JP2010085568A - Electrochemical device and polymeric material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrochemical device having high repeating durability, more specifically, an electro-chromic display element, and a metal complex polymeric material. <P>SOLUTION: In the electrochemical device containing the polymeric material containing metal atoms and ligands capable of being coupled with two or more metal atoms between counter electrodes, at least one of the ligands contains 5-member heterocycle single rings. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel electrochemical device, more specifically, an electrochemical device for performing an electrochromic display element, and a polymer material used therefor.

  In recent years, with the increase in the operating speed of personal computers, the spread of network infrastructure, the increase in capacity and price of data storage, etc., information such as documents and images conventionally provided in printed materials such as paper has become easier. Opportunities for obtaining and browsing electronic information are increasing.

  As a means for browsing such electronic information, conventional liquid crystal displays and CRTs (CRTs), and in recent years, light-emitting displays such as organic electroluminescence displays are mainly used. In particular, when electronic information is document information. It is necessary to keep a close eye on this browsing means for a relatively long time, and these actions are not necessarily human-friendly means. Generally, as a disadvantage of the light-emitting display, flickering causes eye fatigue, inconvenient to carry, and reading There are known problems such as the posture being restricted and the need to adjust the line of sight to the still screen, and the increased power consumption when read for a long time.

  As a display means to compensate for these drawbacks, a reflective display having a so-called memory property that uses outside light and does not consume power for image retention is known. However, it is sufficient for the following reasons. It is hard to say that it has performance.

  For example, a method using a polarizing plate such as a reflective liquid crystal has a low reflectance of about 40% and is difficult to display white, and many of the manufacturing methods used for producing the constituent members are not easy. In addition, the polymer dispersed liquid crystal requires a high voltage and utilizes the difference in refractive index between organic substances, so that the resulting image has insufficient contrast. In addition, the polymer network type liquid crystal has problems such as a high voltage and a complicated TFT circuit required to improve the memory performance. In addition, a display element based on electrophoresis requires a high voltage of 10 V or more, and there is a concern about durability due to electrophoretic particle aggregation. As a method for performing color display using these methods, a method using a color filter is known. In principle, a bright white display cannot be obtained due to the coloring of the color filter.

  In addition, as a method capable of multi-color display that can be driven at a low voltage, an electrochromic (hereinafter abbreviated as EC) display element, an EC method, and an electrodeposition method (hereinafter referred to as ED) using metal or metal salt dissolution precipitation. An electrochemical method such as a combination of the methods is abbreviated. These systems have an advantage that they can be formed with a simple element configuration and can be driven at a low voltage of 3 V or less. The ED method has advantages such as excellent black and white contrast and black quality, and various methods have been disclosed. As such EC materials, polymer materials using bisterpyridine and various metals are used. An EC element is known (Patent Document 1). Such a coordination polymer material has a problem that the repeated durability of the device has not reached the practical level.

In addition to the compounds having pyridine as a coordination atom group as shown in Patent Document 1 as a ligand for forming such a coordination polymer material, there are also compounds using a hetero-fused ring structure as a coordination atom group. Known (Patent Document 2). However, even when a coordination polymer material using a compound having a hetero-fused ring structure is used for an EC display element, there is a problem that the repeated durability of the element has not reached a practical level.
Special table 2007-112957 JP 2008-66542 A

  The present invention has been made in view of the above problems, and an object thereof is to provide an electrochemical device having high repetition durability, more specifically, an electrochromic display element and a metal complex polymer material.

  The above problem has been solved by the following configuration.

  1. An electrochemical device comprising a polymeric material containing a metal atom and a ligand capable of binding to two or more metal atoms between opposing electrodes, wherein at least one of the ligands is a five-membered An electrochemical device comprising a heterocyclic monocycle.

  2. 2. The electrochemical device according to 1 above, wherein at least one of the ligands can bind to three or more metal atoms.

3. At least one of the ligands includes —SH, —COOH, —P═O (OH) ₂ , —OP═O (OH) _2, and —Si (OR) ₃ (R is an alkyl group) in the molecule. 3. The electrochemical device according to 1 or 2 above, which has at least one group selected from

  4). The electrochemical device according to any one of 1 to 3 above, wherein at least one of the ligands has a negative charge when bonded to a metal.

  5. 5. The electrochemical device according to any one of 1 to 4, wherein at least one of the ligands has a metal complex in its structure.

  6). At least 1 sort (s) of the said ligand is a compound represented by following General formula (1), The electrochemical device as described in any one of said 1-5 characterized by the above-mentioned.

  In the formula, A is a nitrogen, oxygen, sulfur, phosphorus or carbon atom, which is a part of a ring component and together with other components forms a 5-membered or 6-membered ring. W represents a substituent or a linking group containing a coordination site, p is an integer of 1 to 4, and when p is 2 or more, W may be different from each other. D represents a coordination atom or a coordination atom group, L represents a linking group between a ring containing A and D, m is an integer of 0 to 4, n is an integer of 1 to 4, p , M and n satisfy the relationship of p + m + n ≦ 4 when the ring containing A is a 5-membered ring, and p + m + n ≦ 5 when the ring is a 6-membered ring. However, at least one of the ring containing A and D is a 5-membered heterocyclic monocycle.

  7). A polymer material containing a metal atom and two or more ligands capable of binding to the metal atom, wherein at least one of the ligands contains a 5-membered heterocyclic monocycle, High polymer material.

  8). 8. The polymer material as described in 7 above, wherein at least one of the ligands can bind to three or more metal atoms.

9. At least one of the ligands includes —SH, —COOH, —P═O (OH) ₂ , —OP═O (OH) ₂ and —Si (OR) ₃ (R is alkyl 9. The polymer material as described in 7 or 8 above, which has at least one group selected from

  10. 10. The polymer material according to any one of 7 to 9, wherein at least one of the ligands has a negative charge when bonded to a metal.

  11. 11. The polymer material according to any one of 7 to 10, wherein at least one of the ligands has a metal complex in its structure.

