition comprising the compound according to claim 1 as a cathodic electrochromic material.

11. The electrochromic composition of claim 10 , wherein the electrochromic composition comprises the compound as a first cathodic electrochromic material, and further comprises a compound represented by the following chemical formula as a second cathodic electrochromic material:

where, X− represents a counter-anion,
R is independently selected from the group consisting of a C 1 -C 20 alkyl, a C 1 -C 20 alkyl substituted with a C 6 -C 40 aryl, benzyl, a 3- to 10-membered ring heterocycloalkyl comprising a heteroatom, a C 6-40 aryl, a C 6-40 aryl substituted with a C 1 -C 20 alkyl, and a C 6-40 heteroaryl comprising a heteroatom selected from N, P, O, and S, and
the second cathodic electrochromic material has discoloration characteristics in which Y is 0.93 to 1.04, L* is 8.35 to 9.35, a* is 41.03 to 46.17, and b* is −23.38 to −24.92 in the color coordinate.

12. The electrochromic composition of claim 11 , wherein the second cathodic electrochromic material is represented by the following chemical formula:

where X− represents a counter anion.

13. The electrochromic composition of claim 11 , wherein a molar ratio of the first cathodic electrochromic material: the second cathodic electrochromic material is 1:1 to 500:1.

14. The electrochromic composition of claim 10 , wherein the electrochromic composition further comprises a counter oxidation compound selected from the group consisting of a ferrocene-based compound and an amine-based compound.

15. The electrochromic composition of claim 14 , wherein the counter oxidation compound is one or more selected from the group consisting of ferrocene, ethyl ferrocene, propyl ferrocene, t-butyl ferrocene, a C 1 -C 20 alkyl ferrocene, a halogenated ferrocene, phenoxazine, 5,10-dihydrophenazine, N,N,N′,N′-tetramethyl-p-phenylenediamine, phenothiazine, 10-methylphenothiazine, and isopropyl phenothiazine.

16. The electrochromic composition of claim 10 , wherein the electrochromic composition further comprises a curing agent selected from the group consisting of an acrylic polymer, polyacrylate, polymethylmethacrylate, polyvinyl acetate, polyurethane, polystyrene, polyacetonitrile, cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, cellulose propionate, hydroxypropylmethyl cellulose, gum, hydrochloride, gellan, carrageenan, pullulan, polyethylene oxide, polypropylene oxide, polyvinyl acetate, poly(N-vinyl pyrrolidone), and polyvinylindene fluoride.

17. An electrochromic device comprising:
a compound, or an electrochromic composition comprising th

Assignees

• Lg Electronics Inc

Inventors

• Koo Sangmo
• Kim Sooyeun
• Park Koun
• An Gukhwan
• Cho Sanggeun

Classifications

• Y02E10/549

  Organic PV cells · CPC title

• C09K2211/1029

  containing one nitrogen atom as the heteroatom · CPC title

• C09K9/02 Primary

  Organic tenebrescent materials · CPC title

• G02F1/1516 Primary

  comprising organic material · CPC title

• C07D401/14

  containing three or more hetero rings · CPC title