JP5648994B2 - Electrochromic compound - Google Patents

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 display electrode, a counter electrode provided to face the display electrode at an interval, and an electrolyte disposed between both electrodes, and the surface on the counter electrode side of the display electrode To develop a different color, and a threshold voltage to enter a color development state, a threshold voltage to enter a decoloration state, or a necessary charge amount to develop a color to a sufficient color density, or a necessary charge to sufficiently decolorize There is disclosed a multicolor display element having a display layer formed by laminating or mixing two or more types of electrochromic compositions having at least one of different amounts.

  However, the viologen compound contained in the electrochromic composition develops blue, green, and the like, and cannot develop yellow necessary for full color.

  The present invention has been made in view of the above-described problems of the prior art, and provides an electrochromic compound and an electrochromic composition capable of developing and decoloring yellow, and a display element and a display device having the electrochromic compound or the electrochromic composition. The purpose is to provide.

  The invention according to claim 1 is an electrochromic compound having 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、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又は置換若しくは無置換のアリール基であり、Ａは、１，３，４−オキサジアゾリレン基又はイソオキサゾリレン基であり、Ｌは、フェニレン基であり、Ｂ⁻及びＣ⁻は、それぞれ独立に、Ｂｒ ⁻ 、Ｃｌ ⁻ 、ＣｌＯ _４ ⁻ 、ＰＦ _６ ⁻ 又はＢＦ _４ ⁻ であり、ｎは、１であり、Ｒ^１及び／又はＲ^２は、スルホン酸基、ホスホン酸基、リン酸基及びカルボキシル基からなる群より選択される一種以上の官能基で置換されていてもよい。）
で表されることを特徴とする。

(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, wherein R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or substituted or an unsubstituted aryl group, a is 1,3,4-oxadiazolylene group or isoxazolylene alkylene group, L is a phenylene group, B ^- and C ^- are each independently, Br ⁻ , Cl ⁻ , ClO ₄ ⁻ , PF ₆ ^— or BF ₄ ^— , n is 1, and R ¹ and / or R ² are sulfonic acid group, phosphonic acid group, phosphoric acid group and carboxyl group It may be substituted with one or more functional groups selected from the group consisting of
It is represented by.

The invention according to claim 2 is the electrochromic compound according to claim 1, wherein R ¹ and R ² are each independently a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted group. It is an unsubstituted aryl group.

According to a third aspect of the present invention, in the electrochromic composition, the electrochromic compound according to the first or second aspect is bound or adsorbed to a structure having conductive or semiconducting nanoscale irregularities. Features.

In the electrochromic composition, the structure having conductive or semiconducting nanoscale unevenness has a general formula.

（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、Ａは、１，３，４−オキサジアゾリレン基又はイソオキサゾリレン基であり、Ｌは、フェニレン基であり、ｎは、１である。）
で表される化合物を反応させることにより得られることを特徴とする。

(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, A is a 1,3,4-oxadiazolylene group or isoxazolylene group , L is a phenylene group , and n is 1. .)
It is obtained by reacting a compound represented by the formula:

  The invention according to claim 5 is sandwiched between the display electrode, the counter electrode provided to face the display electrode at a predetermined interval, and the display electrode and the counter electrode. A display layer comprising an electrolyte that includes the electrochromic compound according to claim 1 or the electrochromic composition according to claim 3 or 4 on a surface of the display electrode on the counter electrode side. Is formed.

  According to a sixth aspect of the present invention, in the display device, the display element according to the fifth aspect and means for driving the display element are provided.

  ADVANTAGE OF THE INVENTION According to this invention, the display element and display apparatus which have the electrochromic compound and electrochromic composition which can color-develop and decolor yellow, and this electrochromic compound or this electrochromic composition can be provided.