  12 The polymer material according to any one of 7 to 11, wherein at least one of the ligands is a compound represented by the following general formula (1).

  In the formula, A is a nitrogen, oxygen, sulfur, phosphorus or carbon atom, which is a part of a ring component and together with other components forms a 5-membered or 6-membered ring. W represents a substituent or a linking group containing a coordination site, p is an integer of 1 to 4, and when p is 2 or more, W may be different from each other. D represents a coordination atom or a coordination atom group, L represents a linking group between a ring containing A and D, m is an integer of 0 to 4, n is an integer of 1 to 4, p , M and n satisfy the relationship of p + m + n ≦ 4 when the ring containing A is a 5-membered ring, and p + m + n ≦ 5 when the ring is a 6-membered ring. However, at least one of the ring containing A and D is a 5-membered heterocyclic monocycle.

  According to the present invention, an electrochemical device excellent in repeated durability, more specifically, an electrochromic display element and a novel metal complex polymer material can be provided.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the inventors of the present invention contain a polymer material containing a metal atom and a ligand capable of binding to two or more metal atoms between or on the electrodes. The present inventors have found that a display element having high durability can be realized by a display element characterized in that at least one of the ligands contains a 5-membered heterocyclic monocycle.

  Details of the present invention will be described below.

  The electrochemical device according to the present invention represents a device that performs current driving or voltage driving, such as an electronic paper device, a field effect transistor, a substrate component wiring, and a liquid crystal display device, and more specifically an electrochromic electronic paper display device.

  The polymer material for electrochemical devices of the present invention is a polymer material containing a metal atom and a ligand capable of binding to two or more metal atoms, and at least one of the ligands is 5 It is characterized by including a membered monocyclic ring. The metal atom of the present invention is not particularly limited as long as it can form a bond with each ligand, but is preferably a metal element included in Groups 1 to 14 of the periodic table, and also from the 4th to 6th periods. The upper metal element is preferable, and the fourth period or fifth period metal element is more preferable from the viewpoint of cost and the like. Among these metal elements, specifically, Mn, Fe, Co, Ni, Cu, Zn, Ru, and Os are preferable, more preferably Mn, Fe, Co, and Ru, and further Mn, Fe, More preferably, it is selected from Ru. The type of metal atom may be one type or two or more types, and it is preferable to use two or more types of metal atoms for multicolor display.

  The ligand of the present invention is characterized in that it can form a bond with two or more metal atoms. When such a ligand is used, such as ligand-metal-ligand -...- metal-ligand or metal-ligand-metal -...- ligand-metal It is possible to polymerize a metal complex compound by forming a bond between a metal and a ligand, and the polymer material of the present invention represents a metal complex polymer material produced by such a combination of a metal and a ligand. . In the present invention, the coordination position represents how many coordination atoms are bonded to one metal. For example, in the case of a tris (2,2′-bipyridine) ruthenium complex, the coordination of 2,2′-bipyridine is used. The locus is bidentate, and in the case of a nickel-salen complex, the coordination position of salen is tetradentate. In the ligand of the present invention, the coordination position can take any value, but is preferably 2 or more, and more preferably 3 or more. In general, as the number of coordination sites increases, the stability of the metal complex increases. However, since the degree of freedom of the complex molecule decreases, a coordination site of 4 or less is preferable.

  In the polymer material of the present invention, another preferred embodiment is a tridentate or higher structure having a structure different from that of a metal atom, a ligand having one or more kinds of coordination positions, and at least one kind of the coordination position. Including a ligand. By using a combination of multiple ligands having different structures in this way, even when multiple metal species are used, it is possible to selectively bind each metal species, and absorption using electrochromic It is possible to change the spectrum efficiently and selectively. In addition, it is possible to immobilize the polymer material of the present invention on a substrate by giving a kind of ligand an adsorption ability to the substrate. Furthermore, when a ligand having two coordination sites is used, the polymer material of the present invention has a two-dimensional extension, but the coordination site has two ligands and three ligands. By using them in combination, it is possible to introduce a three-dimensional structure, and it is possible to adjust the solubility of the polymer material synthesized in an aqueous solvent or an organic solvent. In the present invention, when plural kinds of ligands are mixed, it is preferable that at least one kind of ligand contains an adsorbing group in terms of immobilization on a substrate or the like, and for the purpose of adjusting the solubility of the polymer material. It is preferable to include a ligand having three or more coordination sites, and a combination of a ligand having an adsorbing group, a ligand having three or more coordination sites, and a bidentate ligand. Is more preferable.

  In the ligand forming the polymer material of the present invention, the coordination atom and the coordination atom group can be arbitrarily selected. Typical coordination atoms include nitrogen atom, oxygen atom, sulfur atom, and phosphorus atom, and coordination atom groups include pyridine ring, quinoline ring, pyrazole ring, triazole ring, pyrazolone ring, thiadizole ring, and benzimidazole ring. And a heterocyclic group such as a carboxyl group, a hydroxyl group, an alkoxy group, a mercapto group, an imino group, an amino group, an ether, a sulfide (thioether), and a phosphine. In the ligand forming the polymer material of the present invention, the ligand may be neutral or may have a negative charge when bonded to a metal, but may have a negative charge. Is more preferable. When the ligand has a negative charge, the coordination atom and the coordination group may have a negative charge, or the structure excluding the coordination atom and the coordination group has a negative charge. Also good. In the latter case, the ligand structure preferably has a sulfonic acid group, a carboxyl group, or a phosphoric acid group. In order to strengthen the bond with the metal, it is preferable that at least one coordination atom and coordination group have a negative charge. Furthermore, at least one ligand forming the polymer material of the present invention needs to contain a 5-membered heterocyclic monocycle. Similarly, in the ligand forming the polymer material of the present invention, at least one ligand is pyrrole, indole, isoindole, pyrazole, indazole, imidazole, triazole, benzotriazole, oxazole, benzoxazole, thiazole, benzoate. It is preferable that any one or more of thiazoles are contained as a coordination atom group. By using such a ligand having a 5-membered heterocyclic ring, it is possible to improve the stability of the polymer material, and it is possible to change the operating voltage when used in an electrochromic device. It becomes.

