JP2009048142A - ELECTROCHROMIC COMPOUND, INTERMEDIATE COMPOUND, PROCESS FOR PRODUCING THEM, AND OPTICAL DEVICE USING ELECTROCHROMIC COMPOUND - Google Patents

Abstract

An electrochromic compound having durability, excellent response response, sharp color tone, and capable of stably performing reversible magenta erasing and decoloring display many times and its intermediate compounds and their compounds A manufacturing method and an electrochromic device are provided.
The electrochromic compound uses 2,5-bis (4-pyridyl) -3,4-difluorothiophene as an intermediate compound, which is used as a halide B ₁ -A ₁ -Y, B ₂ -A _2-. Y (where Y represents an anion, A ₁ and A ₂ are an optionally substituted aliphatic hydrocarbon group, and B ₁ and B ₂ are an optionally substituted aliphatic hydrocarbon. A group or an aromatic hydrocarbon group, and at least one of B ₁ and B ₂ has a functional group to be supported on the porous electrode. The electrochromic compound 3 is supported on the porous electrode 4 of the display electrode structure 11 of the electrochromic device 10.
[Selection] Figure 1

Description

  The present invention relates to an electrochromic compound excellent in color development efficiency, response speed, and display color purity, suitable for use as a display device, an intermediate compound thereof, a production method thereof, and an electrochromic device. The present invention relates to an electrochromic compound for decoloration display, an intermediate compound thereof, a production method thereof, and an electrochromic device.

  In recent years, there has been a growing demand for display pigment materials and display elements using the same that are bright and excellent in color purity, have low power consumption, and can be easily applied to full-color display. Conventionally, CRT (Cathode Ray Tube), PDP (Plasma Display Panel), ELD (Electroluminescence Display) VFD (Vacuum Fluorescent Display), FED (Field Emission Display), LED (Light Emitting Diode) and other light emitting elements, DMD (Digital Many technologies have been proposed for non-light emitting elements such as a micromirror display (LCD), a liquid crystal display (LCD), an electrochromic display (ECD), and an electrophoresis display (EPD).

  However, a display device using various light-emitting elements known in the art is used in such a form that the user directly looks at the light emission, and thus has a problem of causing visual fatigue when viewed for a long time.

  In particular, LCD is a technology with increasing demand among non-light emitting elements, and is used for various display applications such as large and small. However, LCD has a narrow viewing angle and is easy to see. There are issues to be improved. In addition, mobile devices such as mobile phones, digital still cameras, and digital video cameras that use LCDs are often used outdoors. Under sunlight, display light is offset and visibility deteriorates. There was also a problem.

  With respect to reflective display elements among non-light emitting elements, various techniques have been proposed in the past due to an increase in demand for electronic paper. For example, a reflective LCD or an electrophoretic display device can be used.

  As the reflective LCD, a GH type liquid crystal system using a dichroic dye, a cholesteric liquid crystal, and the like are known. These methods have the advantage of power saving because they do not use a backlight as compared to conventional transmissive LCDs, but they have a viewing angle dependency and low light reflection efficiency, so There is a problem that the screen becomes dark.

  On the other hand, an electrophoretic display device uses a phenomenon in which charged particles dispersed in a solvent move by an electric field, and has the advantages of low power consumption and no viewing angle dependency. However, when performing full color, it is necessary to apply a juxtaposed mixing method using a color filter, so that there is a problem that the reflectance is lowered and the screen is inevitably darkened.

  In recent years, an electrochromic (hereinafter abbreviated as EC) element has been proposed for a light control mirror, a timepiece, or the like of an automobile. This EC element does not require a polarizing plate, has no viewing angle dependency, has a color development type, has excellent visibility, has a simple structure and can be easily enlarged, and displays various colors depending on the choice of materials. Has the advantage of being possible.

  As an example of a display device using a specific EC element, there is a display device having a structure in which a semiconductor nanoporous layer is provided on at least one of a pair of transparent electrodes and an EC dye is supported on the semiconductor nanoporous layer. (For example, refer to Patent Documents 1 and 2 described later.) These display devices can be held in a static state just by forming an open circuit to block the movement of electrons between the electrodes and maintaining the oxidation-reduction state, so no power is required to maintain the display image and consumption It is excellent in that the power is extremely low.

  An EC display element having a structure in which structural units each supporting yellow, cyan, and magenta EC dyes are stacked and capable of performing full color display is well known (for example, Patent Document 3 described later, 4 and 5), which are well known for viologen compounds (see, for example, Patent Document 6 described later).

  Further, Non-Patent Document 1 described later has a description regarding the synthesis of bis (2-phosphonoethyl) -4,4′-bipyridinium dichloride.

JP 2003-248242 A (paragraph 0008, paragraph 0025, FIGS. 1 and 2) JP 2003-270670 A (paragraph 0008, paragraph 0031, FIGS. 1 to 4) JP 2007-10975 A (paragraph 0028, paragraph 0046) JP 2007-41259 (paragraphs 0011 to 0012, paragraph 0148, FIGS. 1 to 4) JP 2007-121714 A (paragraphs 0071 to 0088) JP-T-2006-519222 (Claims) D. Cummins, et al, “Ultrafast Electrochromic Windows Based on Redox-Chomophore Modified Nanostructured Semiconducting and Conducting Films”, J. Phys. Chem. B, 104 (2000) 11449-11459 (Experimental Sections, Scheme 1.)

  However, in the display devices proposed in Patent Documents 1 and 2, a bipyridine compound called a viologen is used as an EC dye, which originally reversibly blues and decolors. It is not assumed to perform full color display.

  Patent Documents 3, 4, and 5 describe a display device using an EC dye that develops cyan (C), magenta (M), and yellow (Y), which is necessary for full color display. It is possible to achieve perfect colorlessness in the transition from the colored state to the colorless state, and vivid coloration in the transition from the colorless state to the colored state, with excellent response response, sharp colors, and many times. Sufficient consideration has not been given to electrochromic compounds that can perform reversible cyan reversible display in a stable and reversible manner.

  The problem with conventional organic electrochromic compounds was that it was not possible to achieve both complete colorlessness when changing from a colored state to a colorless state and vivid coloration when changing from a colorless state to a colored state. was there.

  Further, the electrochromic compound in the prior art has a problem that the color purity is low and it is difficult to display a precise and clear color image.

  The present invention has been made in order to solve the above-described problems, and the object thereof is to achieve excellent colorlessness, realization of complete colorlessness in a change from a colored state to a colorless state, and colorlessness. It is possible to achieve both vivid color development in the transition from state to color state, durable, excellent response response, sharp color tone, reversible magenta reversible color display stably It is to provide an electrochromic compound which can be repeatedly used, an intermediate compound thereof, a production method thereof, and an electrochromic device.

That is, the present invention relates to an electrochromic compound comprising a compound represented by the formula (1) or a derivative in which a hydrogen atom bonded to a carbon atom of the C ₅ N ring is substituted with another atom or atomic group. It is. However, in Formula (1), a and b are integers satisfying a × b = 2, Y ^b− represents a b-valent anion, and A ₁ and A ₂ are optionally substituted aliphatic hydrocarbons. B ₁ and B ₂ are an optionally substituted aliphatic hydrocarbon group or an aromatic hydrocarbon group, and at least one of B ₁ and B ₂ is for supporting the porous electrode. Has a functional group.

…（１）

... (1)

Further, the present invention relates to 2,5-bis (4-pyridyl) -3,4-difluorothiophene represented by the formula (2), or a hydrogen atom bonded to a carbon atom of the C ₅ N ring is another atom. Alternatively, it relates to an intermediate compound composed of a derivative substituted with an atomic group.