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 a figure which shows the modification of the display element of FIG. It is a figure which shows the synthetic | combination flow of a compound (B). 6 is a diagram showing a reflection spectrum of the display element of Example 1. FIG. It is a figure which shows the result of having coordinate-converted the reflection spectrum of the coloring state of FIG. 5 to the CIE color system. It is a figure which shows the light absorption spectrum of the display substrate in which the display layer of Example 1 is formed. It is a figure which shows the synthetic | combination flow of a compound (E). It is a figure which shows the reflection spectrum of the display element of Example 2. FIG. It is a figure which shows the result of having coordinate-converted the reflection spectrum of the coloring state of FIG. 9 to the CIE color system. It is a figure which shows the light absorption spectrum of the display substrate in which the display layer of Example 2 is formed. 6 is a diagram showing a reflection spectrum of a display element of Comparative Example 1. FIG.

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

  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、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又は置換若しくは無置換のアリール基であり、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、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、２又は３であり、Ｒ^１及び／又はＲ^２は、スルホン酸基、ホスホン酸基、リン酸基及びカルボキシル基からなる群より選択される一種以上の官能基で置換されていてもよい。）
で表される。

(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, wherein R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or substituted Or an unsubstituted aryl group, A is a substituted or unsubstituted 5-membered heterocyclic group containing one or more of N, O, S, or Se, and containing C bonded to L; a substituted or unsubstituted arylene group, B ^- and C ^- are each independently a monovalent anionic, n is 1, 2 or 3, ^{R 1} and / or ^{R 2,} sulfonate And may be substituted with one or more functional groups selected from the group consisting of a group, a phosphonic acid group, a phosphoric acid group, and a carboxyl group.)
It is represented by

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ can impart solubility of the electrochromic compound to the solvent. This facilitates the process of producing the electrochromic composition or display element. In addition, the electrochromic compound of the present invention can develop a yellow color, but by adjusting X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ , magenta or cyan It can also develop color.

In consideration of stability such as heat resistance and light resistance, 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 or It is preferably a group having 1 to 6 carbon atoms.

R ¹ and R ² are preferably each independently a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms or a substituted or unsubstituted aryl group. Thereby, the solubility of the electrochromic compound of this invention can be improved. As a result, the electrochromic compound of the present invention can be easily synthesized and the yield can be improved, and the display layer can be easily formed. In addition, due to the steric hindrance of R ¹ and R ² , association between the electrochromic compounds of the present invention in the display layer can be suppressed, and defects in the oxidation-reduction reaction due to the association can be reduced. The alkyl group may be linear, branched or cyclic, but is preferably branched considering steric hindrance.

The substituent in the alkyl group, alkenyl group, alkynyl group or aryl group of R ¹ and R ² is not particularly limited, but is an alkyl group, aryl group, sulfonic acid group, phosphonic acid group, phosphoric acid group, carboxyl group, trichloro group. A silyl group, a trialkoxysilyl group, a monochlorosilyl group, a monoalkoxysilyl group and the like may be mentioned, and two or more kinds may be used in combination. Among them, alkyl groups having 1 to 4 carbon atoms; halogen groups such as fluoro groups, chloro groups, and bromo groups; halogenated alkyl groups such as trifluoromethyl groups, 2,2,2-trifluoroethyl groups, and pentafluoroethyl groups Groups are preferred.

  The substituent in the heterocyclic group of A is not particularly limited, and examples thereof include a halogen group such as a fluoro group, a chloro group, and a bromo group, a substituted or unsubstituted alkyl group, an aryl group, and an alkoxy group.

  Examples of the arylene group for L include a phenylene group and a naphthylene group.

  The substituent in the arylene group of L is not particularly limited, and examples thereof include a halogen group such as a fluoro group, a chloro group, and a bromo group, a substituted or unsubstituted alkyl group, an aryl group, and an alkoxy group. May be.

  By L, the solubility of the electrochromic compound in the solvent can be imparted. This facilitates the process of producing the electrochromic composition or display element. Moreover, the electrochromic compound of the present invention can develop yellow, but if L is adjusted, it can also develop magenta and cyan.

The monovalent anion is not particularly limited, and examples thereof include Br ⁻ , Cl ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ and BF ₄ ⁻ .

  In consideration of stability such as heat resistance and light resistance, n is preferably 1 or 2.

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

  Although it does not specifically limit as an electrochromic compound of this invention, Electrochromic compounds (1)-(15) are mentioned.

本発明のエレクトロクロミック化合物は、例えば、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７及びＸ^８の少なくとも一つがカルボキシル基又はスルホン酸基である場合、Ｒ^１及び／又はＲ^２がスルホン酸基、ホスホン酸基、リン酸基及びカルボキシル基からなる群より選択される一種以上の官能基で置換されている場合に、導電性又は半導性のナノ構造体に、水素結合等を介して、結合又は吸着することができ、本発明のエレクトロクロミック組成物が得られる。このとき、導電性又は半導性のナノ構造体に対する結合力が大きいことから、Ｒ^１及び／又はＲ^２がホスホン酸基で置換されていることが好ましい。

For example, when at least one of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ is a carboxyl group or a sulfonic acid group, the electrochromic compound of the present invention is R ¹ and In the case where R ² is substituted with one or more functional groups selected from the group consisting of sulfonic acid group, phosphonic acid group, phosphoric acid group and carboxyl group, the conductive or semiconducting nanostructure The electrochromic composition of the present invention can be obtained by bonding or adsorbing via a hydrogen bond or the like. At this time, it is preferable that R ¹ and / or R ² is substituted with a phosphonic acid group because of its high binding force to the conductive or semiconductive nanostructure.

  In addition, the electrochromic composition of the present invention has a general formula in a conductive or semiconducting nanostructure.

（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、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、ｎは、１、２又は３である。）
で表される化合物を反応させることにより得られる。

(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, and A is a substituted or unsubstituted 5-membered heterocyclic group containing one or more of N, O, S, or Se, and containing C bonded to L. Yes, L is a substituted or unsubstituted arylene group, and n is 1, 2 or 3.)
It is obtained by reacting a compound represented by

The compound represented by the general formula (2) reacts with the hydroxyl group on the surface of the conductive or semiconductive nanostructure and can be bonded through a siloxane bond. At this time, it is preferable that D ¹ , D ^2, and D ³ are an alkoxy group such as an ethoxy group or a methoxy group, or a chloro group, because the bonding strength to the conductive or semiconductive nanostructure is large. B is preferably a bromo group, and C is preferably an alkylene group having 1 to 6 carbon atoms.

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ can impart solubility to the solvent of the compound represented by the general formula (3). This facilitates the process of producing the electrochromic composition or display element. In addition, the electrochromic composition of the present invention can develop a yellow color, but by adjusting X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ , magenta or cyan Can also be colored.

In consideration of stability such as heat resistance and light resistance, 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 or It is preferably a group having 1 to 6 carbon atoms.

  The substituent in the heterocyclic group of A is not particularly limited, and examples thereof include a halogen group such as a fluoro group, a chloro group, and a bromo group, a substituted or unsubstituted alkyl group, an aryl group, and an alkoxy group.

  Examples of the arylene group for L include a phenylene group and a naphthylene group.

  The substituent in the arylene group of L is not particularly limited, and examples thereof include a halogen group such as a fluoro group, a chloro group, and a bromo group, a substituted or unsubstituted alkyl group, an aryl group, and an alkoxy group. May be.

  L can impart solubility to the solvent of the compound represented by the general formula (3). This facilitates the process of producing the electrochromic composition or display element. Further, the electrochromic composition of the present invention can develop yellow, but if L is adjusted, it can also develop magenta and cyan.

  In consideration of stability such as heat resistance and light resistance, n is preferably 1 or 2.

  The compound represented by the general formula (3) preferably has a symmetric structure from the viewpoint of ease of synthesis and stability.

  The display element having a display layer containing the electrochromic composition of the present invention thus obtained is excellent in image memory properties, that is, image retention characteristics.

The conductive or semiconducting nanostructure preferably has a specific surface area of 100 m ² / g or more. Thereby, an electrochromic compound can be carried efficiently, and multicolor display excellent in display contrast ratio of color development and decoloration is possible.

  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 nanoparticles 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 contains a metal oxide in terms of transparency and conductivity. The metal oxide 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, etc. Two or more species 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.

  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. The display layer 13 is sandwiched between the display substrate 11 and the counter substrate 12. At this time, in the display layer 13, the electrochromic compound 13b of the present invention is dissolved in the electrolytic solution 13a. At this time, the electrochromic compound 13b is colored by the oxidation-reduction reaction on the surface of the display electrode 11. Further, since the white reflective layer 14 containing white 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. Note that the display substrate 11 and the counter substrate 12 are bonded together with a spacer 15 interposed therebetween.