In the ligand forming the polymer material of the present invention, at least one kind of ligand is —SH, —COOH, —P—O (OH) ₂ , —OP═O (OH) ₂ and —Si in the molecule. It is preferable to have at least one group selected from (OR) ₃ (R represents an alkyl group). Such a group acts as an adsorbing group and can immobilize the polymer material of the present invention on the substrate as described above. It is also possible to adjust the solubility of the polymer material of the present invention.

Further, the polymer material of the present invention may have a counter ion (counter ion) in order to neutralize charges generated by a combination of various ligands and metals. Such counter ions are not particularly limited, but halogen ions, nitrate ions, sulfate ions, acetate ions, perchlorate ions, toluenesulfonate ions, methanesulfonate ions, trifluoromethanesulfonate ions, tetrafluoroborate acids. In addition to ions, tetraphenylborate ions, hexafluorophosphate ions, thiocyanate ions, etc., (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , and (C ₂ F ₅ SO _{2) 3} C ^- imide salts such can also be suitably used. In the polymer material of the present invention, a plurality of these counter ions can be used simultaneously, and the solubility of the polymer material in water or an organic solvent can be adjusted by adjusting various counter ions.

  In the ligand forming the polymer material of the present invention, it is also preferable to use a mixture of a ligand capable of forming a metal complex or a ligand containing a metal complex in the structure. Specific examples of the structure of the metal complex contained in the structure include polydentate chelate complexes such as salen, cyclic complexes such as porphyrin and phthalocyanine, and organometallic complexes such as ferrocene and titanocene, and more preferably organic complexes. More preferably, the metal complex is ferrocene. Use of such a ligand is preferable because the charge transfer rate in the polymer material of the present invention can be adjusted, and it can also be used as an electron source and a hole source. Furthermore, it is preferable because the polymer material of the present invention is effective in improving the heat resistance.

  One preferred embodiment of the ligand forming the polymer material of the present invention is to have a structure represented by the following general formula (1).

  In the formula, A represents a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom or a carbon atom, forms a 5-membered ring or a 6-membered ring with other components, and forms a bond with a metal atom. The ring formed at this time may be an aromatic ring or a non-aromatic ring, but is preferably an aromatic ring, and more preferably a heteroaromatic ring.

  Examples of the ring containing A include heterocyclic rings such as a pyridine ring, a quinoline ring, a pyrazole ring, a triazole ring, a pyrazolone ring, a thiadizole ring, and a benzimidazole ring.

  W represents a substituent or a linking group containing a coordination site. Specific examples of the substituent include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc. ), A cycloalkyl group (for example, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group (for example, vinyl group, allyl group, butenyl group, octenyl group, etc.), cycloalkenyl group (for example, 2-cyclopentene-1 -Yl group, 2-cyclohexen-1-yl group, etc.), alkynyl group (eg, propargyl group, ethynyl group, trimethylsilylethynyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p-tolyl group, m- Chlorophenyl group, o-hexadecanoylaminophenyl group, etc.), compound A cyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, morpholino group, etc. ), A heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group, pyridyloxy group, thiazolyloxy group, oxazolyloxy group, imidazolyloxy group, etc.), halogen atom (for example, , Chlorine atom, bromine atom, iodine atom, fluorine atom, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, tert-butoxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group) Etc.), cycloal Xy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (for example, phenoxy group, 2-naphthyloxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexyl) Thio group etc.), arylthio group (eg phenylthio group, 1-naphthylthio group etc.), heterocyclic thio group (eg pyridylthio group, thiazolylthio group, oxazolylthio group, imidazolylthio group, furylthio group, pyrrolylthio group etc.), a Lucoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), Sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthyl) Aminosulfonyl group, 2-pyridylaminosulfonyl group, morpholinosulfonyl group, pyrrolidinosulfonyl group, etc.), ureido group (for example, methyl group) Id group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group) Propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, formyloxy group, Acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group, ethylcarbonyloxy group, butylcarbonyloxy Octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), acylamino group (for example, acetylamino group, benzoylamino group, formylamino group, pivaloylamino group, lauroylamino group, 3,4,5-tri-) n-octyloxyphenylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, morpholinocarbo Nyl group, piperazinocarbonyl group, etc.), alkanesulfinyl group or arylsulfinyl group (for example, methanesulfinyl group, ethanesulfinyl group, butanesulfinyl group, cyclohexanesulfinyl group, 2-ethylhexanesulfinyl group, dodecanesulfinyl group, phenylsulfinyl group) Group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkanesulfonyl group or arylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, cyclohexanesulfonyl group, 2-ethylhexanesulfonyl group, dodecanesulfonyl group) , Phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, methylamino group, ethylamino group, dimethyl group) Ruamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, N-methylanilino group, diphenylamino group, naphthylamino group, 2-pyridylamino group, etc.), silyloxy group (for example, trimethylsilyl) Oxy group, tert-butyldimethylsilyloxy group, etc.), aminocarbonyloxy group (for example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n) -Octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group, etc.), alkoxycarbonyloxy group (for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n-octyl group) Carbonyloxy group etc.), aryloxycarbonyloxy group (eg phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group etc.), alkoxycarbonylamino group (eg methoxycarbonyl) Amino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group, etc.), aryloxycarbonylamino group (for example, phenoxycarbonylamino group, p-chloro) Phenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group, etc.), sulfamoylamino group (for example, sulfamoylamino group, N, N-dimethylaminosulfuric group) Phonylamino group, Nn-octylaminosulfonylamino group, etc.), mercapto group, arylazo group (eg, phenylazo group, naphthylazo group, p-chlorophenylazo group, etc.), heterocyclic azo group (eg, pyridylazo group, thiazolylazo group, Oxazolylazo group, imidazolylazo group, furylazo group, pyrrolylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group, etc.), imino group (for example, N-succinimido-1-yl group, N-phthalimide- 1-yl group), phosphino group (for example, dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group, etc.), phosphinyl group (for example, phosphinyl group, dioctyloxyphosphinyl group, diethoxyphosphinyl group) Group), phosphinyloxy group (for example, , Diphenoxyphosphinyloxy group, dioctyloxyphosphinyloxy group, etc.), phosphinylamino group (eg, dimethoxyphosphinylamino group, dimethylaminophosphinylamino group, etc.), silyl group (eg, trimethylsilyl) Group, tert-butyldimethylsilyl group, phenyldimethylsilyl group, etc.), cyano group, nitro group, hydroxyl group, sulfo group, carboxyl group and the like. p is an integer of 1 to 4, and when p is 2 or more, the linking groups containing a plurality of substituents or coordination sites represented by W may be different or the same. .