…（２）

... (2)

Further, the present invention includes a step of repeating lithiation of 2,5-bis (4-pyridyl) -3,4-dibromothiophene and then introducing a fluorine group by a fluorinating agent a plurality of times. 2,5-bis (4-pyridyl) -3,4-difluorothiophene represented by 2), or a derivative in which the hydrogen atom bonded to the carbon atom of the C ₅ N ring is substituted by another atom or atomic group The present invention relates to a method for producing an intermediate compound.

In the present invention, the hydrogen atom bonded to the carbon atom of 2,5-bis (4-pyridyl) -3,4-difluorothiophene represented by the above formula (2) or the C ₅ N ring thereof is another An intermediate compound composed of a derivative substituted by an atom or an atomic group is a halide B ₁ -A ₁ -Y, B ₂ -A ₂ -Y (where Y represents an anion, A ₁ and A ₂ are Is an optionally substituted aliphatic hydrocarbon group, B ₁ and B ₂ are an optionally substituted aliphatic hydrocarbon group or an aromatic hydrocarbon group, and at least one of B ₁ and B ₂ Has a functional group to be supported on the porous electrode.), And is bonded to the carbon atom of the compound represented by the above formula (1) or its C ₅ N ring. Electros consisting of derivatives in which atoms are replaced by other atoms or groups of atoms Those relating to the manufacturing method of Rokuromikku compound.

The present invention also uses an electrochromic compound comprising a compound represented by the above formula (1) or a derivative in which the hydrogen atom bonded to the carbon atom of the C ₅ N ring is substituted with another atom or atomic group. The present invention relates to an optical device.

  The electrochromic compound according to the present invention is suitable for use in an electrochromic device having durability, excellent response response, sharp color tone, and capable of reversible cyan color reversible display many times. can do.

The intermediate compound according to the present invention is an electrochromic compound comprising a compound represented by the above formula (1) or a derivative in which the hydrogen atom bonded to the carbon atom of the C ₅ N ring is substituted by another atom or atomic group It can use suitably for the manufacturing method of.

According to the method for producing an intermediate compound according to the present invention, a compound represented by the above formula (1), or a derivative in which the hydrogen atom bonded to the carbon atom of the C ₅ N ring is substituted by another atom or atomic group 2,5-bis (4-pyridyl) -3,4-difluorothiophene represented by the above formula (2), or C thereof, which can be suitably used as an intermediate in a method for producing an electrochromic compound comprising: ₅ A derivative in which the hydrogen atom bonded to the carbon atom of the N ring is substituted with another atom or atomic group can be provided.

According to the method for producing an electrochromic compound according to the present invention, the carbon atom of the 2,5-bis (4-pyridyl) -3,4-difluorothiophene represented by the above formula (2) or its C ₅ N ring is used. An intermediate compound composed of a derivative in which a hydrogen atom to be bonded is substituted by another atom or atomic group is used as a synthesis raw material, and is bonded to the compound represented by the above formula (1) or a carbon atom of the C ₅ N ring. It is possible to synthesize an electrochromic compound composed of a derivative in which a hydrogen atom is substituted with another atom or atomic group.

According to the optical device of the present invention, an electrochromic comprising a compound represented by the above formula (1) or a derivative in which a hydrogen atom bonded to a carbon atom of the C ₅ N ring is substituted with another atom or atomic group Since a compound is used, a high-performance optical device based on electrochromism can be provided.

The intermediate compound of the present invention is an electrochromic compound comprising a compound represented by the above formula (1) or a derivative in which a hydrogen atom bonded to a carbon atom of the C ₅ N ring is substituted with another atom or atomic group Since this intermediate compound can be efficiently synthesized at a high yield, an electrochromic compound can be efficiently synthesized.

The method for producing an intermediate compound of the present invention comprises a compound represented by the above formula (1) or a derivative in which the hydrogen atom bonded to the carbon atom of the C ₅ N ring is substituted with another atom or atomic group. An intermediate for synthesizing an electrochromic compound is synthesized. Since this intermediate compound can be synthesized efficiently and with a high yield, the electrochromic compound can be synthesized efficiently.

In the optical device of the present invention, the first support substrate, the first transparent electrode formed on the first support substrate, and the metal oxide porous electrode formed on the first transparent electrode are provided. A display electrode structure including the second support substrate, a counter electrode structure including a second transparent electrode formed on the second support substrate, and sandwiched between the display electrode structure and the counter electrode structure The first transparent electrode and the second transparent electrode are opposed to each other, and an electrochromic compound is supported on the metal oxide porous electrode, A compound represented by the above formula (1), which has an electrochromic element structure that performs reversible color development by an electrochromic compound by controlling a voltage applied between the transparent electrode and the second transparent electrode. Or C ₅ N hydrogen atom attached to a carbon atom of the ring is a compound consisting of substituted derivatives by another atom or atomic group is used as the electrochromic compound, reversible Hatsusho magenta by controlling the application of the voltage It may be configured as an electrochromic device that performs color. According to this configuration, it is possible to provide an electrochromic device having durability, excellent response response, sharp color tone, and capable of performing reversible magenta color reversible display many times. .

  Further, the electrochromic element structure is a first electrochromic element structure, and a second electrochromic element in which a compound that reversibly develops yellow as the electrochromic compound in the electrochromic element structure is used. And a first electrochromic element structure in which a compound capable of reversibly developing cyan is used as the electrochromic compound in the electrochromic element structure, and the first, second, second 3 electrochromic element structures are preferably stacked to display a full-color image. According to this configuration, it is possible to provide an electrochromic device that has durability against many repetitions of color development and decoloration, is excellent in response response, and can perform full color display with a sharp color tone.

  Hereinafter, an electrochromic compound, an intermediate compound thereof, a production method thereof, and an electrochromic device according to the present invention will be specifically described with reference to the drawings.

  However, the present invention is not limited to the following examples, and a conventionally known configuration can be added as appropriate, and does not depart from the gist of the present invention.

Embodiment According to this embodiment, 2,5-bis (4-pyridyl) -3,4-difluorothiophene (C ₁₄ H ₈ N ₂ SF ₂ ), which is an intermediate compound represented by the formula (2), is , 2,5-bis (4-pyridyl) -3,4-dibromothiophene (C ₁₄ H ₈ N ₂ SBr ₂ ) is lithiated and then the process of introducing a fluorine group is repeated one to several times The electrochromic compound represented by formula (1) can be synthesized using this intermediate compound (formula (2)).

  2,5-bis (4-pyridyl) -3,4-difluorothiophene, which is an intermediate compound represented by the formula (2) according to the present embodiment, is an electrochromic compound represented by the formula (1). It can be suitably used directly in the production method.

  The electrochromic compound represented by the formula (1) according to the present embodiment can be suitably used for an electrochromic device, realizing almost complete colorlessness in a change from a colored state to a colorless state, and colorless. Realization of vivid color development in the change from the state to the color development state can be achieved at the same time, excellent response response, sharp color tone, and reversible cyan color reversible display can be performed stably and repeatedly.

  The electrochromic device according to the present embodiment has an electrolyte layer in which a pair of electrode structures (a display electrode structure and a counter electrode structure) in which at least a transparent electrode is formed on a support substrate are opposed to each other. Is a metal oxide in which an electrochromic compound represented by the formula (1) is supported on at least the display electrode structure of the transparent electrodes constituting the pair of electrode structures In this electrochromic device, a porous electrode is formed, and the voltage applied between a pair of electrode structures is controlled, whereby magenta can be reversibly developed and decolored.

  In the organic electrochromic compound in the prior art, it was not possible to achieve both almost complete colorlessness in the change from the colored state to the colorless state and vivid coloration in the change from the colorless state to the colored state. According to the present invention, by using an electrochromic compound capable of contributing to full-color image formation, which can stably display a clear magenta color development and decoloration many times, it is possible to improve response speed and color development efficiency. An electrochromic device that is excellent, has high color purity, and enables precise image control was obtained.

  In addition, according to the present invention, the visible absorption spectrum shape is almost the same as the spectrum shape in the initial state before the color-decoloring operation after a number of color-decoloration operations with the electrochromic compound, and there is no change. The color development state does not change and does not become unstable, and the color density does not decrease, and it has durability against repeated operation of color development and decoloration many times. Even when the operation is performed, it is possible to reversibly perform clear color development and reversal, and to realize an electrochromic device that displays an image with extremely stable color development. In addition, even in the case of an electrochromic device that performs full-color image display by precise image control, even if the color development required for full-color display is repeated many times by the decoloration of organic electrochromic dyes that can contribute to full color, Clear color display can be performed stably.

  FIG. 1 is a cross-sectional view illustrating a schematic configuration of an example of an electrochromic device according to an embodiment of the present invention.

  As shown in FIG. 1, an electrochromic device 10 includes a display electrode structure 11 having a structure in which a transparent electrode 2 and a porous electrode 4 on which an electrochromic compound 3 of the present invention is supported are provided on a support substrate 1. In addition, a counter electrode structure 12 having a configuration including the transparent electrode 7 and the porous electrode 8 is disposed on the support substrate 6 so as to face each other with the electrolyte layer 5 interposed therebetween.

  In FIG. 1, the porous electrodes 4 and 8 are formed on both of the opposing transparent electrodes 2 and 7, but the present invention is not limited to this configuration, and only one electrode is necessary if necessary. A porous electrode may be formed, and the electrochromic compound 3 may be supported on the porous electrode. Hereinafter, the components will be sequentially described.

<Support substrate>
The supporting substrates 1 and 6 are preferably made of a material having excellent heat resistance and high dimensional stability in the planar direction. Specifically, glass materials and transparent resins can be applied, but the materials are not limited thereto. is not.

  When applying a transparent resin, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamide (PA), polysulfone (PS), polyethersulfone (PES), polyetheretherketone (PEEK) , Polymer materials such as polyphenylene sulfide (PPS), polycarbonate (PC), polyimide (PI), polymethyl methacrylate (PMMA), polystyrene, and the like, and a plastic substrate using any of these can be used.

<Transparent electrode>
The transparent electrodes 2 and 7 are formed by laminating a transparent electrode layer on a predetermined transparent substrate. Examples of the electrode material constituting the transparent electrodes 2 and 7 include a mixture of In ₂ O ₃ and SnO ₂ , a so-called ITO film (tin-doped indium oxide film), and a film coated with SnO ₂ or In ₂ O _3. Etc. The ITO film or a film coated with SnO ₂ or In ₂ O ₃ may be doped with Sn, Sb, F, etc., and the fluorine-doped tin oxide film is called an FTO film. In addition, MgO, ZnO, etc. are applicable. An AZO film in which ZnO is doped with Al, a GZO film in which ZnO is doped with gallium (Ga), a ZnO in which indium (In) is doped, and the like can also be applied.

<Porous electrode>
The porous electrodes 4 and 8 are preferably made of a material having a large surface area in order to ensure a high supporting function of the electrochromic compound described later. Examples thereof include a porous shape having fine pores on the surface and inside, a lot shape, a wire shape, a mesoporous shape, and an aggregated particle shape.

  As materials for the porous electrodes 4 and 8, for example, metals, intrinsic semiconductors, organic semiconductors, carbons, and the like can be used. However, oxide semiconductors, composite oxide semiconductors, and the like are preferable because of high transmittance.

Examples of oxide semiconductors and composite oxide semiconductors include TiO ₂ , SnO ₂ , SrTiO ₃ , WO ₃ , ZnO, Ta ₂ O ₅ , Nb ₂ O ₅ , In ₂ O ₃ , KTiO ₃ , Cu ₂ O, and titanium. Sodium oxide, barium titanate, potassium niobate, SnO ₂ —ZnO, Nb ₂ O ₅ —SrTiO ₃ , Nb ₂ O ₅ —Ta ₂ O ₅ , Nb ₂ O ₅ —ZrO ₂ , Nb ₂ O ₅ —TiO ₂ , _{Ti-SnO 2, Zr-SnO} 2, Sb-SnO 2, Bi-SnO 2, in-SnO 2 and the like, in particular _{TiO 2, SnO 2, Sb-} SnO 2, in-SnO 2 are preferred.

  As for the porous electrode 8, it is more preferable that an organic radical compound is supported on the porous electrode because the storage capacity of the electrode is improved.

<Electrochromic compound>
Next, the electrochromic compound 3 will be described. The electrochromic compound 3 is assumed to be carried on the surface of the porous electrode 4 and the fine pores inside, and in the present invention, the compound represented by the above formula (1) is particularly applied.

However, as described above, in the above formula (1), a and b are integers satisfying a × b = 2, and Y ^b− represents a b-valent anion. This is fluorine ion, chlorine ion, bromine ion, iodine ion, perchlorate ion, periodate ion, hexafluorophosphate ion, hexafluoroantimonate ion, hexafluorostannate ion, phosphate ion, boron fluoride Inorganic acid ions such as hydrogenate ion and tetrafluoroborate ion, thiocyanate ion, benzenesulfonate ion, naphthalenesulfonate ion, naphthalene disulfonate ion, p-toluenesulfonate ion, alkylsulfonate ion, benzenecarboxylate ion , Alkyl carboxylate ions, trihaloalkyl carboxylate ions, alkyl sulfate ions, trihaloalkyl sulfate ions, nicotinate ions, tetracyanoquinodimethane ions and the like.

Further, as described above, in the above formula (1), A ₁ and A ₂ are aliphatic hydrocarbon groups that may be substituted, and B ₁ and B ₂ are aliphatic groups that may be substituted. It is a hydrocarbon group or an aromatic hydrocarbon group, and at least one of A ₁ and A ₂ has a functional group for supporting the electrochromic compound on the porous electrode. A ₁ and A ₂ are necessary for the electrochromic compound to perform reversible color erasing of magenta.

  As the functional group that acts as an adsorbing group for adsorbing the electrochromic compound to the porous electrode, an acidic group such as a phosphonic acid group, a carboxylic acid group, a hydroxyl group, and a sulfonic acid group is preferable, and the phosphonic acid group is particularly preferable because of its high adsorbing ability. The amino group can also be such a functional group. It is also possible to covalently bond to the porous electrode surface using a metal halide.

  The manufacturing method of the pigment | dye compound shown to the said Formula (1) is demonstrated. The dye compound of the above formula (1) is prepared by reacting the intermediate compound of the above formula (2) with a halide represented by the following formula (3) (especially bromide and iodide are preferable) in a suitable solvent. Or can be obtained by direct reaction.

However, X shall be bromine or iodine. A, B is subject to the structure of the _{A 1, A 2, B 1} , B 2.

  Next, a method for producing the compound intermediate represented by the above formula (2) and the electrochromic compound represented by the above formula (1) will be described.

  2A and 2B are diagrams illustrating a manufacturing process according to an embodiment of the present invention. FIG. 2A illustrates an intermediate manufacturing process, and FIG. 2B illustrates an electrochromic compound manufacturing process. It is a figure to do.

As shown in FIGS. 2A and 2A, 2,3,4,5-tetrabromothiophene (C ₄ Br ₄ S) (formula (2-1) in FIG. 2) and formula in FIG. A pyridine compound (or a derivative thereof) represented by (2-2), for example, 4,4,5,5-tetramethyl-2- (4-pyridyl) -1,3,2, -dioxaboron (C ₁₁ H ₁₆ BNO ₂ ) (formula (4) below, formula (2-2a) in FIG. 2), a compound represented by formula (5) below (if R = H, 4- (dihydroxyboryl) pyridine (C ₅ H ₆ BNO ₂ ) (formula (2-2b) in FIG. 2) or 4- (trimethylstannyl) pyridine (C ₈ H ₁₃ NSn) (formula (6) below, in FIG. Formula (2-2c)) is subjected to a coupling reaction with a palladium-based catalyst in an appropriate solvent in the presence of a base as necessary. And by the formula (7), to obtain a compound represented by the formula (2-3) in FIG. 2 (2,5-bis (4-pyridyl) -3,4-dibromo-thiophene).

…（４）

(4)

…（５）
但し、Ｒは水素又は族炭化水素である。

... (5)
Where R is hydrogen or a group hydrocarbon.

…（６）

(6)

…（７）

... (7)

As shown in FIGS. 2 (A) and 2 (b), the obtained compound of formula (7) and formula (2-3) in FIG. One of the bromo groups is lithiated by reacting with a lithiating reagent such as formula (2-4) in the above, C ₄ H ₉ Li). Therefore, the lithiation reagent is preferably reacted in a molar ratio of 1.0 to 1.2 times with respect to the compound of the above formula (7). Here, dehydrated ether, THF, or the like can be used as the reaction solvent, and the reaction temperature is preferably in the range of −10 ° C. to −100 ° C. In this way, the compound (C ₁₄ H ₈ N ₂ SBrLi) represented by the formula (9) in which one of the bromo groups is lithiated and the formula (2-5) in FIG. 2 is produced.

As shown in FIGS. 2 (A) and 2 (c), a compound in which a fluorine group is introduced into the compound of the above formula (7) and the formula (2-3) in FIG. 2 by subsequently reacting with an appropriate fluorinating agent. (8), the compound shown in (2-7) in FIG. 2, 2,5-bis (4-pyridyl) -3-fluoro-4-bromothiophene, C ₁₄ H ₈ N ₂ SBrF) is produced. As the fluorinating agent, known ones such as SF ₄ , SbF ₅ , NaBF ₄ , NH ₄ BF ₄ can be used, but N-fluorobenzenesulfonamide (formula (2-6) in FIG. 2), C ₆ H ₆ NO ₂ S) is preferably used.

  At this time, as shown in FIGS. 2A and 2D, the compound of the following formula (8) into which the fluorine group was introduced and the compound of the formula (2-7) in FIG. 2 is reacted with the compound of the formula (2-5) in FIG. 2, and according to the following reaction formula, the compound of the above formula (1), the formula (2-8) in FIG. Since the compound, the above formula (2)), the above formula (7), and the compound of the formula (2-3) in FIG. 2 are formed, the stoichiometric theoretical yield is 50%.

  Reaction formula: compound of formula (8) + compound of formula (9) → compound of formula (1) + compound of formula (7)

…（８）

... (8)

…（９）

... (9)

  If the same process is repeated with n = 1, 2, 3, 4, 5,... For the compound of the above formula (7) produced by this reaction, the stoichiometric theoretical yield is 1/2. (= 50%), 3/4 (= 75%), 7/8 (= 87.5%), 15/16 (= 93.75%), 31/32 (= 96.875%), and so on. It will increase. Considering the complexity of the process and the yield, it is preferable to repeat this process about 1 to 4 times in order to obtain the compound of the above formula (1). For the purification after the reaction, a known purification method such as recrystallization or column purification can be used.

  As described above, the intermediate compound (2,5-bis (4-pyridyl) -3,4-difluorothiophene) represented by the above formula (2) for the synthesis of the electrochromic compound of the present invention is synthesized. Can do.

  Next, the manufacturing method of the electrochromic compound shown to said Formula (1) is demonstrated.

  As shown in FIG. 2 (B), the above-mentioned formula (2) synthesized by the step shown in FIG. 2 (A), the intermediate compound and halide shown in formula (2-8) in FIG. 2 (in FIG. 2) (2-9a)) and (2-9b) can be reacted to synthesize the target electrochromic compound represented by the above formula (1) and formula (2-10) in FIG. it can.

The compound represented by the above formula (1) or formula (2-10) in FIG. 2 is Y ^b− which is a b-valent anion, and A which is an aliphatic hydrocarbon group which may be substituted. ₁ , A ₂ , and B ₁ and B ₂ which are optionally substituted aliphatic hydrocarbon groups or aromatic hydrocarbon groups, all of the structures selected as appropriate can be synthesized. In addition, it was confirmed that magenta, which is the object of the present invention, is clear and sharp and has good repeatability, can be developed and decolored.

  Although expressed as divalent in the above formula (1), when magenta color is developed, a monovalent radical state is obtained by a reduction reaction. This compound can be stabilized in a monovalent state, and was confirmed to be extremely excellent as an electrochromic compound for magenta coloring.

In the above description, the synthesis of the intermediate compound represented by the above formula (2) and the electrochromic compound represented by the above formula (1) has been described. In the above description, FIG. By using a pyridine compound derivative in which the hydrogen atom bonded to the C (carbon) atom of the C ₅ N ring of the pyridine compound represented by the formula (2-2) in a) is substituted with another atom or atomic group, C _{5 A} 2,5-bis (4-pyridyl) -3,4-difluorothiophene derivative in which the hydrogen atom bonded to the C (carbon) atom of the N ring is replaced by another atom or atomic group can be synthesized. By using this derivative, a derivative of the electrochromic compound represented by the above formula (1) can be synthesized.

  Specific examples of the electrochromic compound represented by the above formula (1) are shown in the following formulas (10) to (15). The compounds represented by the following formulas (10) to (15) can be regarded as 2,5-bis (4-pyridyl) thiophene derivatives, respectively.

…（１０）

(10)

…（１１）

... (11)

…（１２）

(12)

…（１３）

... (13)

…（１４）

... (14)

…（１５）

... (15)

In the compounds represented by the above formulas (10) to (15), the hydrogen atom bonded to the C (carbon) atom of the C ₅ N ring may be substituted with another atom or atomic group. Needless to say good things.

<Supporting of electrochromic compound on porous electrode>
Next, a method for supporting the electrochromic compound made of 2,5-bis (4-pyridyl) thiophene derivative on the porous electrode 4 will be described. For example, a method of adsorbing on the surface of the porous electrode 4 can be applied. As this specific method, a spin coating method or the like, a natural adsorption method of immersing in a solution of a compound to be supported, or the like can be applied, and a natural adsorption method that does not require a special apparatus is particularly suitable.

  As a natural adsorption method, a solution is prepared by dissolving a predetermined electrochromic compound in a predetermined solvent, and a transparent substrate on which a porous electrode 4 that has been previously dried is formed is immersed in this solution. And a method of applying a solution in which a predetermined electrochromic compound is dissolved to the porous electrode 4. In this natural adsorption method, the compound of the present invention has a phosphonic acid group in its structure, and can be reliably supported on the porous electrode 4.

  Examples of the solvent for dissolving the electrochromic compound include water, alcohol, acetonitrile, propionitrile, dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, esters, carbonates, ketones, and carbonization. Hydrogen or the like can be applied, and these may be used alone or in combination as appropriate. In particular, from the viewpoint of solubility, it is preferable to use water.

  A method of supporting the electrochromic compound on the surface of the porous electrode by chemical bonding is also suitable. A predetermined functional group such as an alkyl group, phenyl group, ester group, amide group, etc. is interposed between the surface of the porous electrode and the electrochromic compound skeleton to chemistry the electrochromic compound on the surface of the porous electrode. It can also be supported by bonding.

  Further, after the surface of the porous electrode is surface-modified with a silane coupling agent or the like, the electrochromic compound can be chemically bonded and supported. Since the electrochromic compound is firmly supported on the surface of the porous electrode by such a strong force due to the chemical bond, the durability of the electrochromic device can be improved. In addition, an electrolyte layer made of a material having a high electrochromic compound solubility can be used, and the range of the electrochromic compound to be used is widened and the degree of freedom of selection is increased.

  Although FIG. 1 shows an example in which the electrochromic compound 3 is supported only on the porous electrode 4 on the display electrode structure 11 side, the electrochromic device of the present invention is not limited to this configuration. .

  That is, a predetermined electrochromic compound may be supported on the porous electrode 8 on the counter electrode structure 12 side. In this case, it is necessary to select materials so that the coloring reaction and the decoloring reaction occur according to the reverse reaction of the oxidation reaction and the reduction reaction, respectively.

  For example, when the organic EC dye carried on the porous electrode 4 becomes a radical state by the reduction reaction and develops color, the porous electrode 8 has the same color tone as the organic EC dye carried on the porous electrode 4 in a steady state. Yes, select an electrochromic compound that develops color by oxidation reaction.

  As described above, by adopting a configuration in which the electrochromic compound is supported in both the electrode structures 11 and 12, the color display density can be sufficiently increased. Therefore, in the finally obtained electrochromic device, color development is achieved. Clarification and image clarity can be improved.

<Electrolyte>
The electrolyte layer 5 has a configuration in which a supporting electrolyte is dissolved in a solvent. Examples of the supporting electrolyte include lithium salts such as LiCl, LiBr, LiI, LiBF ₄ , LiClO ₄ , LiPF ₆ , and LiCF ₃ SO ₃ , potassium salts such as KCl, KI, and KBr, and NaCl, NaI, for example. And sodium salts such as NaBr, and tetraalkylammonium salts such as tetraethylammonium borofluoride, tetraethylammonium perchlorate, tetrabutylammonium borofluoride, tetrabutylammonium perchlorate, and tetrabutylammonium halide.

  A known redox compound may be added to the electrolyte layer 5 as necessary. As the redox substance, for example, a ferrocene derivative, a tetracyanoquinodimethane derivative, a benzoquinone derivative, a phenylenediamine derivative, or the like can be applied.

  As said solvent, the thing which melt | dissolves a supporting electrolyte and does not melt | dissolve the electrochromic compound mentioned above is selected. For example, it is appropriately selected from water, acetonitrile, dimethylformamide, propylene carbonate, dimethyl sulfoxide, propylene carbonate, gamma butyrolactone, 3-methoxypropionitrile and the like.

Further, a so-called matrix material may be applied to the electrolyte layer 5. Matrix material can be appropriately selected depending on the purpose, for example, skeletal unit _{respectively, - (CC-O) n} -, - (CC (CH 3) -O) n -, - (CC-N ) _N- , or-(C-C-S) _n- , polyethylene oxide, polypropylene oxide, polyethyleneimine, and polyethylene sulfide. Note that these skeleton units may have a branched structure as the main chain structure. Polymethyl methacrylate, polyvinylidene fluoride, polyvinylidene chloride, polycarbonate, and the like are also suitable.

  The electrolyte layer 5 may be a polymer solid electrolyte layer. In this case, it is preferable to add a predetermined plasticizer to the polymer of the matrix material. As the plasticizer, when the matrix polymer is hydrophilic, water, ethyl alcohol, isopropyl alcohol, and a mixture thereof are preferable. When the matrix polymer is hydrophobic, propylene carbonate, dimethyl carbonate, ethylene carbonate, γ- Preferred are butyrolactone, acetonitrile, sulfolane, dimethoxyethane, ethyl alcohol, isopropyl alcohol, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, n-methylpyrrolidone, and mixtures thereof.

  A method for manufacturing the electrochromic device of the present invention will be described. The display electrode structure 11 is produced. A transparent electrode 2 is formed on a support substrate 1 having a predetermined material and film thickness, and then a porous electrode 4 is formed. After that, for example, the dye is supported by being immersed in an organic EC dye aqueous solution, and a washing process and a drying process are performed with an ethanol solution.

  Subsequently, the counter electrode structure 12 is produced by forming the transparent electrode 7 on the support substrate 6 having a predetermined material and film thickness, and then forming the porous electrode 8. However, the detailed formation method of the porous electrodes 4 and 8 shall follow the method mentioned above. The electrode for supporting the organic EC dye is also appropriately selected to be both or one.

  Next, a solution for the electrolyte layer is prepared. Subsequently, the display electrode structure 11 and the counter electrode structure 12 are bonded together using a predetermined adhesive. At this time, an injection port is formed in a part so that an electrolytic solution can be injected in a later process. . Thereafter, an electrolytic solution is injected from the injection port and sealed with a resin adhesive, whereby an electrochromic device having an opposing electrode structure is manufactured.

  Next, a display method using the electrochromic device 10 of the present invention will be described.

  In the electrochromic device 10 of FIG. 1, the surface of the porous electrode 4 carries an electrochromic compound represented by the formula (1) that hardly absorbs in the visible region in a steady state. A predetermined lead wire is connected to the pair of electrode structures 11 and 12 constituting the electrochromic device 10 to constitute a display device. When a predetermined voltage is applied through a predetermined lead wire, electrons are transferred between the porous electrode 4 and the electrochromic compound material carried on the porous electrode 4, and an electrochemical reduction reaction occurs in the electrochromic compound, and radicals are generated. The state becomes magenta.

  The porous electrode 8 on the counter electrode structure 12 side is charged with a charge opposite to that of the organic EC dye (when the organic EC dye is charged with a negative charge by a reduction reaction, the porous electrode 8 is + The color development function by the dye is enhanced and stabilized.

  An example of the thickness of each layer constituting the electrochromic device shown in FIG. 1 is as follows.

Thickness of support substrate 1 = 10 μm to 10 mm,
Support substrate 6 thickness = 10 μm to 10 mm,
The thickness of the transparent electrode 2 = 40 nm to 1000 nm,
The thickness of the transparent electrode 7 = 40 nm to 1000 nm,
The thickness of the porous electrode 4 = 1.5 μm to 30 μm,
Thickness of porous electrode 8 = 1.5 μm to 30 μm,
Display electrode structure 11 thickness = 11 μm to 11 mm,
The thickness of the counter electrode structure 12 = 11 μm to 11 mm,
The distance between the transparent electrode 2 and the transparent electrode 7 is 1 μm to 1 mm.

  The electrochromic device of the present invention is not limited to the configuration shown in FIG. 1, but can be applied to a device configuration capable of multicolor display. That is, the structure is the same as that of the electrochromic structure shown in FIG. 1, and an electrochromic compound that becomes a radical state by an electrochemical reaction and develops color in cyan (C) and yellow (Y) is applied to a predetermined porous electrode. An electrode structure is produced by supporting the substrate, and using these three layers, a layered structure of magenta (M), yellow (Y), and cyan (C) is used to reversibly display color. Thus, an electrochromic device with a full color display can be obtained.

  As an electrochromic compound (organic EC dye), a dye having an absorption maximum in the yellow region (range of 430 to 490 nm), magenta region (range of 500 to 580 nm), and cyan region (range of 600 to 700 nm) should be used. Is desirable.

  The electrochromic device for full-color display sandwiches an electrolyte layer so that a pair of electrode structures (a display electrode structure and a counter electrode structure) having at least a transparent electrode formed on a support substrate face each other. A metal oxide porous electrode carrying an electrochromic compound is formed on at least the display electrode structure of the transparent electrodes constituting the pair of electrode structures. The color development can be performed by controlling the voltage applied between the electrode structures, and (a) a metal oxide porous electrode carrying the electrochromic compound represented by the above formula (1) is formed. An electrochromic element structure capable of reversible magenta color reversal, and (b) an elect capable of reversible yellow color development. A chromic element structure, (c) an electrochromic element structure capable of performing reversible color development of cyan, is formed by stacking three element structures, and controls the voltage applied to each electrochromic element structure By doing so, a full color image can be displayed as a whole.

  FIG. 3 is a cross-sectional view illustrating a schematic configuration of an example of an electrochromic device capable of performing color display according to an embodiment of the present invention.

  Each of the electrochromic element structures 10A, 10B, and 10C shown in FIG. 3 has the same configuration as the electrochromic device shown in FIG.

  The electrochromic device capable of performing color display shown in FIG. 3 includes: (a) a first support substrate (support substrates 1a, 1b, 1c), and a first transparent substrate formed on the first support substrate. Display electrode structure 11a including electrodes (transparent electrodes 2a, 2b, 2c) and a first metal oxide porous electrode (porous electrodes 4a, 4b, 4c) formed on the first transparent electrode 11b, 11c, (b) a second support substrate (support substrates 6a, 6b, 6c), a second transparent electrode (transparent electrodes 7a, 7b, 7c) formed on the second support substrate, And counter electrode structures 12a, 12b, 12c including a second metal oxide porous electrode (porous electrodes 8a, 8, 8c) formed on the second transparent electrode, and (c) a display electrode Structures 11a, 11b, 11 and counter electrode structures 12a, 1 b, and includes an electrolyte layer 5a which is sandwiched, 5b, and 5c by 12c.

  The first transparent electrode (2a, 2b, 2c) and the second transparent electrode (7a, 7b, 7c) are arranged to face each other through the electrolyte layers 5a, 5b, 5c, and an electrochromic compound (organic EC The dyes 3a, 3b, 3c) are carried on the first metal oxide porous electrodes (4a, 4b, 4c) to form the electrochromic element structures 10A, 10B, 10C.

  The electrochromic element structures 10A, 10B, and 10C are stacked, and the first transparent electrodes (2a, 2b, and 2c) and the second transparent electrodes (7a, 10c) of the electrochromic element structures 10A, 10B, and 10C are stacked. By controlling the voltage applied between 7b and 7c), reversible color erasing with the electrochromic compound can be performed.

  The electrochromic compounds (organic EC dyes 3a, 3b, 3c) supported on the first metal oxide porous electrodes (4a, 4b, 4c) of the electrochromic element structures 10A, 10B, 10C, respectively, If the viewing direction is above 3, magenta, yellow, and cyan are assumed.

  In FIG. 3, porous electrodes 4a, 8a; 4b, 8b; 4c, 8c are formed on any of the opposing transparent electrodes 2a, 7a; 2b, 7b; 2c, 7c; Is not limited to this configuration, and a porous electrode may be formed only on one electrode as necessary, and the electrochromic compounds 3a, 3b, and 3c may be supported on the porous electrode.

  The electrochromic compound used in the electrochromic device shown in FIG. 1 and FIG. 3 is in a decolored state without absorption in the visible light region when no voltage is applied, and visible when a voltage is applied. A compound that absorbs in the light region and becomes a colored state. Conversely, when a voltage is applied, the compound is in a decolored state with no absorption in the visible light region, and absorbs in the visible light region when no voltage is applied. It may be any of a compound that exhibits a colored state or a compound that can be in a multi-colored state that varies in color depending on the magnitude of applied voltage, and can be appropriately selected according to the purpose. A full color image can be displayed by controlling the voltage applied to each of the bodies 10A, 10B, and 10C.

  In addition, in the electrochromic device shown in FIGS. 1 and 3, in order to perform active matrix driving, a first transparent electrode (transparent electrodes 2, 2a) is provided on a first support substrate (support substrates 1, 1a, 1b, 1c). 2b, 2c) are formed as fractions, that is, a plurality of fractions that are mutually independent so as to correspond to each pixel are formed in a matrix, and the first metal oxide porous is formed on each fraction. A thin film transistor (porous electrode 4, 4a, 4b, 4c) is formed, and a thin film transistor (TFT) connected by a gate line and a source line is formed on the first transparent electrode corresponding to each fraction. It can also be set as the apparatus which has the structure to do. According to this apparatus, by controlling the voltage applied to the thin film transistor, it is possible to control the color development / decoloration in the fraction corresponding to each pixel of the electrochromic element structures 10A, 10B, and 10C.

  Furthermore, in the electrochromic device shown in FIG. 1 having the above-described configuration, the transparent electrode 2 is fractionated and formed to correspond to the pixels, that is, in order to perform active matrix driving, the first corresponding to cyan, magenta, and yellow. A matrix-like transparent electrode 2 composed of a plurality of fractions composed of a first fraction, a second fraction, and a third fraction is formed on a support substrate 1, and a porous electrode 4 is formed on the first, second, and third fractions. And forming an electrochromic compound capable of developing cyan, magenta, and yellow on the porous electrode 4 formed on the first, second, and third fractions, respectively. Corresponding to the third fraction, a device having a configuration in which a thin film transistor connected by a gate line and a source line is formed and arranged on the transparent electrode 2 can be provided. According to this apparatus, by controlling the voltage applied to the thin film transistor, it is possible to control the color development / decoloration in the first, second, and third fractions corresponding to the respective pixels.

  Next, specific examples of the electrochromic device of the present invention and a comparative example thereof will be described.

Example (Synthesis of electrochromic compound intermediate (compound represented by the above formula (2)))
Under an argon atmosphere, 2.4 g (6 mmol) of 2,3,4,5-tetrabromothiophene, 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine 2 .71 g (13.2 mmol), Pd (PPh ₃ ) ₄ 18 mg (0.156 mmol), Na ₂ CO ₃ 3.81 g (36 mmol), 1,4-dioxane 50 mL, and water 36 mL were refluxed at 110 ° C. for 48 hours. After cooling, ethyl acetate and water were added and stirred well, and the organic layer and ethyl acetate from which the aqueous layer was newly extracted were combined. This was washed with brine and dried to obtain a solid. This solid was recrystallized with a THF / hexane mixed solvent to obtain 2.0 g of light yellow crystals (compound represented by the above formula (7)) (yield = 85%).
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 8.77-8.75 (d, 4H), 7.73-7.72 (d, 4H).

1.98 g (5 mmol) of the compound represented by the above formula (7) thus obtained was dissolved in 150 mL of dry THF. To this, 2 mL (5.2 mmol) of a 2.6M hexane solution of n-butyllithium was dropped at −78 ° C. in an argon atmosphere, and the mixture was allowed to react for 30 minutes. Subsequently, 1.58 g (5 mmol) of N-fluorobenzenesulfonimide was added as a fluorinating agent. In the same way,
1 mL of n-butyllithium solution, 0.79 g of N-fluorobenzenesulfonimide,
n-butyllithium solution 0.5 mL, N-fluorobenzenesulfonimide 0.39 g,
0.25 mL of n-butyllithium solution and 0.20 g of N-fluorobenzenesulfonimide were reacted.

That is, the same process was repeated 4 times in total. The reaction solution was returned to room temperature, diluted hydrochloric acid and ethyl acetate were added, and the organic layer was collected, washed with brine and dried. Purification by silica gel column chromatography gave 0.9 g (yield = 65%) of pale pink crystals (intermediate compound represented by the above formula (2)). The corresponding stoichiometric yield is 93.75%.
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 8.72 (d, 4H, J = 5.1 Hz), δ 7.64 (d, 4H, J = 5.4 Hz),
19F-NMR (400 MHz, DMSO-d6): δ 31.66 (s, 2F) vs hexafluorobenzene.

(Synthesis of electrochromic compound formula (1))
The electrochromic compound represented by the above formulas (10) to (15) is obtained by using a known method (Patent Document 6, Non-patent) using the intermediate compound represented by the above formula (2) obtained by the above method. Reference 1)).

(Preparation of display electrode structure)
On a support substrate 1 made of glass having a thickness of 1.1 mm, a 15 Ω / □ FTO film (transparent electrode 2) was formed in a plane. Next, polyethylene glycol was dissolved at a rate of 5% by weight in a slurry in which 15% by weight of titanium oxide having a primary particle diameter of 20 nm was dispersed in an aqueous hydrochloric acid solution having a pH of about 1.0 to prepare a coating material. This paint was applied on the FTO film by a squeegee method. Next, an FTO substrate on which a titanium oxide porous electrode 4 having a film thickness of 5 μm is formed by performing a drying treatment at 80 ° C. for 15 minutes on a hot plate and further sintering at 500 ° C. for 1 hour in an electric furnace. Obtained.

(Support of electrochromic compound on porous electrode)
The FTO substrate on which the porous electrode 4 made of the titanium oxide film was formed was immersed in a 5 mM aqueous solution of a predetermined electrochromic compound produced as described above for 24 hours, and the electrochromic compound was supported on the titanium oxide electrode. . Thereafter, washing treatment and drying treatment were performed with an ethanol solution.

(Preparation of counter electrode structure)
On a support substrate 6 made of glass having a thickness of 1.1 mm, a 15Ω / □ FTO film (transparent electrode 7) was formed in a plane. Next, polyethylene glycol was dissolved at a ratio of 5% by weight in a slurry in which 20% by weight of antimony-doped tin oxide having a primary particle diameter of 20 nm was dispersed in an acidic aqueous solution to prepare a paint. This paint was applied on the FTO film by a squeegee method. Next, the FTO was dried on a hot plate at 80 ° C. for 15 minutes, further sintered in an electric furnace at 500 ° C. for 1 hour, and an antimony-doped tin oxide porous electrode 8 having a film thickness of 12 μm was formed. A substrate was obtained.

(Preparation of solution for electrolyte layer)
As the electrolyte layer 5 forming solution, a solution obtained by dissolving 0.1 mol / L of lithium perchlorate in gamma-butyrolaclone, dehydrating and degassing was applied.

(Lamination of electrode structure)
Adhering the display electrode structure (substrate with a dye-carrying titanium oxide porous electrode) and counter electrode structure (substrate with an antimony-doped tin oxide porous electrode) produced as described above to a thermoplastic film having a thickness of 50 μm The adhesive was used and bonded at 90 ° C. by heat fusion. At this time, an injection port was formed in a part so that the electrolyte solution could be injected by a process described later. The distance between the display and the transparent electrode of the counter electrode structure was 50 μm.

(Injection of electrolyte solution)
The electrolyte was vacuum injected from the inlet. Thereafter, the injection port was sealed with an epoxy-based thermosetting resin, thereby completing an electrochromic device including electrode structures facing each other with the electrolyte layer sandwiched therebetween.

(Evaluation example 1 of electrochromic device)
As the electrochromic compound, the compound represented by the above formula (11) was applied.

  FIG. 4 is a diagram showing a visible absorption spectrum at the time of color development of the electrochromic device in the example (evaluation example 1) according to the embodiment of the present invention. In FIG. 4, the vertical axis represents absorbance (arbitrary unit), and the horizontal axis represents wavelength (nm).

  The electrochromic device in the example (evaluation example 1) was almost colorless in a normal state because the ultraviolet absorption edge of the compound represented by the formula (11) was 400 nm or less. When a voltage of -1.5 V was applied between the display and the transparent electrode of the counter electrode structure of this device, the color immediately became vivid magenta. The response speed of the color display change due to color generation / decoloration was about 140 ms, which was a sufficiently good speed for practical use. Furthermore, when 0.5 V was applied between the display and the counter electrode structure, it became transparent again immediately. The response speed of the color display change due to color generation / erasure was about 90 ms.

  Further, -1.5 V and 0.5 V were alternately applied 1 million times at 1 Hz between the display of the electrochromic device and the transparent electrode of the counter electrode structure in this example (Evaluation Example 1). Even after voltage application was repeated 10,000 times, the shape of the visible absorption spectrum showed almost no change from the initial state, and it was confirmed that it had practically sufficiently excellent durability.

(Evaluation example 2 of electrochromic device)
Instead of the compound represented by the above formula (11) in Evaluation Example 1, the compound represented by the above formula (13) was applied.

  FIG. 5 is a diagram showing a visible absorption spectrum at the time of color development of the electrochromic device in the example (evaluation example 2) according to the embodiment of the present invention. In FIG. 5, the vertical axis represents absorbance (arbitrary unit), and the horizontal axis represents wavelength (nm).

The electrochromic device in the example (evaluation example 2) was almost colorless in a normal state because the ultraviolet absorption edge of the compound represented by the above formula (13) was 400 nm or less. When this apparatus was evaluated in the same manner as in Example (Evaluation Example 1), vivid magenta color development was confirmed, and the response speeds were 150 ms and 90 ms, respectively. Even after 1 million repetitions of color development and decoloration, the shape of the visible absorption spectrum hardly changed from the initial state, and the initial state and characteristics did not change.
Comparative Example (Comparative Example 1 of Electrochromic Device)
Instead of the compound represented by the above formula (11) in Evaluation Example 1, a compound represented by the following formula (16) was applied.

  FIG. 6 is a diagram showing a visible absorption spectrum at the time of color development of the electrochromic device in Comparative Example 1 according to the embodiment of the present invention. In FIG. 6, the vertical axis indicates absorbance (arbitrary unit), and the horizontal axis indicates wavelength (nm).

  In the electrochromic device in Comparative Example 1, since the ultraviolet absorption edge of the compound represented by the following formula (16) is around 420 nm, slightly yellow coloring was observed in a normal state. When evaluated in the same manner as in the electrochromic device in the examples (Evaluation Example 1 and Evaluation Example 2), the color developed when the voltage was applied was vivid, and the response speed and the repeated durability were also good as in the examples.

…（１６）

... (16)

(Comparative example 2 of electrochromic device)
Instead of the compound represented by the above formula (11) in Evaluation Example 1, a compound represented by the following formula (17) was applied.

  FIG. 7 is a diagram showing a visible absorption spectrum at the time of color development of the electrochromic device in Comparative Example 2 according to the embodiment of the present invention. In FIG. 7, the vertical axis represents absorbance (arbitrary unit), and the horizontal axis represents wavelength (nm).

  In the electrochromic device in Comparative Example 2, since the ultraviolet absorption edge of the compound represented by the following formula (17) is around 420 nm, slightly yellow coloring was observed in a normal state. When evaluated in the same manner as in the electrochromic device in the examples (Evaluation Example 1 and Evaluation Example 2), the color developed when the voltage was applied was vivid, and the response speed and the repeated durability were also good as in the examples.

…（１７）

... (17)

(Comparative example 3 of electrochromic device)
Instead of the compound represented by the above formula (11) in the evaluation example 1, a compound represented by the following formula (18) was applied.

  FIG. 8 is a diagram showing a visible absorption spectrum at the time of color development of the electrochromic device in Comparative Example 3 according to the embodiment of the present invention. In FIG. 8, the vertical axis represents absorbance (arbitrary unit), and the horizontal axis represents wavelength (nm).

  In the electrochromic device in Comparative Example 3, since the ultraviolet absorption edge of the compound represented by the following formula (18) is around 420 nm, slightly yellow coloring was observed in a normal state. When evaluated in the same manner as in the electrochromic device in the examples (Evaluation Example 1 and Evaluation Example 2), the color developed when the voltage was applied was vivid, and the response speed and the repeated durability were also good as in the examples.

…（１８）

... (18)

(Comparative example 4 of electrochromic device)
Instead of the compound represented by the formula (11) in the evaluation example 1, a compound represented by the following formula (19) was applied.

  FIG. 9 is a diagram showing a visible absorption spectrum at the time of color development of the electrochromic device in Comparative Example 4 according to the embodiment of the present invention. In FIG. 9, the vertical axis represents absorbance (arbitrary unit), and the horizontal axis represents wavelength (nm).

  In the electrochromic device in Comparative Example 4, since the ultraviolet absorption edge of the compound represented by the following formula (19) was around 420 nm, slightly yellow coloring was observed in a normal state. When evaluated in the same manner as in the electrochromic device in the examples (Evaluation Example 1 and Evaluation Example 2), the color developed when the voltage was applied was vivid, and the response speed and the repeated durability were also good as in the examples.

…（１９）

... (19)

(Comparative Example 5 of electrochromic device)
Instead of the compound represented by the above formula (11) in the evaluation example 1, a compound represented by the following formula (20) was applied.

  FIG. 10 is a diagram showing a visible absorption spectrum at the time of color development of the electrochromic device in Comparative Example 5 according to the embodiment of the present invention. In FIG. 10, the vertical axis represents absorbance (arbitrary unit), and the horizontal axis represents wavelength (nm).

  The electrochromic device in Comparative Example 5 was almost colorless in a normal state because the ultraviolet absorption edge of the compound represented by the formula (20) was 400 nm or less. When evaluated in the same manner as the electrochromic device in the examples (Evaluation Example 1 and Evaluation Example 2), the response speed and the repeated durability were good as in the example, but the color development during voltage application was broad, It was purple. As a magenta coloring dye, color purity is inferior.

…（２０）

... (20)

  The compound represented by the above formula (16) can be regarded as a 2,5-bis (4-pyridyl) furan derivative, and the above formulas (17), (18), (19), (20) Can be considered to be 2,5-bis (4-pyridyl) thiophene derivatives.

  As is clear from the above results, according to the method of the present invention, it is extremely excellent in response, colorless at the time of decoloring, and sharply developed in color, and stably and reversibly displays the color. A magenta-colored electrochromic compound and an electrochromic device capable of producing the same were obtained.

  The electrochromic device according to the present invention can be used for display elements, display plates, antiglare mirrors, dimming elements, optical switches, optical memories and the like used for various applications.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to the above-mentioned embodiment, Various deformation | transformation based on the technical idea of this invention is possible.

  For example, the organic electrochromic compound is not limited to those shown in the above (10) to (15), and can be arbitrarily changed as necessary, and can be used in the chromic device shown in FIGS. .

  As described above, according to the present invention, an electrochromic compound useful for improving the performance of an electrochromic device and an intermediate compound used for the synthesis thereof can be provided.

It is sectional drawing explaining schematic structure of an example of the electrochromic apparatus by embodiment of this invention. It is a figure explaining the manufacturing process of an intermediate body and an electrochromic compound same as the above. It is sectional drawing explaining schematic structure of an example of the electrochromic apparatus which can perform a color display same as the above. It is a figure which shows the visible absorption spectrum at the time of color development of the electrochromic apparatus in an Example (evaluation example 1) same as the above. It is a figure which shows the visible absorption spectrum at the time of color development of the electrochromic apparatus in an Example (evaluation example 1) same as the above. It is a figure which shows the visible absorption spectrum at the time of color development of the electrochromic apparatus in a comparative example same as the above. It is a figure which shows the visible absorption spectrum at the time of color development of the electrochromic apparatus in a comparative example same as the above. It is a figure which shows the visible absorption spectrum at the time of color development of the electrochromic apparatus in a comparative example same as the above. It is a figure which shows the visible absorption spectrum at the time of color development of the electrochromic apparatus in a comparative example same as the above. It is a figure which shows the visible absorption spectrum at the time of color development of the electrochromic apparatus in a comparative example same as the above.

Explanation of symbols

1, 1a, 1b, 1c, 6, 6a, 6b, 6c ... support substrate,
2, 2a, 2b, 2c, 7, 7a, 7b, 7c ... transparent electrodes,
3, 3a, 3b, 3c ... Organic EC dye,
4, 4a, 4b, 4c, 8, 8a, 8, 8c ... porous electrodes,
5, 5a, 5b, 5c ... electrolyte layer,
10A, 10B, 10C ... electrochromic element structure,
10 ... Electrochromic device,
11, 11a, 11b, 11c ... display electrode structure,
12, 12a, 12b, 12c ... counter electrode structure

Claims (9)

An electrochromic compound comprising a compound represented by the formula (1) or a derivative in which a hydrogen atom bonded to a carbon atom of the C ₅ N ring is substituted with another atom or an atomic group.

... (1)
However, in the above formula (1), a and b are integers satisfying a × b = 2, Y ^b− represents a b-valent anion, and A ₁ and A ₂ are optionally substituted aliphatic carbonizations. It is a hydrogen group, B ₁ and B ₂ are an optionally substituted aliphatic hydrocarbon group or an aromatic hydrocarbon group, and at least one of B ₁ and B ₂ is supported on the porous electrode. It has a functional group. 2,5-bis (4-pyridyl) -3,4-difluorothiophene represented by the formula (2), or a hydrogen atom bonded to a carbon atom of the C ₅ N ring is substituted by another atom or atomic group. An intermediate compound comprising a derivative.

... (2)   The intermediate compound according to claim 2 for synthesizing the electrochromic compound according to claim 1.   The intermediate compound according to claim 2, comprising a step of repeating lithiation of 2,5-bis (4-pyridyl) -3,4-dibromothiophene and then introducing a fluorine group by a fluorinating agent a plurality of times. Manufacturing method.   The method for producing an intermediate compound according to claim 4 for synthesizing the electrochromic compound according to claim 1. The intermediate compound according to claim 2 is a halide B ₁ -A ₁ -Y, B ₂ -A ₂ -Y (where Y represents an anion, and A ₁ and A ₂ may be substituted) A good aliphatic hydrocarbon group, B ₁ and B ₂ are an optionally substituted aliphatic hydrocarbon group or an aromatic hydrocarbon group, and at least one of B ₁ and B ₂ is a porous electrode 2. The method for producing an electrochromic compound according to claim 1, further comprising a step of reacting with a functional group for supporting the electrochromic compound.   An optical device using the electrochromic compound according to claim 1. A display electrode structure including a first support substrate, a first transparent electrode formed on the first support substrate, and a metal oxide porous electrode formed on the first transparent electrode;
A counter electrode structure including a second support substrate, a second transparent electrode formed on the second support substrate;
An electrolyte layer sandwiched between the display electrode structure and the counter electrode structure, wherein the first transparent electrode and the second transparent electrode are arranged to face each other, and the electrochromic compound is the metal An electrochromic element structure that is supported on an oxide porous electrode and that performs reversible color development by an electrochromic compound by controlling a voltage applied between the first transparent electrode and the second transparent electrode. The electrochromic compound according to claim 1 is used as the electrochromic compound, and the electrochromic device is configured as an electrochromic device that performs reversible color erasing of magenta by controlling the application of the voltage. 8. The optical device according to 7.   A second electrochromic element structure in which the electrochromic element structure is a first electrochromic element structure, and a compound that reversibly develops yellow as the electrochromic compound in the electrochromic element structure is used. And a third electrochromic element structure in which a compound capable of reversibly developing cyan is used as the electrochromic compound in the electrochromic element structure, and the first, second, and third The optical device according to claim 8, wherein the electrochromic element structures are stacked to display a full color image.

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