FIG. 2 shows a modification of the display element 10. The display element 20 has the same configuration as the display element 10 except that a display layer 23 containing an electrochromic compound 13b is formed on the surface of the display electrode 11a on the counter electrode 12a side instead of the display layer 13. . The display layer 23 can be formed using a dipping method, a vapor deposition method, a spin coating method, a printing method, an inkjet method, or the like. R ¹ and / or R ² is a kind selected from the group consisting of sulfonic acid group, phosphonic acid group, phosphoric acid group, carboxyl group, trichlorosilyl group, trialkoxysilyl group, monochlorosilyl group and monoalkoxysilyl group. When substituted with the above functional group, the display electrode 11a having a hydroxyl group on the surface can be surface-treated with the electrochromic compound 13b.

  FIG. 3 shows a modification of the display element 10. The display element 30 is the same as the display element 10 except that the display layer 33 containing the electrochromic composition 33b of the present invention is formed on the surface of the display electrode 11a on the counter electrode 12b side instead of the display layer 13. It is the composition. The display layer 33 can be formed using a dipping method, a vapor deposition method, a spin coating method, a printing method, an inkjet method, or the like.

  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 13a, 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 electrolytic solution 13a, 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 white reflective layer 14 can be formed by applying a coating liquid containing white pigment particles and a resin on the counter electrode 12.

  Although it does not specifically limit as a white pigment particle, Metal oxides, such as a titanium oxide, an aluminum oxide, a zinc oxide, a silicon oxide, a cesium oxide, an yttrium oxide, are mentioned.

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

  Instead of forming the white reflective layer 14, white pigment particles may be dispersed in the polymer electrolyte.

  A method for driving the display elements 10, 20, and 30 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, 20, and 30 can be applied to display devices such as an electronic book, an electronic signboard, and an electronic shelf label.

Example 1
[Synthesis of Compound (B)]
FIG. 4 shows a synthesis flow of the compound (B).

  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. The reaction solution was gradually discharged into ice water and then neutralized with dilute aqueous sodium hydroxide solution to precipitate the product. The precipitated product was filtered, washed successively with water and methanol, and dried to obtain 8.3 g of compound (A).

  Compound (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 were added with nitrogen. The reaction flask was charged and stirred at 90 ° C. for 12 hours, and then allowed to cool. The reaction solution was diluted with chloroform and then filtered. The filtrate was washed with water and dried over anhydrous sodium sulfate, and chloroform was distilled off. The resulting 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 compound (B). When the LC / MS of the compound (B) was measured, the mass-to-charge ratio of the molecular ion peak was 450.

[Production of display element]
As the display substrate 11, a 30 mm × 30 mm glass substrate 11 b (manufactured by AGC Fabrictech) having a display electrode 11 a made of SnO ₂ formed on the entire upper surface was used. When the resistance between the end portions of the display electrode 11a was measured, it was about 20Ω.

  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. The display substrate 11 on which the nanoparticle aggregate was formed was immersed in a 0.02 mass% toluene solution of 3-bromopropyltrichlorosilane for 30 minutes to surface-treat the nanoparticle aggregate. Further, the display substrate 11 on which the surface-treated nanoparticle aggregate was formed was immersed in a 0.1% by mass toluene solution of the compound (B) and refluxed for 2 hours to surface-treat the nanoparticle aggregate. The display layer 33 containing the electrochromic composition 33b was formed.

  On the other hand, an ITO film having a thickness of about 150 nm was formed on the entire upper surface of the 30 mm × 30 mm glass substrate 12b by sputtering. Next, after applying a liquid in which 25% by mass of 2-ethoxyethyl acetate was added to the thermosetting conductive carbon ink CH10 (manufactured by Jujo Chemical Co., Ltd.) on the ITO film by using a spin coating method. The counter electrode 12a was formed by annealing at 120 ° C. for 15 minutes, and the counter substrate 12 was obtained.

  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 having an average primary particle size of 300 nm (manufactured by Ishihara Sangyo Co., Ltd.) are added to an electrolytic solution 13a in which 20% by mass of tetrabutylammonium perchlorate is dissolved in dimethyl sulfoxide (DMSO). The liquid dispersed in mass% was sealed in the cell to form the white reflective layer 14, and the display element 30 was obtained.

[Color development test]
When a negative electrode was connected to the display electrode 11a of the display element 30, a positive electrode was connected to the counter electrode 12a, and a voltage of 3.0 V was applied for 1 second, a yellow color was developed. Next, when a voltage of −4.5 V was applied for 2 seconds, the color was completely erased and returned to white. In addition, it was confirmed that the display element 30 was excellent in image holding characteristics because a colored state was maintained even when a voltage of 3.0 V was applied for 1 second and then left for 300 seconds without applying a voltage. It was.

  When the diffused light was irradiated to the display element 30 in a colored state and a decolored state using a spectrocolorimeter LCD-5000 (manufactured by Otsuka Electronics Co., Ltd.), a reflection spectrum shown in FIG. 5 was obtained. FIG. 6 shows the result of coordinate conversion of the reflection spectrum in the colored state of FIG. 5 into the CIE color system. From FIG. 5 and FIG. 6, it was confirmed that the display element 30 developed a yellow color because the width of the region having low reflectance in the visible region was narrow.

[Measurement of light absorption spectrum]
The display substrate 11 on which the display layer 33 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 20% by mass of tetrabutylammonium was dissolved in dimethyl sulfoxide (DMSO). When a voltage of -1.5 V was applied using a potentiostat ALS-660C (manufactured by BAS), yellow color was developed.

  A deuterium tungsten halogen light source DH-2000 (manufactured by Ocean Optics) was used to irradiate the quartz cell with light, and the transmitted light was detected by a spectrometer USB4000 (manufactured by Ocean Optics). A spectrum was obtained.

  From FIG. 7, it was confirmed that the colored display layer 33 has a sharp absorption peak in the vicinity of 470 nm.

(Example 2)
[Synthesis of Compound (E)]
FIG. 8 shows a synthesis flow of the compound (E).

  A reaction flask was charged with 4.0 g of 4-bromoacetophenone, 4.6 g of ethyl 4-bromobenzoate and 30 ml of 1,4-dioxane, and 4.4 g of potassium tert-butoxide was gradually added, followed by stirring at 90 ° C. for 1 hour. And allowed to cool. The reaction solution was diluted with 80 ml of water, and 7 ml of acetic acid was added to precipitate the product. The precipitated product was filtered, washed with water and dried to obtain 2.6 g of compound (C).

  Hydroxylamine hydrochloride (5.6 g), sodium hydroxide (1.6 g) and ethanol (40 ml) were charged into a reaction flask and stirred at 40 ° C. for 10 minutes. Next, 3.8 g of compound (C) was added and stirred for 1 hour under reflux, then 2.9 g of sodium hydroxide was added and stirred for 4 hours under reflux and allowed to cool. Ethanol was distilled off from the reaction solution, and the residue was dissolved in water. Further, after filtration, washing with water and drying, 0.81 g of compound (D) was obtained.

  Compound (D) 0.57 g, 4-pyridineboronic acid 0.39 g, dichlorobis (triphenylphosphine) palladium (II) 0.11 g, sodium carbonate 0.48 g, water 5 ml and 1,4-dioxane 15 ml The reaction flask was charged and stirred at 90 ° C. for 3 hours, and then allowed to cool. The reaction solution was diluted with chloroform and then filtered. 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 / acetone mixed solvent (volume ratio 1/1) as an eluent to obtain 0.23 g of compound (E). When GC / MS of the compound (E) was measured, the mass to charge ratio of the molecular ion peak was 377.

[Production of display element]
The display layer 33 containing the electrochromic composition 33b is formed by surface-treating the nanoparticle aggregate in the same manner as in Example 1 except that the compound (E) is used instead of the compound (B). A display element 30 was obtained.

[Color development test]
When a negative electrode was connected to the display electrode 11a of the display element 30, a positive electrode was connected to the counter electrode 12a, and a voltage of 3.0 V was applied for 1 second, a yellow color was developed. Next, when a voltage of −4.5 V was applied for 2 seconds, the color was completely erased and returned to white. In addition, it was confirmed that the display element 30 was excellent in image holding characteristics because a colored state was maintained even when a voltage of 3.0 V was applied for 1 second and then left for 300 seconds without applying a voltage. It was.

  Using a spectrocolorimeter LCD-5000 (manufactured by Otsuka Electronics Co., Ltd.), when the diffused light was irradiated on the display element 30 in the colored state and the decolored state, the reflection spectrum shown in FIG. 9 was obtained. FIG. 10 shows the result of coordinate conversion of the reflection spectrum in the colored state of FIG. 9 into the CIE color system. From FIG. 9 and FIG. 10, it was confirmed that the display element 30 developed a yellow color because the width of the region having low reflectance in the visible region was narrow.

[Measurement of light absorption spectrum]
The display substrate 11 on which the display layer 33 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 20% by mass of tetrabutylammonium was dissolved in dimethyl sulfoxide (DMSO). When a voltage of -1.5 V was applied using a potentiostat ALS-660C (manufactured by BAS), yellow color was developed.

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

  From FIG. 11, it was confirmed that the display layer 33 in a colored state has a sharp absorption peak in the vicinity of 430 nm.

Example 3
[Synthesis of Electrochromic Compound (1)]
0.45 g of compound (B), an appropriate amount of ethyl bromide, 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, 0.30 g of electrochromic compound (1) was obtained.

[Production of display element]
As the display substrate 11 and the counter substrate 12, 30 mm × 30 mm glass substrates 11 b and 12 b (manufactured by AGC Fabrictech) each having a display electrode 11 a and a counter electrode 12 a made of SnO ₂ formed on the entire upper surface were used. .

  The display substrate 11 and the counter substrate 12 were bonded through a 75 μm spacer 15 to obtain a cell. Next, a 1% by mass water / 2,2,3,3-tetrafluoropropanol mixed solvent (mass ratio 1/9) solution of the electrochromic compound (1) 13b was added to tetrabutylammonium perchlorate and dimethyl sulfoxide ( With respect to a solution obtained by dissolving 20% by mass with respect to DMSO), an electrolytic solution 13a added with 50% by mass was sealed in the cell, and the display element 10 in a form in which the white reflective layer 14 was not formed was obtained. .

[Color development test]
When a negative electrode was connected to the display electrode 11a of the display element 10 and a positive electrode was connected to the counter electrode 12a, and a voltage of 3.0 V was applied for 2 seconds, yellow was developed. Next, when a voltage of −3.0 V was applied for 4 seconds, it completely disappeared and returned to colorless and transparent. In addition, it was confirmed that the display element 10 was excellent in image holding characteristics because a colored state was maintained even after being applied for 3.0 seconds without applying a voltage after applying a voltage of 3.0 V for 2 seconds. It was.

Example 4
[Synthesis of Electrochromic Compound (15)]
0.45 g of compound (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 electrochromic compound (15) was obtained.

[Production of display element]
Using the sputtering method, 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 30 mm × 30 mm glass substrate 11b, whereby 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 0.9% by mass 2,2,3,3-tetrafluoropropanol solution of the electrochromic compound (15) was applied, and annealed at 120 ° C. for 10 minutes to collect nanoparticles. The display layer 33 containing the electrochromic composition 33b was formed by adsorbing the electrochromic compound (15) on the surface of the body.

  On the other hand, an ITO film having a thickness of about 150 nm was formed on the entire upper surface of the 30 mm × 30 mm glass substrate 12b by sputtering. Next, after applying a liquid in which 25% by mass of 2-ethoxyethyl acetate was added to the thermosetting conductive carbon ink CH10 (manufactured by Jujo Chemical Co., Ltd.) on the ITO film by using a spin coating method. The counter electrode 12a was formed by annealing at 120 ° C. for 15 minutes, and the counter substrate 12 was obtained.

  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 having an average primary particle size of 300 nm (manufactured by Ishihara Sangyo Co., Ltd.) are added to an electrolytic solution 13a in which 20% by mass of tetrabutylammonium perchlorate is dissolved in dimethyl sulfoxide (DMSO). The liquid dispersed in mass% was sealed in the cell to form the white reflective layer 14, and the display element 30 was obtained.

[Color development test]
When a negative electrode was connected to the display electrode 11a of the display element 30, a positive electrode was connected to the counter electrode 12a, and a voltage of 3.0 V was applied for 1 second, a yellow color was developed. Next, when a voltage of −4.5 V was applied for 2 seconds, the color was completely erased and returned to white. In addition, it was confirmed that the display element 30 was excellent in image holding characteristics because a colored state was maintained even when a voltage of 3.0 V was applied for 1 second and then left for 300 seconds without applying a voltage. It was.

(Comparative Example 1)
[Production of display element]
A chemical formula is applied to the display substrate 11 on which the nanoparticle aggregate is formed using a spin coating method.

で表されるビオロゲン化合物の１質量％２，２，３，３−テトラフルオロプロパノール溶液を塗布し、１２０℃で１０分間アニール処理して、ナノ粒子集積体の表面にビオロゲン化合物を吸着させて、エレクトロクロミック組成物３３ｂを含む表示層３３を形成した以外は、実施例１と同様にして、表示素子３０を得た。

A 1 mass% 2,2,3,3-tetrafluoropropanol solution of a viologen compound represented by the following formula is applied, and annealed at 120 ° C. for 10 minutes to adsorb the viologen compound on the surface of the nanoparticle aggregate, A display element 30 was obtained in the same manner as in Example 1 except that the display layer 33 including the electrochromic composition 33b was formed.

[Color development test]
When a negative electrode was connected to the display electrode 11a of the display element 30, a positive electrode was connected to the counter electrode 12a, and a voltage of 3.0 V was applied for 1 second, a blue color was developed. Next, when a voltage of −4.5 V was applied for 2 seconds, the color was completely erased and returned to white. In addition, it was confirmed that the display element 30 was excellent in image holding characteristics because a colored state was maintained even when a voltage of 3.0 V was applied for 1 second and then left for 300 seconds without applying a voltage. It was.

  Using a spectrocolorimeter LCD-5000 (manufactured by Otsuka Electronics Co., Ltd.), the display element 30 in a colored state was irradiated with diffused light, and a reflection spectrum shown in FIG. 12 was obtained. From FIG. 12, it was confirmed that the display element 30 develops a blue color because the width of the region having low reflectance in the visible region is wide and the light absorption is broad.

DESCRIPTION OF SYMBOLS 10, 20, 30 Display element 11 Display substrate 11a Display electrode 11b Transparent substrate 12 Counter substrate 12a Counter electrode 12b Substrate 13, 23 Display layer 13a Electrolytic solution 13b Electrochromic compound 14 White reflective layer 15 Spacer 33 Display layer 33b Electrochromic composition

JP 2006-106669 A

Claims (6)

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, wherein R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or substituted or an unsubstituted aryl group, a is 1,3,4-oxadiazolylene group or isoxazolylene alkylene group, L is a phenylene group, B ^- and C ^- are each independently, Br ⁻ , Cl ⁻ , ClO ₄ ⁻ , PF ₆ ^— or BF ₄ ^— , n is 1, and R ¹ and / or R ² are sulfonic acid group, phosphonic acid group, phosphoric acid group and carboxyl group It may be substituted with one or more functional groups selected from the group consisting of
An electrochromic compound represented by the formula: ^{2. The} electrochromic according to claim 1, wherein R ¹ and R ² are each independently a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms or a substituted or unsubstituted aryl group. Compound. An electrochromic composition, wherein the electrochromic compound according to claim 1 or 2 is bonded or adsorbed to a structure having conductive or semiconducting nanoscale irregularities . Structures with conductive or semiconducting nanoscale irregularities have a general formula

(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 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, A is a 1,3,4-oxadiazolylene group or isoxazolylene group , L is a phenylene group , and n is 1. .)
An electrochromic composition obtained by reacting a compound represented by the formula: 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. ,
A display layer containing the electrochromic compound according to claim 1 or 2 or the electrochromic composition according to claim 3 or 4 is formed on a surface of the display electrode on the counter electrode side. Display element. A display element according to claim 5;
A display device comprising means for driving the display element.

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