  D represents a coordination atom or a coordination atom group. Typical coordination atoms include nitrogen atom, oxygen atom, sulfur atom and phosphorus atom. Coordination atom groups include pyridine ring, quinoline ring and furan ring. , Heterocyclic rings such as thiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxazole ring, thiazole ring, triazole ring, pyrazolone ring, thiadiazole ring, benzimidazole ring, carboxyl group, hydroxyl group, alkoxy group, mercapto group, imino group, An amino group, ether, sulfide (thioether), phosphine, etc. are mentioned.

  L represents a ring containing A and a linking group of D and can be freely selected as long as it functions as a linking group, and may have a substituent at any position, and a part of It may be substituted with an atom. The linking group is preferably a hydrocarbon linking group, more preferably a linear, branched or cyclic alkylene group or arylene group, still more preferably a linear alkylene group, and a methylene group. Is more preferable.

  m is an integer of 0 to 4, n is an integer of 1 to 4, l, m and n are 1 + m + n ≦ 4 when the ring is a 5-membered ring, and when the ring is a 6-membered ring Satisfies the relationship of l + m + n ≦ 5. However, at least one of the ring containing A and D is a 5-membered heterocyclic monocycle.

  Although the specific example of the ligand used for formation of the polymeric material of this invention below and containing a 5-membered heterocyclic monocycle is illustrated, this invention is not limited to these.

  Moreover, although it is a ligand used for formation of the polymeric material of this invention, Comprising: The specific example of the ligand represented by the said General formula (1) is illustrated, this invention is not limited to these.

  Moreover, although the other specific example of the ligand used for formation of the polymeric material of this invention is illustrated, this invention is not limited to these.

The ligands according to the present invention are disclosed in Dalton Trans. 2003, 2069-2079 and Chem. Lett. 1999, 1129-1130, and well-known methods such as Suzuki coupling and Still coupling.

  The polymer material of the present invention can be synthesized by mixing the ligand and metal salt in a solvent or without a solvent. Specifically, the ligand and the metal salt can be obtained by heating at room temperature or in an aqueous solvent such as acetic acid or an organic solvent such as methanol, ethanol or dimethylformamide. These reaction conditions vary depending on the selected ligand, metal salt and solvent, but those skilled in the art can easily conceive the conditions. After the formation of the polymer, the resulting mixture may be further heated, and the solvent can be evaporated by heating to form a powder or a thin film. The molar ratio of the ligand and metal at this time can be arbitrarily selected depending on the type of ligand used, but more preferably, ligand: metal = 1: 1 to 1: 3 (molar ratio). More preferably 1: 1 to 1: 1.5, and still more preferably 1: 1 to 1: 1.2.

  Furthermore, the polymer material of the present invention may be contained in the electrolyte or may be immobilized on the electrode surface. The method of immobilizing on the electrode surface is a method of introducing a group that chemically or physically adsorbs with the electrode surface into the ligand that forms the polymer material of the present invention, or simply a solution containing the polymer material of the present invention. And a method of forming a thin film on the electrode surface by coating and drying.

  In addition, as long as the polymer material of the present invention is contained in the display element of the present invention, its usage and efficacy are not limited. Details will be described below, but preferably used as an EC compound or a mediator compound, more preferably used as a mediator compound, and most preferably used as a counter electrode reactant as a mediator compound. .

  The electrochromic display element of the present invention will be described in detail below.

(Display side transparent substrate)
The substantially transparent substrate used in the present invention is a substrate having a visible light transmittance of at least 50% or more, more preferably 80% or more. Examples of such transparent substrates include polyester (for example, polyethylene terephthalate), polyimide, polymethyl methacrylate, polystyrene, polypropylene, polyethylene, polyamide, nylon, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethersulfone, and silicone resin. Polymer films such as polyacetal resins, fluororesins, cellulose derivatives, polyolefins, plate-like substrates, glass substrates and the like are preferably used.

(Opposite substrate)
As the counter substrate, in addition to the transparent substrate used for the display-side transparent substrate, an opaque substrate such as an inorganic substrate such as a metal substrate or a ceramic substrate can be used.

(Display side transparent electrode)
The transparent electrode is not particularly limited as long as it is transparent and conducts electricity. For example, Indium Tin Oxide (ITO: Indium Tin Oxide), Indium Zinc Oxide (IZO: Indium Zinc Oxide), Fluorine Doped Tin Oxide (FTO), Indium Oxide, Zinc Oxide, Platinum, Gold, Silver, Rhodium, Copper, Examples thereof include chromium, carbon, aluminum, silicon, amorphous silicon, and BSO (Bismuth Silicon Oxide).

  In addition, polythiophene, polypyrrole, polyaniline, polyacetylene, polyparaphenylene, polyselenophenylene, etc., and their modifying compounds can be used alone or in combination.

  The surface resistance value is preferably 100Ω / □ or less, and more preferably 10Ω / □ or less. The thickness of the transparent electrode is not particularly limited, but is generally 0.1 to 20 μm.

(Transparent porous electrode)
As a transparent electrode, a nanoporous electrode having a nanoporous structure can be provided on the electrode layer. The nanoporous electrode is substantially transparent when a display element is formed, and can carry an electroactive substance such as an electrochromic material.

  The nanoporous structure as used in the present invention refers to a state in which an infinite number of nanometer-sized pores exist in a layer and ionic species contained in the electrolyte can move within the nanoporous structure.

  As a method for forming such a nanoporous electrode, a dispersion containing fine particles constituting the nanoporous electrode is formed in layers by an ink jet method, a screen printing method, a blade coating method, etc., and then heated at a predetermined temperature. A method of making porous by drying, baking, a method of making nanoporous by anodizing or photoelectrochemical etching after forming an electrode layer by sputtering, CVD, atmospheric pressure plasma, etc. Is mentioned. Also, the sol-gel method, Adv. Mater. It can also be formed by the method described in 2006, 18, 2980-2983.

The main components of the fine particles constituting the nanoporous electrode are metals such as Cu, Al, Pt, Ag, Pd and Au, metal oxides such as ITO, SnO ₂ , TiO ₂ and ZnO, carbon nanotubes, glassy carbon, and diamond. It can be selected from carbon electrodes such as like carbon and nitrogen-containing carbon, and is preferably selected from metal oxides such as ITO, SnO ₂ , TiO ₂ , and ZnO.

  In order for the nanoporous electrode to have transparency, it is preferable to use fine particles having an average particle diameter of about 5 nm to 10 μm. As the shape of the fine particles, those having an arbitrary shape such as an indefinite shape, a needle shape, and a spherical shape can be used.

  The film thickness of the nanoporous electrode is preferably in the range of 0.1 to 10 μm, more preferably in the range of 0.25 to 5 μm.

(Counter electrode)
The counter electrode can be used without particular limitation as long as it conducts electricity.

  In addition to the same material as the transparent electrode, metals having no transparency such as platinum, gold, silver, copper, aluminum, zinc, nickel, titanium, bismuth and the like, alloys thereof, carbon and the like can be preferably used.

(Porous carbon electrode)
Porous carbon electrodes that can be adsorbed and supported include graphite, non-graphitizable carbon, graphitizable carbon, composite carbon, and carbon compounds obtained by doping carbon with boron, nitrogen, phosphorus, etc. Can be mentioned. Examples of the shape of the carbon particles include mesophase microspheres and fibrous graphite. Mesophase spherules can be obtained by firing coal tar pitch or the like at 350 to 500 ° C., and further classifying these spherules and graphitizing by high-temperature firing can provide a good porous carbon electrode. In addition, fibrous graphite can be obtained from pitch-based, PAN-based, and vapor-grown fibers.

(Grid electrode)
A grid electrode (auxiliary electrode) can be attached to at least one of the counter electrodes according to the present invention.

  The auxiliary electrode is preferably made of a material having a lower electrical resistance than the main electrode portion. For example, metals such as platinum, gold, silver, copper, aluminum, zinc, nickel, titanium, and bismuth and alloys thereof can be preferably used.

  The auxiliary electrode can be installed either between the main electrode portion and the substrate, or on the surface of the main electrode portion opposite to the substrate. In any case, it is only necessary that the auxiliary electrode is electrically connected to the main electrode portion.

  There are no particular restrictions on the arrangement pattern of the auxiliary electrodes. It can be appropriately formed according to the required performance, such as linear, mesh, or circular. When the main electrode part is divided into a plurality of parts, the divided electrode parts may be connected to each other. However, in the case where the main electrode portion is a transparent electrode provided on the substrate on the display side, the auxiliary electrode is required to be provided with a shape and frequency that do not impair the visibility of the display element.

  As a method of forming the auxiliary electrode, a known method can be used. For example, patterning may be performed by patterning by photolithography, printing, ink jet, electrolytic plating, electroless plating, or exposure and development using a silver salt photosensitive material.

  Although the line width and line interval of the auxiliary electrode pattern of the present invention may be arbitrary values, it is necessary to increase the line width in order to increase the conductivity. On the other hand, when an auxiliary electrode is attached to the transparent electrode, from the viewpoint of visibility, the area coverage of the auxiliary electrode viewed from the display element observation side is preferably 30% or less, and more preferably 10% or less.

  Thus, from the viewpoint of transmittance and conductivity, the line width of the auxiliary electrode is preferably 1 μm or more and 100 μm or less, and the line interval is preferably 50 μm to 1000 μm.

(Electrode manufacturing method)
A known method can be used to form the transparent electrode and the metal auxiliary electrode. For example, mask deposition may be performed on the substrate by sputtering or the like, or patterning may be performed by photolithography after the entire surface is formed.

  Electrodes can also be formed by electrolytic plating, electroless plating, printing methods, and ink jet methods.

  After forming an electrode pattern including a catalyst layer having a monomer polymerization ability on a substrate using an inkjet method, a monomer component that is polymerized by the catalyst and becomes a conductive polymer layer after polymerization is added, It is also possible to form a metal electrode pattern by polymerizing and further performing metal plating such as silver on the conductive polymer layer, and the process is greatly reduced because no photoresist or mask pattern is used. It can be simplified.

  When the electrode material is formed by coating, known methods such as a dipping method, a spinner method, a spray method, a roll coater method, a flexographic printing method, and a screen printing method can be used.

  Among the ink jet systems, the following electrostatic ink jet can print a highly viscous liquid continuously with high accuracy, and is preferably used for forming the transparent electrode and the metal auxiliary electrode of the present invention. The viscosity of the ink is preferably 30 mPa · s or more, and more preferably 100 mPa · s or more.

(Electrostatic inkjet)
In the display element of the present invention, at least one of the transparent electrode of the composite electrode and the metal auxiliary electrode has a liquid discharge head having a nozzle with an internal diameter of 30 μm or less for discharging a charged liquid, and supplies a solution into the nozzle. Preferably, it is formed using a liquid discharge apparatus including a supply unit that performs the discharge voltage application unit that applies a discharge voltage to the solution in the nozzle.

  Furthermore, it is preferable that the solution in the nozzle is formed using a discharge device provided with a convex meniscus forming means for forming a state where the solution rises in a convex shape from the nozzle tip.

  In addition, an operation control unit that controls application of a drive voltage for driving the convex meniscus forming unit and application of a discharge voltage by the discharge voltage application unit is provided, and the operation control unit applies the discharge voltage by the discharge voltage application unit. It is also preferable to use a liquid ejection apparatus having a first ejection control unit that applies a driving voltage to the convex meniscus forming means when ejecting liquid droplets while performing the above.

  In addition, an operation control unit that controls driving of the convex meniscus forming unit and voltage application by the discharge voltage applying unit is provided, and the operation control unit is configured to swell the solution by the convex meniscus forming unit and apply the discharge voltage. And a second discharge control unit that performs synchronization with the liquid discharge device, wherein the operation control means is configured to supply the liquid at the tip of the nozzle after the swell operation of the solution and the application of the discharge voltage. It is also a preferred form to use a liquid ejection apparatus having a liquid level stabilization control unit that performs operation control for drawing the surface inward.

  By producing an electrode pattern using such an electrostatic inkjet, it is advantageous that an electrode having excellent on-demand characteristics, little waste material, and excellent dimensional accuracy can be obtained.

(TFT)
The TFT can be used by appropriately selecting a material used in a known semiconductor manufacturing technique used in a liquid crystal display or the like, and further, Japanese Patent Application Laid-Open Nos. 10-125924, 10-135481, and 10-190001. An organic TFT made of an organic compound described in JP 2000-307172 A or the like may be used.

  The TFT formed for each pixel is selected by a wiring (not shown) and controls the corresponding transparent pixel electrode. TFTs are extremely effective in preventing crosstalk between pixels. The TFT is formed so as to occupy one corner of the transparent pixel electrode, for example, but the transparent pixel electrode may overlap the TFT in the stacking direction. Specifically, the gate line and the data line are connected to the TFT, the gate electrode of each TFT is connected to each gate line, and one of the source and drain of each TFT is connected to the data line. The other drain is electrically connected to the transparent pixel electrode. The driving elements other than TFTs may be other materials as long as they can be formed on a transparent substrate by a matrix driving circuit used in a flat display element such as a liquid crystal display.

  FIG. 1 is a block diagram of a display device. Transparent pixel electrodes 12 corresponding to the respective pixels and TFTs 13 corresponding thereto are arranged in a matrix, and the counter electrode side of the capacitor serves as a common electrode. A gate line (scanning line wiring) 140 is connected to the gate electrode of the TFT 13, and the other of the source and drain of the TFT 13 is connected to a data line (signal line wiring) 150. The other of the source and drain of the TFT 13 is connected to the transparent pixel electrode 12. The gate line 140 is connected to the gate line driving circuit 120, and the data line 150 is connected to the data line driving circuits 100 and 110. The gate line driving circuit 120 and the data line driving circuits 100 and 110 are connected to the signal control unit 130.

(Electrolyte solvent)
Solvents are generally used in electrochemical cells and batteries, and dissolve various additives such as electrochromic compounds used in the present invention, metal salt compounds that are reversibly dissolved and precipitated by electrochemical redox reactions, and promoters. Any solvent can be used.

  Specifically, acetic anhydride, methanol, ethanol, tetrahydrofuran, propylene carbonate, nitromethane, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoamide, ethylene carbonate, dimethoxyethane, γ-butyrolactone, γ-valerolactone, sulfolane, dimethoxy Ethane, propiononitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethyl sulfoxide, dioxolane, sulfolane, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, ethyldimethyl phosphate, tributyl phosphate, phosphorus Tripentyl phosphate trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, phosphate Ridecyl, tris phosphate (trifluoromethyl), tris phosphate (pentafluoroethyl), triphenyl polyethylene glycol phosphate, polyethylene glycol, and the like can be used. In particular, the organic solvent according to the present invention is preferably an organic solvent having a boiling point in the range of 120 to 300 ° C. that can remain in the electrolyte without causing volatilization after the electrolyte is formed. For example, propylene carbonate, ethylene Carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, butylene carbonate, γ-butyl lactone, tetramethyl urea, sulfolane, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, 2- (N-methyl) -2 -Pyrrolidinone, hexamethylphosphortriamide, N-methylpropionamide, N, N-dimethylacetamide, N-methylacetamide, N, N-dimethylformamide, N-methylformamide, butyronitrile, propionitrile, acetyla Ton, 4-methyl-2-pentanone, acetic anhydride, dimethoxyethane, diethoxyfuran, tetrahydrofuran, ethylene glycol, diethylene glycol, triethylene glycol monobutyl ether, tricresyl phosphate, 2-ethylhexyl phosphate, dioctyl phthalate, dioctyl sebacate, etc. Can be mentioned.

  Among the above organic solvents, it is preferable to use carboxylic acid ester compounds such as propylene carbonate, ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, butylene carbonate, and γ-butyl lactone.

  Furthermore, room temperature molten salts can also be used as solvents. The room temperature molten salt is a salt composed of ion pairs that are melted at room temperature (that is, in a liquid state) consisting only of ion pairs that do not contain a solvent component, and usually has a melting point of 20 ° C. or lower, A salt consisting of an ion pair that is liquid at a temperature above. The room temperature molten salt can be used alone or in combination of two or more.

  These electrolyte solvents may be used alone or in a combination of two or more.

  In the present invention, particularly preferably used solvents are compounds represented by the following general formulas (S1) and (S2).

[Compounds Represented by General Formulas (S1) and (S2)]
In the display element of the present invention, the electrolyte preferably contains a compound represented by the following general formula (S1) or (S2).

In the formula, L represents an oxygen atom or an alkylene group, and Rs ₁₁ to Rs ₁₄ each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxyalkyl group or an alkoxy group.

In the formula, Rs ₂₁ and Rs ₂₂ each represents an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxyalkyl group or an alkoxy group.

  First, the detail of the compound represented by general formula (S1) is demonstrated.

In the general formula (S1), L represents an oxygen atom or CH ₂ , and Rs ₁₁ to Rs ₁₄ each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxyalkyl group, or an alkoxy group, These substituents may be further substituted with an arbitrary substituent.

  Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and the like as aryl groups. Examples of the cycloalkyl group such as phenyl group, naphthyl group and the like include, for example, a cyclopentyl group, cyclohexyl group and the like, an alkoxyalkyl group, for example, a β-methoxyethyl group, a γ-methoxypropyl group and the like, as an alkoxy group, Examples thereof include a methoxy group, an ethoxy group, a propyloxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, and a dodecyloxy group.

  Hereinafter, although the specific example of a compound represented by general formula (S1) is shown, in this invention, it is not limited only to these illustrated compounds.

  Next, details of the compound represented by formula (S2) according to the present invention will be described.

In the general formula (S2), Rs ₂₁ and Rs ₂₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxyalkyl group, or an alkoxy group.

  Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and the like as aryl groups. Examples of the cycloalkyl group such as phenyl group, naphthyl group and the like include, for example, a cyclopentyl group, cyclohexyl group and the like, an alkoxyalkyl group, for example, a β-methoxyethyl group, a γ-methoxypropyl group and the like, as an alkoxy group, Examples thereof include a methoxy group, an ethoxy group, a propyloxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, and a dodecyloxy group.

  Hereinafter, although the specific example of a compound represented by general formula (S2) is shown, in this invention, it is not limited only to these illustrated compounds.

  Of the compounds represented by the general formulas (S1) and (S2) exemplified above, the exemplary compounds (S1-1), (S1-2), and (S2-3) are particularly preferable.

  Furthermore, as a solvent which can be used in the present invention, J.P. A. Riddick, W.M. B. Bunger, T.A. K. Sakano, “Organic Solvents”, 4th ed. , John Wiley & Sons (1986). Marcus, “Ion Solvation”, John Wiley & Sons (1985), C.I. Reichardt, “Solvents and Solvent Effects in Chemistry”, 2nd ed. VCH (1988), G .; J. et al. Janz, R.A. P. T.A. Tomkins, “Nonqueous Electronics Handbook”, Vol. 1, Academic Press (1972).

(Thickener added with electrolyte)
In the display element of the present invention, a thickener can be used for the electrolyte. For example, gelatin, gum arabic, poly (vinyl alcohol), hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate, cellulose acetate butyrate, poly ( Vinylpyrrolidone), poly (alkylene glycol), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly ( Styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (PVC Alkylidene), poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, poly (amides), polyvinyl butyral, butyral resins and the like.

  These thickeners may be used in combination of two or more. Moreover, the compound as described in pages 71-75 of Unexamined-Japanese-Patent No. 64-13546 can be mentioned. Among these, the compounds preferably used are polyvinyl alcohols, polyvinyl pyrrolidones, hydroxypropyl celluloses, and polyalkylene glycols from the viewpoint of compatibility with various additives and improvement in dispersion stability of white particles.

(Porous white scattering layer)
In the present invention, a porous white scattering layer can be provided from the viewpoint of further enhancing display contrast and white display reflectance.

  The porous white scattering layer applicable to the present invention can be formed by applying and drying an aqueous mixture of an aqueous polymer and a white pigment that is substantially insoluble in the electrolyte solvent.

  In the present invention, “substantially insoluble in an electrolyte solvent” is defined as a state in which the dissolved amount per kg of electrolyte solvent is 0 g or more and 10 g or less at a temperature of −20 ° C. to 120 ° C. The amount of dissolution can be determined by a known method such as a component determination method using a chromatogram or a gas chromatogram.

In the present invention, examples of the water-based polymer that does not substantially dissolve in the electrolyte solvent include a water-soluble polymer and a polymer dispersed in the water-based solvent. Examples of water-soluble compounds include proteins such as gelatin and gelatin derivatives, or cellulose derivatives, natural compounds such as starch, gum arabic, dextran, pullulan, and carrageenan polysaccharides, polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrolidone, and acrylamide polymers. And synthetic polymer compounds such as derivatives thereof. As gelatin derivatives, acetylated gelatin, phthalated gelatin, polyvinyl alcohol derivatives as terminal alkyl group-modified polyvinyl alcohol, terminal mercapto group-modified polyvinyl alcohol, and cellulose derivatives include hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose and the like. It is done. Furthermore, Research Disclosure and those described in pages (71) to (75) of JP-A No. 64-13546, US Pat. No. 4,960,681, JP-A No. 62-245260, etc. superabsorbent polymers described, namely -COOM or -SO 3 M _(M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers (e.g., sodium methacrylate in the vinyl monomer having a methacrylic acid Copolymers with ammonium, potassium acrylate, etc.) are also used. Two or more of these binders can be used in combination.

  In the present invention, polyvinyl alcohol, polyethylene glycol, and polyvinylpyrrolidone compounds can be preferably used.

  Polymers dispersed in an aqueous solvent include latexes such as natural rubber latex, styrene butadiene rubber, butadiene rubber, nitrile rubber, chloroprene rubber, isoprene rubber, polyisocyanate, epoxy, acrylic, silicon, polyurethane, Examples thereof include a thermosetting resin in which urea, phenol, formaldehyde, epoxy-polyamide, melamine, alkyd resin, vinyl resin and the like are dispersed in an aqueous solvent. Of these polymers, it is preferable to use an aqueous polyurethane resin described in JP-A-10-76621.

  The average molecular weight of the water-based polymer of the present invention is preferably in the range of 10,000 to 2,000,000, more preferably in the range of 30,000 to 500,000 on a weight average basis.

  Examples of the white pigment applicable in the present invention include titanium dioxide (anatase type or rutile type), barium sulfate, calcium carbonate, aluminum oxide, zinc oxide, magnesium oxide and zinc hydroxide, magnesium hydroxide, magnesium phosphate, Magnesium hydrogen phosphate, alkaline earth metal salt, talc, kaolin, zeolite, acidic clay, glass, organic compounds such as polyethylene, polystyrene, acrylic resin, ionomer, ethylene-vinyl acetate copolymer resin, benzoguanamine resin, urea-formalin resin, A melamine-formalin resin, a polyamide resin, or the like may be used alone or in combination, or in a state having voids that change the refractive index in the particles.

In the present invention, among the white particles, titanium dioxide is preferably used. In particular, titanium dioxide surface-treated with an inorganic oxide (Al ₂ O ₃ , AlO (OH), SiO _2, etc.), in addition to these surface treatments. Titanium dioxide that has been treated with an organic substance such as trimethylolethane, triethanolamine acetate, or trimethylcyclosilane is more preferably used.

  Of these white particles, it is more preferable to use titanium oxide or zinc oxide from the viewpoint of coloring prevention at high temperature and the reflectance of the element due to the refractive index.

  In the present invention, the water mixture of the water-based compound and the white pigment is preferably in a form in which the white pigment is dispersed in water according to a known dispersion method. The mixing ratio of the aqueous compound / white pigment is preferably 1 to 0.01, more preferably 0.3 to 0.05 in terms of volume ratio.

  The thickness of the porous white scattering layer is preferably in the range of 5 to 50 μm, more preferably in the range of 10 to 30 μm.

  As the alcohol solvent, a compound having high solubility in water such as methanol, ethanol, isopropanol is preferably used, and the mixing ratio with the water / alcohol solvent is preferably in the range of 0.5 to 20 by mass ratio, More preferably, it is the range of 2-10.

  In the present invention, the medium for applying the water mixture of the water-based compound and the white pigment may be at any position as long as it is on the component between the counter electrodes of the display element, but on the electrode surface of at least one of the counter electrodes. It is preferable to give to.

  As a method for applying to a medium, for example, a coating method, a liquid spraying method, a spraying method via a gas phase, a method of flying droplets using vibration of a piezoelectric element, for example, a piezoelectric inkjet head, Examples thereof include a bubble jet (registered trademark) type ink jet head that causes droplets to fly using a thermal head that uses bumping, and a spray type that sprays liquid by air pressure or liquid pressure.

  As a coating method, it can select suitably from a well-known coating method. For example, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnation coater, reverse roller coater, transfer roller coater, curtain coater, double roller coater, slide hopper coater, gravure coater, kiss roll coater, bead coater, Examples include cast coaters, spray coaters, calendar coaters, and extrusion coaters.

  Drying of the water mixture of the aqueous compound and the white pigment applied on the medium may be performed by any method as long as water can be evaporated. For example, heating from a heat source, a heating method using infrared light, a heating method using electromagnetic induction, and the like can be given. Further, water evaporation may be performed under reduced pressure.

  Porous as used in the present invention refers to the formation of a porous white scattering material by applying a water admixture of the water-based compound and the white pigment onto the electrode and drying it, and then the silver or silver is chemically treated on the scattering material. After supplying an electrolyte solution containing the compound contained in the structure, it can be sandwiched between opposing electrodes, giving a potential difference between the opposing electrodes, causing a silver dissolution precipitation reaction, and penetrating ions that can move between the electrodes Tell the state.

  In the display element of the present invention, it is desirable to carry out a curing reaction of the water-based compound with a curing agent during or after applying and drying the water mixture described above.

  Examples of the hardener used in the present invention include, for example, U.S. Pat. No. 4,678,739, column 41, 4,791,042, JP-A-59-116655, and 62-245261. No. 61-18942, 61-249054, 61-245153, JP-A-4-218044, and the like. More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide) Ethane, etc.), N-methylol hardeners (dimethylolurea, etc.), boric acid, metaboric acid or polymer hardeners (compounds described in JP-A-62-234157). When gelatin is used as the aqueous compound, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination. Moreover, when using polyvinyl alcohol, it is preferable to use boron-containing compounds such as boric acid and metaboric acid.

  These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of the aqueous compound. In addition, it is possible to perform heat treatment and humidity adjustment during the curing reaction in order to increase the film strength.

(Electrolytes)
The “electrolyte” as used in the present invention generally refers to a substance that dissolves in a solvent such as water and exhibits a ionic conductivity in a solution (hereinafter referred to as “narrowly defined electrolyte”). A mixture containing other metals, compounds, or the like, regardless of whether it is an electrolyte or a non-electrolyte, is called an electrolyte (“broadly defined electrolyte”).

(Supporting electrolyte)
As the supporting electrolyte used in the present invention, salts, acids, and alkalis that are usually used in the field of electrochemistry or the field of batteries can be used.

  There are no particular limitations on the salts, and for example, inorganic ion salts such as alkali metal salts and alkaline earth metal salts; quaternary ammonium salts; cyclic quaternary ammonium salts; quaternary phosphonium salts and the like can be used.

Specific examples of the salts include halogen ions, SCN ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , PF _{^{6 -, AsF 6 -, CH}} 3 COO -, CH 3 (C 6 H 4) SO 3 -, and _{(C 2 F 5 SO 2)} 3 C - Li salt having a counter anion selected from, Na salt or K salt is mentioned.

Also, halogen ions, SCN ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ A quaternary ammonium salt having a counter anion selected from CH ₃ COO ⁻ , CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , and (C ₂ F ₅ SO ₂ ) ₃ C ⁻ , specifically, (CH ₃ ) ₄ NBF ₄ , (C ₂ H ₅ ) ₄ NBF ₄ , (n-C ₄ H ₉ ) ₄ NBF ₄ , (C ₂ H ₅ ) ₄ NBr, (C ₂ H ₅ ) ₄ NClO ₄ , (n-C) ₄ H ₉ ) ₄ NClO ₄ , CH ₃ (C ₂ H ₅ ) ₃ NBF ₄ , (CH ₃ ) ₂ (C ₂ H ₅ ) ₂ NBF ₄ , (CH ₃ ) ₄ NSO ₃ CF ₃ , (C ₂ H _{5 ) 4 NSO 3 CF 3, (} n-C 4 H 9) ₄ NSO ₃ CF ₃ , and a compound represented by the following formula can be given.

Also, halogen ions, SCN ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , A phosphonium salt having a counter anion selected from CH ₃ COO ⁻ , CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , and (C ₂ F ₅ SO ₂ ) ