JP2012224548A - Electrochromic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an electrochromic compound capable of maintaining a colored state for a long period; an electrochromic composition; a display element; and a display device.SOLUTION: The electrochromic compound can be expressed by the general formula.

Description

  The present invention relates to an electrochromic compound, an electrochromic composition, a display element, and a display device.

  In recent years, electronic paper has been known as an electronic medium that replaces paper. Electronic paper is used like a paper display device.

  As display devices for electronic paper, reflection type liquid crystal display devices, electrophoretic display devices, and the like are known. However, it is very difficult to display multiple colors while ensuring white reflectance and contrast ratio. In general, a color filter is provided for multicolor display. In addition to the light absorbing by the color filter, one pixel is divided into, for example, red, green, and blue, so that the white reflectance decreases. As a result, the contrast ratio decreases.

  On the other hand, an electrochromic display device is known as a reflective display device without a color filter. An electrochromic display device is expected as a multicolor display device because it can generate various colors depending on the structure of the electrochromic compound.

Patent Document 1 includes a general formula A- (CX ₂ ) _n -B.
(However, A is a monovalent linking group, B is a redox chromophore, X is a halogen atom, and n is an integer of 1 or more.)
The electrochromic compound represented by these is disclosed.

  However, it is desired to maintain the colored state for a longer time.

  The present invention has been made in view of the above-described problems of the prior art, and an object thereof is to provide an electrochromic compound, an electrochromic composition, a display element, and a display device that can maintain a colored state for a long time.

  The electrochromic compound of the present invention has the general formula

（式中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７、Ｘ^８及びＸ^９は、それぞれ独立に、水素原子、ハロゲン基、ヒドロキシル基、ニトロ基、シアノ基、カルボキシル基、置換若しくは無置換のアルコキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、置換若しくは無置換のアルキルカルボニル基、置換若しくは無置換のアリールカルボニル基、アミノカルボニル基、置換若しくは無置換のモノアルキルアミノカルボニル基、置換若しくは無置換のジアルキルアミノカルボニル基、置換若しくは無置換のモノアリールアミノカルボニル基、置換若しくは無置換のジアリールアミノカルボニル基、スルホン酸基、置換若しくは無置換のアルコキシスルホニル基、置換若しくは無置換のアリールオキシスルホニル基、置換若しくは無置換のアルキルスルホニル基、置換若しくは無置換のアリールスルホニル基、アミノスルホニル基、置換若しくは無置換のモノアルキルアミノスルホニル基、置換若しくは無置換のジアルキルアミノスルホニル基、置換若しくは無置換のモノアリールアミノスルホニル基、置換若しくは無置換のジアリールアミノスルホニル基、アミノ基、置換若しくは無置換のモノアルキルアミノ基、置換若しくは無置換のジアルキルアミノ基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアリール基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のアリールオキシ基、置換若しくは無置換のアルキルチオ基、置換若しくは無置換のアリールチオ基又は置換若しくは無置換の複素環基であり、Ｙは、パーハロアルキル基であり、Ｚは、カルボキシル基、ホスホン酸基、スルホン酸基、リン酸基又はヒドロキシル基であり、Ｅは、オキシ基、チオ基又はセレノ基であり、Ｒ^１及びＲ^２は、それぞれ独立に、置換若しくは無置換のアルキレン基、置換若しくは無置換のアルケニレン基、置換若しくは無置換のアルキニレン基、置換若しくは無置換のアリーレン基又は置換若しくは無置換のアラルキレン基であり、Ａ⁻及びＢ⁻は、それぞれ独立に、１価のアニオンである。）
で表される化合物である。

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ are each independently a hydrogen atom, a halogen group, a hydroxyl group, a nitro group, or a cyano group. , Carboxyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group, substituted or unsubstituted A monoalkylaminocarbonyl group, a substituted or unsubstituted dialkylaminocarbonyl group, a substituted or unsubstituted monoarylaminocarbonyl group, a substituted or unsubstituted diarylaminocarbonyl group, a sulfonic acid group, a substituted or unsubstituted alkoxysulfonyl group, Substituted or unsubstituted aryloxysulfoni Group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted or unsubstituted Monoarylaminosulfonyl group, substituted or unsubstituted diarylaminosulfonyl group, amino group, substituted or unsubstituted monoalkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkyl group, substituted or unsubstituted Substituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted of A reelthio group or a substituted or unsubstituted heterocyclic group, Y is a perhaloalkyl group, Z is a carboxyl group, a phosphonic acid group, a sulfonic acid group, a phosphoric acid group or a hydroxyl group, and E is an oxy R ¹ and R ² are each independently a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted group, a thio group or a seleno group An arylene group or a substituted or unsubstituted aralkylene group, and A ^- and B ^- are each independently a monovalent anion.)
It is a compound represented by these.

  The electrochromic compound of the present invention has the general formula

（式中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７、Ｘ^８、Ｘ^９、Ｘ^１０及びＸ^１１は、それぞれ独立に、水素原子、ハロゲン基、ヒドロキシル基、ニトロ基、シアノ基、カルボキシル基、置換若しくは無置換のアルコキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、置換若しくは無置換のアルキルカルボニル基、置換若しくは無置換のアリールカルボニル基、アミノカルボニル基、置換若しくは無置換のモノアルキルアミノカルボニル基、置換若しくは無置換のジアルキルアミノカルボニル基、置換若しくは無置換のモノアリールアミノカルボニル基、置換若しくは無置換のジアリールアミノカルボニル基、スルホン酸基、置換若しくは無置換のアルコキシスルホニル基、置換若しくは無置換のアリールオキシスルホニル基、置換若しくは無置換のアルキルスルホニル基、置換若しくは無置換のアリールスルホニル基、アミノスルホニル基、置換若しくは無置換のモノアルキルアミノスルホニル基、置換若しくは無置換のジアルキルアミノスルホニル基、置換若しくは無置換のモノアリールアミノスルホニル基、置換若しくは無置換のジアリールアミノスルホニル基、アミノ基、置換若しくは無置換のモノアルキルアミノ基、置換若しくは無置換のジアルキルアミノ基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアリール基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のアリールオキシ基、置換若しくは無置換のアルキルチオ基、置換若しくは無置換のアリールチオ基又は置換若しくは無置換の複素環基であり、Ｙは、パーハロアルキル基であり、Ｚは、カルボキシル基、ホスホン酸基、スルホン酸基、リン酸基又はヒドロキシル基であり、Ｌは、置換若しくは無置換のアリーレン基であり、Ｒ^１及びＲ^２は、それぞれ独立に、置換若しくは無置換のアルキレン基、置換若しくは無置換のアルケニレン基、置換若しくは無置換のアルキニレン基、置換若しくは無置換のアリーレン基又は置換若しくは無置換のアラルキレン基であり、Ａ⁻及びＢ⁻は、それぞれ独立に、１価のアニオンであり、ｎは０以上３以下の整数である。）
で表される化合物である。

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ and X ¹¹ are each independently a hydrogen atom, a halogen group, or a hydroxyl group. Nitro group, cyano group, carboxyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group Substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, sulfonic acid group, substituted or unsubstituted Substituted alkoxysulfonyl group, substituted or unsubstituted Alkyloxysulfonyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted Or an unsubstituted monoarylaminosulfonyl group, a substituted or unsubstituted diarylaminosulfonyl group, an amino group, a substituted or unsubstituted monoalkylamino group, a substituted or unsubstituted dialkylamino group, a substituted or unsubstituted alkyl group, A substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, A substituted or unsubstituted arylthio group or a substituted or unsubstituted heterocyclic group, Y is a perhaloalkyl group, and Z is a carboxyl group, a phosphonic acid group, a sulfonic acid group, a phosphoric acid group or a hydroxyl group. , L is a substituted or unsubstituted arylene group, and R ¹ and R ² are each independently a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, substituted or an unsubstituted arylene group or a substituted or unsubstituted aralkylene group, a ^- and B ^- are each independently a monovalent anionic, n represents a an integer of 0 to 3).
It is a compound represented by these.

  The electrochromic compound of the present invention has the general formula

（式中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７及びＸ^８は、それぞれ独立に、水素原子、ハロゲン基、ヒドロキシル基、ニトロ基、シアノ基、カルボキシル基、置換若しくは無置換のアルコキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、置換若しくは無置換のアルキルカルボニル基、置換若しくは無置換のアリールカルボニル基、アミノカルボニル基、置換若しくは無置換のモノアルキルアミノカルボニル基、置換若しくは無置換のジアルキルアミノカルボニル基、置換若しくは無置換のモノアリールアミノカルボニル基、置換若しくは無置換のジアリールアミノカルボニル基、スルホン酸基、置換若しくは無置換のアルコキシスルホニル基、置換若しくは無置換のアリールオキシスルホニル基、置換若しくは無置換のアルキルスルホニル基、置換若しくは無置換のアリールスルホニル基、アミノスルホニル基、置換若しくは無置換のモノアルキルアミノスルホニル基、置換若しくは無置換のジアルキルアミノスルホニル基、置換若しくは無置換のモノアリールアミノスルホニル基、置換若しくは無置換のジアリールアミノスルホニル基、アミノ基、置換若しくは無置換のモノアルキルアミノ基、置換若しくは無置換のジアルキルアミノ基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアリール基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のアリールオキシ基、置換若しくは無置換のアルキルチオ基、置換若しくは無置換のアリールチオ基又は置換若しくは無置換の複素環基であり、Ｙは、パーハロアルキル基であり、Ｚは、カルボキシル基、ホスホン酸基、スルホン酸基、リン酸基又はヒドロキシル基であり、Ａは、Ｎ、Ｏ、Ｓ又はＳｅを１個以上含み、Ｌと結合するＣを含む置換又は無置換の５員環の複素環基であり、Ｌは、置換又は無置換のアリーレン基であり、Ｒ^１及びＲ^２は、それぞれ独立に、置換若しくは無置換のアルキレン基、置換若しくは無置換のアルケニレン基、置換若しくは無置換のアルキニレン基、置換若しくは無置換のアリーレン基又は置換若しくは無置換のアラルキレン基であり、Ｂ⁻及びＣ⁻は、それぞれ独立に、１価のアニオンであり、ｎは１以上３以下の整数である。）
で表される化合物である。

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are each independently a hydrogen atom, a halogen group, a hydroxyl group, a nitro group, a cyano group, or a carboxyl group. Substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group, substituted or unsubstituted monoalkylamino Carbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, sulfonic acid group, substituted or unsubstituted alkoxysulfonyl group, substituted or unsubstituted A substituted aryloxysulfonyl group, Substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted or unsubstituted monoaryl Aminosulfonyl group, substituted or unsubstituted diarylaminosulfonyl group, amino group, substituted or unsubstituted monoalkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl Group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl A thio group or a substituted or unsubstituted heterocyclic group, Y is a perhaloalkyl group, Z is a carboxyl group, a phosphonic acid group, a sulfonic acid group, a phosphoric acid group or a hydroxyl group, and A is N , O, S, or Se, and a substituted or unsubstituted 5-membered heterocyclic group containing C bonded to L, L is a substituted or unsubstituted arylene group, R ¹ and Each R ² is independently a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted aralkylene group; B ^- and C ^- are each independently a monovalent anion, and n is an integer of 1 to 3.
It is a compound represented by these.

  The electrochromic compound of the present invention has the general formula

（式中、Ｘ^１、Ｘ^２、Ｘ^３及びＸ^４は、それぞれ独立に、水素原子、ハロゲン基、ヒドロキシル基、ニトロ基、シアノ基、カルボキシル基、置換若しくは無置換のアルコキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、置換若しくは無置換のアルキルカルボニル基、置換若しくは無置換のアリールカルボニル基、アミノカルボニル基、置換若しくは無置換のモノアルキルアミノカルボニル基、置換若しくは無置換のジアルキルアミノカルボニル基、置換若しくは無置換のモノアリールアミノカルボニル基、置換若しくは無置換のジアリールアミノカルボニル基、スルホン酸基、置換若しくは無置換のアルコキシスルホニル基、置換若しくは無置換のアリールオキシスルホニル基、置換若しくは無置換のアルキルスルホニル基、置換若しくは無置換のアリールスルホニル基、アミノスルホニル基、置換若しくは無置換のモノアルキルアミノスルホニル基、置換若しくは無置換のジアルキルアミノスルホニル基、置換若しくは無置換のモノアリールアミノスルホニル基、置換若しくは無置換のジアリールアミノスルホニル基、アミノ基、置換若しくは無置換のモノアルキルアミノ基、置換若しくは無置換のジアルキルアミノ基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアリール基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のアリールオキシ基、置換若しくは無置換のアルキルチオ基、置換若しくは無置換のアリールチオ基又は置換若しくは無置換の複素環基であり、Ｙは、パーハロアルキル基であり、Ｚは、カルボキシル基、ホスホン酸基、スルホン酸基、リン酸基又はヒドロキシル基であり、Ａは、置換又は無置換のベンゼン由来のｎ価の基であり、Ｒ^１及びＲ^２は、それぞれ独立に、置換若しくは無置換のアルキレン基、置換若しくは無置換のアルケニレン基、置換若しくは無置換のアルキニレン基、置換若しくは無置換のアリーレン基又は置換若しくは無置換のアラルキレン基であり、Ｂ⁻及びＣ⁻は、それぞれ独立に、１価のアニオンであり、ｎは２以上６以下の整数であり、ｍは１以上ｎ−１以下の整数である。）
で表される化合物である。

(Wherein X ¹ , X ² , X ³ and X ⁴ are each independently a hydrogen atom, halogen group, hydroxyl group, nitro group, cyano group, carboxyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or Unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group Substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, sulfonic acid group, substituted or unsubstituted alkoxysulfonyl group, substituted or unsubstituted aryloxysulfonyl group, substituted or unsubstituted Alkyls Phonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted or unsubstituted monoarylaminosulfonyl group, substituted or Unsubstituted diarylaminosulfonyl group, amino group, substituted or unsubstituted monoalkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted Alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted A heterocyclic group, Y is a perhaloalkyl group, Z is a carboxyl group, a phosphonic acid group, a sulfonic acid group, a phosphoric acid group or a hydroxyl group, and A is an n derived from a substituted or unsubstituted benzene. Each of R ¹ and R ² is independently a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group or a substituted group or an unsubstituted aralkylene group, B ^- and C ^- are each independently a monovalent anionic, n is 2 to 6 integer, m is 1 or n-1 an integer .)
It is a compound represented by these.

  In the electrochromic composition of the present invention, the electrochromic compound of the present invention is bonded or adsorbed to a conductive or semiconducting nanostructure.

  The electrochromic composition of the present invention has a general formula of conductive or semiconducting nanostructures.

（式中、Ｂは、ハロゲン基であり、Ｃは、アルキレン基であり、Ｄ^１は、ハロゲン基又はアルコキシ基であり、Ｄ^２及びＤ^３は、それぞれ独立に、ハロゲン基、アルコキシ基又はアルキル基である。）
で表される化合物を反応させた後、一般式

(In the formula, B is a halogen group, C is an alkylene group, D ¹ is a halogen group or an alkoxy group, and D ² and D ³ are each independently a halogen group, an alkoxy group or an alkyl group. Group.)
After reacting the compound represented by general formula

（式中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７、Ｘ^８及びＸ^９は、それぞれ独立に、水素原子、ハロゲン基、ヒドロキシル基、ニトロ基、シアノ基、カルボキシル基、置換若しくは無置換のアルコキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、置換若しくは無置換のアルキルカルボニル基、置換若しくは無置換のアリールカルボニル基、アミノカルボニル基、置換若しくは無置換のモノアルキルアミノカルボニル基、置換若しくは無置換のジアルキルアミノカルボニル基、置換若しくは無置換のモノアリールアミノカルボニル基、置換若しくは無置換のジアリールアミノカルボニル基、スルホン酸基、置換若しくは無置換のアルコキシスルホニル基、置換若しくは無置換のアリールオキシスルホニル基、置換若しくは無置換のアルキルスルホニル基、置換若しくは無置換のアリールスルホニル基、アミノスルホニル基、置換若しくは無置換のモノアルキルアミノスルホニル基、置換若しくは無置換のジアルキルアミノスルホニル基、置換若しくは無置換のモノアリールアミノスルホニル基、置換若しくは無置換のジアリールアミノスルホニル基、アミノ基、置換若しくは無置換のモノアルキルアミノ基、置換若しくは無置換のジアルキルアミノ基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアリール基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のアリールオキシ基、置換若しくは無置換のアルキルチオ基、置換若しくは無置換のアリールチオ基又は置換若しくは無置換の複素環基であり、Ｙは、パーハロアルキル基であり、Ｅは、オキシ基、チオ基又はセレノ基であり、Ｒ^１は、置換若しくは無置換のアルキレン基、置換若しくは無置換のアルケニレン基、置換若しくは無置換のアルキニレン基、置換若しくは無置換のアリーレン基又は置換若しくは無置換のアラルキレン基であり、Ａ⁻は、１価のアニオンである。）
で表される化合物を反応させて製造されている。

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ are each independently a hydrogen atom, a halogen group, a hydroxyl group, a nitro group, or a cyano group. , Carboxyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group, substituted or unsubstituted A monoalkylaminocarbonyl group, a substituted or unsubstituted dialkylaminocarbonyl group, a substituted or unsubstituted monoarylaminocarbonyl group, a substituted or unsubstituted diarylaminocarbonyl group, a sulfonic acid group, a substituted or unsubstituted alkoxysulfonyl group, Substituted or unsubstituted aryloxysulfoni Group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted or unsubstituted Monoarylaminosulfonyl group, substituted or unsubstituted diarylaminosulfonyl group, amino group, substituted or unsubstituted monoalkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkyl group, substituted or unsubstituted Substituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted of A Riruchio group or a substituted or unsubstituted heterocyclic group, Y is a perhaloalkyl group, E is an oxy group, a thio group, or a seleno group, R ¹ is a substituted or unsubstituted alkylene group, a substituted Or an unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group or a substituted or unsubstituted aralkylene group, and A ⁻ is a monovalent anion.)
It is manufactured by making the compound represented by these react.

  The electrochromic composition of the present invention has a general formula of conductive or semiconducting nanostructures.

（式中、Ｂは、ハロゲン基であり、Ｃは、アルキレン基であり、Ｄ^１は、ハロゲン基又はアルコキシ基であり、Ｄ^２及びＤ^３は、それぞれ独立に、ハロゲン基、アルコキシ基又はアルキル基である。）
で表される化合物を反応させた後、一般式

(In the formula, B is a halogen group, C is an alkylene group, D ¹ is a halogen group or an alkoxy group, and D ² and D ³ are each independently a halogen group, an alkoxy group or an alkyl group. Group.)
After reacting the compound represented by general formula

（式中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７、Ｘ^８、Ｘ^９、Ｘ^１０及びＸ^１１は、それぞれ独立に、水素原子、ハロゲン基、ヒドロキシル基、ニトロ基、シアノ基、カルボキシル基、置換若しくは無置換のアルコキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、置換若しくは無置換のアルキルカルボニル基、置換若しくは無置換のアリールカルボニル基、アミノカルボニル基、置換若しくは無置換のモノアルキルアミノカルボニル基、置換若しくは無置換のジアルキルアミノカルボニル基、置換若しくは無置換のモノアリールアミノカルボニル基、置換若しくは無置換のジアリールアミノカルボニル基、スルホン酸基、置換若しくは無置換のアルコキシスルホニル基、置換若しくは無置換のアリールオキシスルホニル基、置換若しくは無置換のアルキルスルホニル基、置換若しくは無置換のアリールスルホニル基、アミノスルホニル基、置換若しくは無置換のモノアルキルアミノスルホニル基、置換若しくは無置換のジアルキルアミノスルホニル基、置換若しくは無置換のモノアリールアミノスルホニル基、置換若しくは無置換のジアリールアミノスルホニル基、アミノ基、置換若しくは無置換のモノアルキルアミノ基、置換若しくは無置換のジアルキルアミノ基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアリール基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のアリールオキシ基、置換若しくは無置換のアルキルチオ基、置換若しくは無置換のアリールチオ基又は置換若しくは無置換の複素環基であり、Ｙは、パーハロアルキル基であり、Ｌは、置換若しくは無置換のアリーレン基であり、Ｒ^１は、置換若しくは無置換のアルキレン基、置換若しくは無置換のアルケニレン基、置換若しくは無置換のアルキニレン基、置換若しくは無置換のアリーレン基又は置換若しくは無置換のアラルキレン基であり、Ａ⁻は、１価のアニオンであり、ｎは０以上３以下の整数である。）
で表される化合物を反応させて製造されている。

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ and X ¹¹ are each independently a hydrogen atom, a halogen group, or a hydroxyl group. Nitro group, cyano group, carboxyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group Substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, sulfonic acid group, substituted or unsubstituted Substituted alkoxysulfonyl group, substituted or unsubstituted Alkyloxysulfonyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted Or an unsubstituted monoarylaminosulfonyl group, a substituted or unsubstituted diarylaminosulfonyl group, an amino group, a substituted or unsubstituted monoalkylamino group, a substituted or unsubstituted dialkylamino group, a substituted or unsubstituted alkyl group, A substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, A substituted or unsubstituted arylthio group or a substituted or unsubstituted heterocyclic group; Y is a perhaloalkyl group; L is a substituted or unsubstituted arylene group; and R ¹ is a substituted or unsubstituted arylene group. An alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group or a substituted or unsubstituted aralkylene group, A ⁻ is a monovalent anion, and n is It is an integer of 0 or more and 3 or less.)
It is manufactured by making the compound represented by these react.

  The electrochromic composition of the present invention has a general formula of conductive or semiconducting nanostructures.

（式中、Ｃは、ハロゲン基であり、Ｄは、アルキレン基であり、Ｅ^１は、ハロゲン基又はアルコキシ基であり、Ｅ^２及びＥ^３は、それぞれ独立に、ハロゲン基、アルコキシ基又はアルキル基である。）
で表される化合物を反応させた後、一般式

Wherein C is a halogen group, D is an alkylene group, E ¹ is a halogen group or an alkoxy group, and E ² and E ³ are each independently a halogen group, an alkoxy group or an alkyl group. Group.)
After reacting the compound represented by general formula

（式中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７及びＸ^８は、それぞれ独立に、水素原子、ハロゲン基、ヒドロキシル基、ニトロ基、シアノ基、カルボキシル基、置換若しくは無置換のアルコキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、置換若しくは無置換のアルキルカルボニル基、置換若しくは無置換のアリールカルボニル基、アミノカルボニル基、置換若しくは無置換のモノアルキルアミノカルボニル基、置換若しくは無置換のジアルキルアミノカルボニル基、置換若しくは無置換のモノアリールアミノカルボニル基、置換若しくは無置換のジアリールアミノカルボニル基、スルホン酸基、置換若しくは無置換のアルコキシスルホニル基、置換若しくは無置換のアリールオキシスルホニル基、置換若しくは無置換のアルキルスルホニル基、置換若しくは無置換のアリールスルホニル基、アミノスルホニル基、置換若しくは無置換のモノアルキルアミノスルホニル基、置換若しくは無置換のジアルキルアミノスルホニル基、置換若しくは無置換のモノアリールアミノスルホニル基、置換若しくは無置換のジアリールアミノスルホニル基、アミノ基、置換若しくは無置換のモノアルキルアミノ基、置換若しくは無置換のジアルキルアミノ基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアリール基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のアリールオキシ基、置換若しくは無置換のアルキルチオ基、置換若しくは無置換のアリールチオ基又は置換若しくは無置換の複素環基であり、Ｙは、パーハロアルキル基であり、Ａは、Ｎ、Ｏ、Ｓ又はＳｅを１個以上含み、Ｌと結合するＣを含む置換又は無置換の５員環の複素環基であり、Ｌは、置換又は無置換のアリーレン基であり、Ｒ^１は、置換若しくは無置換のアルキレン基、置換若しくは無置換のアルケニレン基、置換若しくは無置換のアルキニレン基、置換若しくは無置換のアリーレン基又は置換若しくは無置換のアラルキレン基であり、Ｂ⁻は、１価のアニオンであり、ｎは１以上３以下の整数である。）
で表される化合物を反応させて製造されている。

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are each independently a hydrogen atom, a halogen group, a hydroxyl group, a nitro group, a cyano group, or a carboxyl group. Substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group, substituted or unsubstituted monoalkylamino Carbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, sulfonic acid group, substituted or unsubstituted alkoxysulfonyl group, substituted or unsubstituted A substituted aryloxysulfonyl group, Substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted or unsubstituted monoaryl Aminosulfonyl group, substituted or unsubstituted diarylaminosulfonyl group, amino group, substituted or unsubstituted monoalkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl Group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl A thio group or a substituted or unsubstituted heterocyclic group, Y is a perhaloalkyl group, A is one or more of N, O, S or Se, and is a substituted or unsubstituted group containing C bonded to L Wherein L is a substituted or unsubstituted arylene group, R ¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene. A group, a substituted or unsubstituted arylene group or a substituted or unsubstituted aralkylene group, B ⁻ is a monovalent anion, and n is an integer of 1 to 3.
It is manufactured by making the compound represented by these react.

  The electrochromic composition of the present invention has a general formula of conductive or semiconducting nanostructures.

（式中、Ｃは、ハロゲン基であり、Ｄは、アルキレン基であり、Ｅ^１は、ハロゲン基又はアルコキシ基であり、Ｅ^２及びＥ^３は、それぞれ独立に、ハロゲン基、アルコキシ基又はアルキル基である。）
で表される化合物を反応させた後、一般式

Wherein C is a halogen group, D is an alkylene group, E ¹ is a halogen group or an alkoxy group, and E ² and E ³ are each independently a halogen group, an alkoxy group or an alkyl group. Group.)
After reacting the compound represented by general formula

（式中、Ｘ^１、Ｘ^２、Ｘ^３及びＸ^４は、それぞれ独立に、水素原子、ハロゲン基、ヒドロキシル基、ニトロ基、シアノ基、カルボキシル基、置換若しくは無置換のアルコキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、置換若しくは無置換のアルキルカルボニル基、置換若しくは無置換のアリールカルボニル基、アミノカルボニル基、置換若しくは無置換のモノアルキルアミノカルボニル基、置換若しくは無置換のジアルキルアミノカルボニル基、置換若しくは無置換のモノアリールアミノカルボニル基、置換若しくは無置換のジアリールアミノカルボニル基、スルホン酸基、置換若しくは無置換のアルコキシスルホニル基、置換若しくは無置換のアリールオキシスルホニル基、置換若しくは無置換のアルキルスルホニル基、置換若しくは無置換のアリールスルホニル基、アミノスルホニル基、置換若しくは無置換のモノアルキルアミノスルホニル基、置換若しくは無置換のジアルキルアミノスルホニル基、置換若しくは無置換のモノアリールアミノスルホニル基、置換若しくは無置換のジアリールアミノスルホニル基、アミノ基、置換若しくは無置換のモノアルキルアミノ基、置換若しくは無置換のジアルキルアミノ基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアリール基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のアリールオキシ基、置換若しくは無置換のアルキルチオ基、置換若しくは無置換のアリールチオ基又は置換若しくは無置換の複素環基であり、Ｙは、パーハロアルキル基であり、Ａは、置換又は無置換のベンゼン由来のｎ価の基であり、Ｒ^１は、置換若しくは無置換のアルキレン基、置換若しくは無置換のアルケニレン基、置換若しくは無置換のアルキニレン基、置換若しくは無置換のアリーレン基又は置換若しくは無置換のアラルキレン基であり、Ｂ⁻は、１価のアニオンであり、ｎは２以上６以下の整数であり、ｍは１以上ｎ−１以下の整数である。）
で表される化合物を反応させて製造されている。

(Wherein X ¹ , X ² , X ³ and X ⁴ are each independently a hydrogen atom, halogen group, hydroxyl group, nitro group, cyano group, carboxyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or Unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group Substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, sulfonic acid group, substituted or unsubstituted alkoxysulfonyl group, substituted or unsubstituted aryloxysulfonyl group, substituted or unsubstituted Alkyls Phonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted or unsubstituted monoarylaminosulfonyl group, substituted or Unsubstituted diarylaminosulfonyl group, amino group, substituted or unsubstituted monoalkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted Alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted A heterocyclic group, Y is a perhaloalkyl group, A is an n-valent group derived from a substituted or unsubstituted benzene, R ¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted An alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group or a substituted or unsubstituted aralkylene group, B ⁻ is a monovalent anion, and n is an integer of 2 to 6. , M is an integer of 1 to n-1.
It is manufactured by making the compound represented by these react.

  The display element of the present invention includes a display electrode, a counter electrode provided to face the display electrode at a predetermined interval, and an electrolyte sandwiched between the display electrode and the counter electrode. A display layer containing the electrochromic compound of the present invention or the electrochromic composition of the present invention is formed on the surface of the display electrode on the side where the counter electrode is provided.

  The display device of the present invention includes the display element of the present invention and means for driving the display element.

  According to the present invention, it is possible to provide an electrochromic compound, an electrochromic composition, a display element, and a display device that can maintain a colored state for a long time.

It is a figure which shows an example of the display element of this invention. It is a figure which shows the modification of the display element of FIG. It is the light absorption spectrum of the coloring state of the display substrate of Example 1 and Comparative Example 1. It is a figure which shows the evaluation result of the memory property test of Example 1 and Comparative Example 1.

  Next, the form for implementing this invention is demonstrated with drawing.

  The electrochromic compound of the present invention is a compound represented by the general formulas (1) to (4).

  In the electrochromic compound of the present invention, since the hydrocarbon group having a perhaloalkyl group at the end is bonded to the nitrogen atom of the pyridinium ion, the absolute value of the reduction potential is reduced and the colored state is maintained for a long time. That is, it has excellent memory performance.

  Although it does not specifically limit as a halogen atom in a perhaloalkyl group, A fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, A fluorine atom is preferable.

The monovalent anion is not particularly _{^{limited, CF 3 SO 3 -, Br}} -, Cl -, ClO 4 -, PF 6 -, BF 4 - , and the like.

  The electrochromic compound of the present invention preferably has a symmetric structure from the viewpoint of ease of synthesis and stability.

  Although it does not specifically limit as a compound represented by General formula (1), The compound represented by Chemical formula (1-1)-(1-12) is mentioned.

なお、一般式（１）で表される化合物は、シアンを発色及び消色することができる。

The compound represented by the general formula (1) can develop and decolor cyan.

  Although it does not specifically limit as a compound represented by General formula (2), The compound represented by Chemical formula (2-1)-(2-9) is mentioned.

なお、一般式（２）で表される化合物は、マゼンタを発色及び消色することができる。

The compound represented by the general formula (2) can develop and decolor magenta.

  Although it does not specifically limit as a compound represented by General formula (3), The compound represented by Chemical formula (3-1)-(3-8) is mentioned.

なお、一般式（３）で表される化合物は、イエローを発色及び消色することができる。

The compound represented by the general formula (3) can develop and decolor yellow.

  Although it does not specifically limit as a compound represented by General formula (4), The compound represented by Chemical formula (4-1)-(4-8) is mentioned.

なお、一般式（４）で表される化合物は、イエローを発色及び消色することができる。

The compound represented by the general formula (4) can develop and decolor yellow.

  As described above, since the compounds represented by the general formulas (1) to (4) can develop and decolor the three primary colors magenta, yellow, and cyan, they can be applied to full-color display elements.

  In the electrochromic composition of the present invention, the electrochromic compound of the present invention is bonded or adsorbed to a conductive or semiconducting nanostructure. Specifically, in the electrochromic compound of the present invention, Z is a carboxyl group, a phosphonic acid group, a sulfonic acid group, a phosphoric acid group or a hydroxyl group. Bound or adsorbed to the nanostructure. At this time, it is preferable that Z is a phosphonic acid group because of its high binding force to the conductive or semiconducting nanostructure.

  In addition, the electrochromic composition of the present invention is represented by the general formula (6) or (7) after reacting the conductive or semiconducting nanostructure with the compound represented by the general formula (5). The compound represented by the general formula (8) is reacted with the conductive or semiconducting nanostructure, and then the general formula (9) or (10) is used. It is produced by reacting the compounds shown.

  The compound represented by the general formula (5) or (8) can react with a hydroxyl group on the surface of the conductive or semiconductive nanostructure to form a siloxane bond.

At this time, in the compound represented by the general formula (5), since the binding force to the conductive or semiconductive nanostructure is large, D ¹ , D ² and D ³ are ethoxy groups, methoxy groups, etc. An alkoxy group or a chloro group is preferred. B is preferably a bromo group, and C is preferably an alkylene group having 1 to 6 carbon atoms. Similarly, in the compound represented by the general formula (8), since the bonding force to the conductive or semiconductive nanostructure is large, E ¹ , E ² and E ³ are ethoxy groups, methoxy groups, etc. An alkoxy group or a chloro group is preferred. C is preferably a bromo group, and D is preferably an alkylene group having 1 to 6 carbon atoms.

  The compound represented by the general formula (6), (7), (9) or (10) preferably has a symmetric structure from the viewpoint of ease of synthesis and stability.

  The conductive or semiconducting nanostructure is not particularly limited, and examples thereof include structures having nanoscale irregularities such as nanoparticle aggregates and nanoporous structures.

  The material constituting the conductive or semiconductive nanostructure is not particularly limited, but titanium oxide, zinc oxide, tin oxide, alumina, zirconium oxide, cerium oxide, silica, yttrium oxide, oxygen boron, magnesium oxide, Strontium titanate, potassium titanate, barium titanate, calcium titanate, calcium oxide, ferrite, hafnium oxide, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide, vanadium oxide, aluminosilicate , Calcium phosphate, aluminosilicate, and the like, and two or more of them may be used in combination. Among these, titanium oxide, zinc oxide, tin oxide, alumina, zirconium oxide, iron oxide, magnesium oxide, indium oxide or tungsten oxide are preferable because multicolor display excellent in response speed of color development and decoloration is possible. Titanium is particularly preferred.

  The nanoparticles constituting the conductive or semiconductive nanostructure preferably have an average primary particle size of 30 nm or less. This improves the light transmittance and increases the specific surface area.

The conductive or semiconducting nanostructure preferably has a specific surface area of 100 m ² / g or more. Thereby, multicolor display excellent in the display contrast ratio of color emission / erasure becomes possible.

  FIG. 1 shows an example of the display element of the present invention. The display element 10 includes a display substrate 11 on which a display electrode 11a is formed, and a counter substrate 12 on which a counter electrode 12a provided to face the display electrode 11a at a predetermined interval is formed. Have. Moreover, the display layer 13 containing the electrochromic compound 13a of the present invention is formed on the surface of the display electrode 11a on the side where the counter electrode 12a is provided. Specifically, in the electrochromic compound 13a, since Z is a carboxyl group, a phosphonic acid group, a sulfonic acid group, a phosphoric acid group or a hydroxyl group, the display electrode 11a having a hydroxyl group on the surface via a hydrogen bond or the like. Bound to or adsorbed to. Further, an electrolyte solution 14 is filled between the display substrate 11 and the counter substrate 12. At this time, the electrochromic compound 13a is colored and decolored by oxidation-reduction reaction on the surface of the display electrode 11.

  Further, since the reflective layer 15 containing white pigment particles is formed on the surface of the counter electrode 12 on the display electrode 11 side, the display element 10 is a reflective display element. Further, the display substrate 11 and the counter substrate 12 are bonded together with a spacer 16 interposed therebetween.

  A method for forming the display layer 13 is not particularly limited, and examples thereof include a dipping method, a vapor deposition method, a spin coating method, a printing method, and an ink jet method.

  FIG. 2 shows a modification of the display element 10. The display element 20 includes a display layer 13 including the electrochromic composition 13a of the present invention instead of the display layer 13 including the electrochromic compound 13a formed on the surface of the display electrode 11a on the side where the counter electrode 12b is provided. The structure is the same as that of the display element 10 except that the layer 23 is formed.

  A method for forming the display layer 23 is not particularly limited, and examples thereof include a dipping method, a vapor deposition method, a spin coating method, a printing method, and an ink jet method.

  The display substrate 11 is a transparent substrate 11b on which display electrodes 11a are formed.

The material constituting the display electrode 11a is not particularly limited as long as it is transparent, but tin-doped indium oxide (hereinafter referred to as ITO), fluorine-doped tin oxide (hereinafter referred to as FTO), and antimony doped. An inorganic material such as tin oxide (hereinafter referred to as ATO) can be used. Among these, an inorganic material containing indium oxide, tin oxide, or zinc oxide is preferable because a thin film can be easily formed by sputtering, and InSnO, GaZnO, SnO, In ₂ O ₃ , and ZnO are particularly preferable.

  Examples of the material constituting the transparent substrate 11b include glass and plastic. At this time, if a plastic film is used as the transparent substrate 11b, a lightweight and flexible display element can be manufactured.

  The counter substrate 12 is a substrate 12b on which a counter electrode 12a is formed.

  Although it does not specifically limit as a material which comprises the counter electrode 12a, ITO, FTO, a zinc oxide, zinc, platinum, carbon etc. are mentioned. At this time, when the counter electrode 12a includes a material that reduces (or oxidizes) when the electrochromic compound is oxidized (or reduced), a display element capable of stable color development and decoloration is obtained.

  Examples of the material constituting the substrate 12b include glass and plastic.

  Instead of the counter substrate 12, a metal plate such as a zinc plate may be used.

  As the electrolytic solution 14, a solution in which a supporting salt is dissolved in a solvent, an ionic liquid, or the like is used. For this reason, ionic conductivity is high.

The supporting salt is not particularly limited, but LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , CF ₃ SO ₃ Li, CF ₃ COOLi, KCl, NaClO ₃ , NaCl, NaBF ₄ , NaSCN, KBF ₄ , Mg (ClO ₄ ) ₂ , metal salts such as Mg (BF ₄ ) ₂ ; quaternary ammonium salts such as tetrabutylammonium perchlorate and tetrabutylammonium hexafluorophosphate.

  The solvent is not particularly limited, but propylene carbonate, acetonitrile, γ-butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, Examples include polyethylene glycol and alcohols.

  Instead of the electrolyte solution 14, a gel electrolyte; a solid electrolyte such as a polymer electrolyte may be used. Examples of the polymer electrolyte include perfluorosulfonic acid polymers. Thereby, the display element excellent in durability can be produced.

  The reflective layer 15 can be formed by applying a coating liquid containing white pigment particles and a resin (not shown) on the counter electrode 12.

  The material constituting the white pigment particles is not particularly limited, and examples thereof include metal oxides such as titanium oxide, aluminum oxide, zinc oxide, silicon oxide, cesium oxide, and yttrium oxide.

  The white pigment particles preferably have an average particle size of 50 to 400 nm in consideration of reflectance.

  Instead of forming the reflective layer 15, white pigment particles may be dispersed in the polymer electrolyte.

  A method for driving the display elements 10 and 20 is not particularly limited as long as a predetermined voltage can be applied between the display electrode 11a and the counter electrode 12a. At this time, if a passive driving method is used, an inexpensive display device can be obtained. In addition, when an active driving method is used, a display device capable of high-speed and high-definition display is obtained. Note that active driving can be easily performed by providing an active driving element on the counter substrate 12.

  The display elements 10 and 20 can be applied to display devices such as an electronic book, an electronic signboard, and an electronic shelf label.

Example 1
[Synthesis of Compound Represented by Chemical Formula (3-1)]
4-Bromobenzoic acid hydrazide (5.7 g), 4-bromobenzoic acid (10.0 g) and phosphorus oxychloride (13 ml) were charged into a reaction flask, stirred at 110 ° C. for 3 hours, and then allowed to cool. Next, the reaction solution was gradually discharged into ice water and then neutralized with dilute aqueous sodium hydroxide solution to precipitate the product. Further, the precipitated product was filtered, washed successively with water and methanol, and dried to obtain 8.3 g of intermediate (A).

  Intermediate (A) 4.6 g, 4-pyridineboronic acid 3.1 g, dichlorobis (triphenylphosphine) palladium (II) 0.84 g, cesium carbonate 11.7 g, water 24 ml and 1,4-dioxane 60 ml The reaction flask replaced with was charged at 90 ° C. for 12 hours and then allowed to cool. Next, the reaction solution was diluted with chloroform and then filtered. Further, the filtrate was washed with water and dried over anhydrous sodium sulfate, and chloroform was distilled off. The obtained solid was purified by silica gel column chromatography using a chloroform / ethanol mixed solvent (volume ratio 20/1) as an eluent to obtain 2.8 g of intermediate (B).

  Intermediate (B) 1.0 g, trifluoromethanesulfonic acid 2,2,2-trifluoroethyl 1.0 g and toluene 20 ml were charged into a reaction flask, stirred at 100 ° C. for 2 hours, and then allowed to cool. Next, the precipitated product was filtered, washed with 2-propanol, and dried to obtain 2.15 g of intermediate (C).

  Intermediate (C) 0.5 g, 4-bromomethylbenzylphosphonic acid 0.2 g and dimethylformamide 3.0 ml were charged, reacted at 90 ° C. for 1.5 hours, and then allowed to cool. Next, the reaction liquid was discharged into ice-cooled 2-propanol, dispersed, and then recovered and dried under reduced pressure at 100 ° C. for 2 days to obtain 0.33 g of the compound represented by the chemical formula (3-1). Obtained.

［表示素子の作製］
スパッタ法を用いて、４０ｍｍ×４０ｍｍのガラス基板１１ｂの上面の１６ｍｍ×２３ｍｍの領域に、厚さが約１００ｎｍのＩＴＯからなる表示電極１１ａを形成して、表示基板１１を得た。表示電極１１ａの端部間の抵抗を測定したところ、約２００Ωであった。

[Production of display element]
A display electrode 11a made of ITO having a thickness of about 100 nm was formed in a 16 mm × 23 mm region on the upper surface of a 40 mm × 40 mm glass substrate 11b by sputtering, and the display substrate 11 was obtained. When the resistance between the end portions of the display electrode 11a was measured, it was about 200Ω.

  Next, a dispersion liquid SP210 of titanium oxide nanoparticles (manufactured by Showa Titanium Co., Ltd.) is applied onto the display electrode 11a using a spin coating method, and annealed at 120 ° C. for 15 minutes to obtain a nanoparticle aggregate. Formed. Furthermore, using a spin coating method, a 1% by mass 2,2,3,3-tetrafluoropropanol solution of the compound represented by the chemical formula (3-1) was applied, and annealed at 120 ° C. for 10 minutes, The display layer 23 containing the electrochromic composition 23b was formed by adsorbing the compound represented by the chemical formula (3-1) on the surface of the nanoparticle assembly.

  On the other hand, the counter electrode 12a made of ITO having a thickness of about 150 nm was formed on the entire upper surface of the 40 mm × 40 mm glass substrate 12b by sputtering to obtain the counter substrate 12.

  The display substrate 11 and the counter substrate 12 were bonded through a 75 μm spacer 15 to obtain a cell. Next, titanium oxide particles CR50 having an average primary particle size of 300 nm (made by Ishihara Sangyo Co., Ltd.) in an electrolytic solution 14 in which 0.2 mol% of tetrabutylammonium perchlorate was dissolved in dimethyl sulfoxide (DMSO). A liquid in which 35% by mass was dispersed was sealed in the cell to form the reflective layer 15, and the display element 20 was obtained.

[Color development test]
When a negative electrode was connected to the display electrode 11a of the display element 20, a positive electrode was connected to the counter electrode 12a, and a voltage of 3.0 V was applied for 1 second, yellow was developed. Next, when a voltage of −4.5 V was applied for 2 seconds, the color was completely erased.

[Measurement of light absorption spectrum]
The display substrate 11 on which the display layer 23 is formed is put in a quartz cell, a platinum electrode is used as a counter electrode, and an Ag / Ag ⁺ electrode RE-7 (manufactured by BAS) is used as a reference electrode. The quartz cell was filled with an electrolytic solution in which 0.2 mol% of tetrabutylammonium was dissolved in dimethyl sulfoxide (DMSO). When a voltage of −1.01 V (vs. Ag / Ag ⁺ electrode) was applied using a potentiostat ALS-660C (manufactured by BAS), yellow was developed.

  From this, it was confirmed that the absolute value of the reduction potential was small.

  When a quartz cell was irradiated with light using a deuterium tungsten halogen light source DH-2000 (Ocean Optics) and the transmitted light was detected with a spectrometer USB4000 (Ocean Optics), the light absorption shown in FIG. A spectrum was obtained.

  From FIG. 3, it was confirmed that the display substrate 11 in the colored state has a maximum absorption wavelength around 450 nm.

[Memory test]
When a negative electrode was connected to the display electrode 11a of the display element 20, a positive electrode was connected to the counter electrode 12a, and a voltage of 3.0 V was applied for 1 second, yellow was developed. Next, the connection between the display electrode 11a and the counter electrode 12a, the negative electrode, and the positive electrode was released, and a disconnected state was obtained.

  Using a halogen light source HL-2000-HP (manufactured by Ocean Optics), the display element 20 is irradiated with light from an angle of 45 °, and reflected light having a wavelength of 450 nm is a spectrometer USB4000 (manufactured by Ocean Optics). The result shown in FIG. 4 was obtained. The reflectance in the decolored state before applying the voltage was 100%, and the reflectance in the saturated coloring state immediately after the voltage was applied was 0%.

  From FIG. 4, even after 1400 seconds had passed since the voltage was applied, only about 25% was erased, confirming that the memory performance was excellent.

(Comparative Example 1)
[Synthesis of Compound (C)]
0.45 g of Intermediate (B), 2.0 g of diethyl 8-bromooctylphosphonate, 3 ml of 1-propanol and 6 ml of water were charged into a reaction flask, stirred at 90 ° C. for 40 hours, and then allowed to cool. The reaction solution was discharged into a mixed solution of 15 ml of water and 30 ml of ethyl acetate, and the aqueous layer was separated. The obtained aqueous layer and 20 ml of concentrated hydrochloric acid were charged into a reaction flask, stirred at 90 ° C. for 23 hours, and then allowed to cool. Water was distilled off from the reaction solution, and the tar-like residue was dissolved in methanol, and then dropped into a 2-propanol / ethanol mixed solvent (volume ratio 2/1) with stirring to crystallize the product. It was. Further, after filtration, washing with 2-propanol and drying, 0.40 g of compound (C) was obtained.

［表示素子の作製］
化学式（３−１）で表される化合物の代わりに、化合物（Ｃ）を用いた以外は、実施例１と同様にして、表示素子を得た。

[Production of display element]
A display device was obtained in the same manner as in Example 1 except that the compound (C) was used instead of the compound represented by the chemical formula (3-1).

[Color development test]
When a negative electrode was connected to the display electrode 11a of the display element, a positive electrode was connected to the counter electrode 12a, and a voltage of 3.0 V was applied for 1 second, yellow was developed. Next, when a voltage of −4.5 V was applied for 2 seconds, the color was completely erased.

[Measurement of light absorption spectrum]
A display substrate on which a display layer is formed is put in a quartz cell, and a platinum electrode is used as a counter electrode, and Ag / Ag ⁺ electrode RE-7 (manufactured by BAS) is used as a reference electrode, and tetrabutyl perchlorate is used. The quartz cell was filled with an electrolytic solution in which 0.2 mol% of ammonium was dissolved in dimethyl sulfoxide (DMSO). When a voltage of −1.08 V (vs. Ag / Ag ⁺ electrode) was applied using a potentiostat ALS-660C (manufactured by BAS), yellow was developed.

  From this, it was confirmed that the absolute value of the reduction potential was larger than that of Example 1.

  When a quartz cell was irradiated with light using a deuterium tungsten halogen light source DH-2000 (manufactured by Ocean Optics) and the transmitted light was detected by a spectrometer USB4000 (manufactured by Ocean Optics), the light absorption shown in FIG. A spectrum was obtained.

  From FIG. 3, it was confirmed that the display substrate in the colored state has a maximum absorption wavelength around 450 nm.

[Memory test]
When a negative electrode was connected to the display electrode 11a of the display element, a positive electrode was connected to the counter electrode 12a, and a voltage of 3.0 V was applied for 1 second, yellow was developed. Next, the connection between the display electrode 11a and the counter electrode 12a, the negative electrode, and the positive electrode was released, and a disconnected state was obtained.

  Using a halogen light source HL-2000-HP (manufactured by Ocean Optics), the display element is irradiated with light from an angle of 45 °, and the reflected light having a wavelength of 450 nm is applied with a spectrometer USB4000 (manufactured by Ocean Optics). As a result, the result shown in FIG. 4 was obtained.

  From FIG. 4, when 350 seconds passed after applying a voltage, it was decolored about 50% and it was confirmed that memory property is inferior to Example 1. FIG.

DESCRIPTION OF SYMBOLS 10, 20 Display element 11 Display substrate 11a Display electrode 11b Transparent substrate 12 Counter substrate 12a Counter electrode 12b Substrate 13 Display layer 13a Electrochromic compound 14 Electrolytic solution 15 Reflective layer 16 Spacer 23 Display layer 23a Electrochromic composition

JP 2009-215464 A

Claims (11)

General formula

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ are each independently a hydrogen atom, a halogen group, a hydroxyl group, a nitro group, or a cyano group. , Carboxyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group, substituted or unsubstituted A monoalkylaminocarbonyl group, a substituted or unsubstituted dialkylaminocarbonyl group, a substituted or unsubstituted monoarylaminocarbonyl group, a substituted or unsubstituted diarylaminocarbonyl group, a sulfonic acid group, a substituted or unsubstituted alkoxysulfonyl group, Substituted or unsubstituted aryloxysulfoni Group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted or unsubstituted Monoarylaminosulfonyl group, substituted or unsubstituted diarylaminosulfonyl group, amino group, substituted or unsubstituted monoalkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkyl group, substituted or unsubstituted Substituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted of A reelthio group or a substituted or unsubstituted heterocyclic group, Y is a perhaloalkyl group, Z is a carboxyl group, a phosphonic acid group, a sulfonic acid group, a phosphoric acid group or a hydroxyl group, and E is an oxy R ¹ and R ² are each independently a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted group, a thio group or a seleno group An arylene group or a substituted or unsubstituted aralkylene group, and A ^- and B ^- are each independently a monovalent anion.)
An electrochromic compound, which is a compound represented by the formula: General formula

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ and X ¹¹ are each independently a hydrogen atom, a halogen group, or a hydroxyl group. Nitro group, cyano group, carboxyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group Substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, sulfonic acid group, substituted or unsubstituted Substituted alkoxysulfonyl group, substituted or unsubstituted Alkyloxysulfonyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted Or an unsubstituted monoarylaminosulfonyl group, a substituted or unsubstituted diarylaminosulfonyl group, an amino group, a substituted or unsubstituted monoalkylamino group, a substituted or unsubstituted dialkylamino group, a substituted or unsubstituted alkyl group, A substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, A substituted or unsubstituted arylthio group or a substituted or unsubstituted heterocyclic group, Y is a perhaloalkyl group, and Z is a carboxyl group, a phosphonic acid group, a sulfonic acid group, a phosphoric acid group or a hydroxyl group. , L is a substituted or unsubstituted arylene group, and R ¹ and R ² are each independently a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, substituted or an unsubstituted arylene group or a substituted or unsubstituted aralkylene group, a ^- and B ^- are each independently a monovalent anionic, n represents a an integer of 0 to 3).
An electrochromic compound, which is a compound represented by the formula: General formula

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are each independently a hydrogen atom, a halogen group, a hydroxyl group, a nitro group, a cyano group, or a carboxyl group. Substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group, substituted or unsubstituted monoalkylamino Carbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, sulfonic acid group, substituted or unsubstituted alkoxysulfonyl group, substituted or unsubstituted A substituted aryloxysulfonyl group, Substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted or unsubstituted monoaryl Aminosulfonyl group, substituted or unsubstituted diarylaminosulfonyl group, amino group, substituted or unsubstituted monoalkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl Group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl A thio group or a substituted or unsubstituted heterocyclic group, Y is a perhaloalkyl group, Z is a carboxyl group, a phosphonic acid group, a sulfonic acid group, a phosphoric acid group or a hydroxyl group, and A is N , O, S, or Se, and a substituted or unsubstituted 5-membered heterocyclic group containing C bonded to L, L is a substituted or unsubstituted arylene group, R ¹ and Each R ² is independently a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted aralkylene group; B ^- and C ^- are each independently a monovalent anion, and n is an integer of 1 to 3.
An electrochromic compound, which is a compound represented by the formula: General formula

(Wherein X ¹ , X ² , X ³ and X ⁴ are each independently a hydrogen atom, halogen group, hydroxyl group, nitro group, cyano group, carboxyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or Unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group Substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, sulfonic acid group, substituted or unsubstituted alkoxysulfonyl group, substituted or unsubstituted aryloxysulfonyl group, substituted or unsubstituted Alkyls Phonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted or unsubstituted monoarylaminosulfonyl group, substituted or Unsubstituted diarylaminosulfonyl group, amino group, substituted or unsubstituted monoalkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted Alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted A heterocyclic group, Y is a perhaloalkyl group, Z is a carboxyl group, a phosphonic acid group, a sulfonic acid group, a phosphoric acid group or a hydroxyl group, and A is an n derived from a substituted or unsubstituted benzene. Each of R ¹ and R ² is independently a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group or a substituted group or an unsubstituted aralkylene group, B ^- and C ^- are each independently a monovalent anionic, n is 2 to 6 integer, m is 1 or n-1 an integer .)
An electrochromic compound, which is a compound represented by the formula:   An electrochromic composition, wherein the electrochromic compound according to any one of claims 1 to 4 is bonded or adsorbed to a conductive or semiconducting nanostructure. General formula for conductive or semiconducting nanostructures

(In the formula, B is a halogen group, C is an alkylene group, D ¹ is a halogen group or an alkoxy group, and D ² and D ³ are each independently a halogen group, an alkoxy group or an alkyl group. Group.)
After reacting the compound represented by general formula

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ are each independently a hydrogen atom, a halogen group, a hydroxyl group, a nitro group, or a cyano group. , Carboxyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group, substituted or unsubstituted A monoalkylaminocarbonyl group, a substituted or unsubstituted dialkylaminocarbonyl group, a substituted or unsubstituted monoarylaminocarbonyl group, a substituted or unsubstituted diarylaminocarbonyl group, a sulfonic acid group, a substituted or unsubstituted alkoxysulfonyl group, Substituted or unsubstituted aryloxysulfoni Group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted or unsubstituted Monoarylaminosulfonyl group, substituted or unsubstituted diarylaminosulfonyl group, amino group, substituted or unsubstituted monoalkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkyl group, substituted or unsubstituted Substituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted of A Riruchio group or a substituted or unsubstituted heterocyclic group, Y is a perhaloalkyl group, E is an oxy group, a thio group, or a seleno group, R ¹ is a substituted or unsubstituted alkylene group, a substituted Or an unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group or a substituted or unsubstituted aralkylene group, and A ⁻ is a monovalent anion.)
The electrochromic composition characterized by being manufactured by making the compound represented by these react. General formula for conductive or semiconducting nanostructures

(In the formula, B is a halogen group, C is an alkylene group, D ¹ is a halogen group or an alkoxy group, and D ² and D ³ are each independently a halogen group, an alkoxy group or an alkyl group. Group.)
After reacting the compound represented by general formula

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ and X ¹¹ are each independently a hydrogen atom, a halogen group, or a hydroxyl group. Nitro group, cyano group, carboxyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group Substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, sulfonic acid group, substituted or unsubstituted Substituted alkoxysulfonyl group, substituted or unsubstituted Alkyloxysulfonyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted Or an unsubstituted monoarylaminosulfonyl group, a substituted or unsubstituted diarylaminosulfonyl group, an amino group, a substituted or unsubstituted monoalkylamino group, a substituted or unsubstituted dialkylamino group, a substituted or unsubstituted alkyl group, A substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, A substituted or unsubstituted arylthio group or a substituted or unsubstituted heterocyclic group; Y is a perhaloalkyl group; L is a substituted or unsubstituted arylene group; and R ¹ is a substituted or unsubstituted arylene group. An alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group or a substituted or unsubstituted aralkylene group, A ⁻ is a monovalent anion, and n is It is an integer of 0 or more and 3 or less.)
The electrochromic composition characterized by being manufactured by making the compound represented by these react. General formula for conductive or semiconducting nanostructures

Wherein C is a halogen group, D is an alkylene group, E ¹ is a halogen group or an alkoxy group, and E ² and E ³ are each independently a halogen group, an alkoxy group or an alkyl group. Group.)
After reacting the compound represented by general formula

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are each independently a hydrogen atom, a halogen group, a hydroxyl group, a nitro group, a cyano group, or a carboxyl group. Substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group, substituted or unsubstituted monoalkylamino Carbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, sulfonic acid group, substituted or unsubstituted alkoxysulfonyl group, substituted or unsubstituted A substituted aryloxysulfonyl group, Substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted or unsubstituted monoaryl Aminosulfonyl group, substituted or unsubstituted diarylaminosulfonyl group, amino group, substituted or unsubstituted monoalkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl Group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl A thio group or a substituted or unsubstituted heterocyclic group, Y is a perhaloalkyl group, A is one or more of N, O, S or Se, and is a substituted or unsubstituted group containing C bonded to L Wherein L is a substituted or unsubstituted arylene group, R ¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene. A group, a substituted or unsubstituted arylene group or a substituted or unsubstituted aralkylene group, B ⁻ is a monovalent anion, and n is an integer of 1 to 3.
The electrochromic composition characterized by being manufactured by making the compound represented by these react. General formula for conductive or semiconducting nanostructures

Wherein C is a halogen group, D is an alkylene group, E ¹ is a halogen group or an alkoxy group, and E ² and E ³ are each independently a halogen group, an alkoxy group or an alkyl group. Group.)
After reacting the compound represented by general formula

(Wherein X ¹ , X ² , X ³ and X ⁴ are each independently a hydrogen atom, halogen group, hydroxyl group, nitro group, cyano group, carboxyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or Unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, aminocarbonyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group Substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, sulfonic acid group, substituted or unsubstituted alkoxysulfonyl group, substituted or unsubstituted aryloxysulfonyl group, substituted or unsubstituted Alkyls Phonyl group, substituted or unsubstituted arylsulfonyl group, aminosulfonyl group, substituted or unsubstituted monoalkylaminosulfonyl group, substituted or unsubstituted dialkylaminosulfonyl group, substituted or unsubstituted monoarylaminosulfonyl group, substituted or Unsubstituted diarylaminosulfonyl group, amino group, substituted or unsubstituted monoalkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted Alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted A heterocyclic group, Y is a perhaloalkyl group, A is an n-valent group derived from a substituted or unsubstituted benzene, R ¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted An alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group or a substituted or unsubstituted aralkylene group, B ⁻ is a monovalent anion, and n is an integer of 2 to 6. , M is an integer of 1 to n-1.
The electrochromic composition characterized by being manufactured by making the compound represented by these react. A display element comprising: a display electrode; a counter electrode provided to face the display electrode at a predetermined interval; and an electrolyte sandwiched between the display electrode and the counter electrode. ,
The electrochromic compound according to any one of claims 1 to 4 or the electrochromic composition according to any one of claims 5 to 9 on a surface of the display electrode on which the counter electrode is provided. A display element comprising a display layer containing an object. A display element according to claim 10;
A display device comprising means for driving the display element.

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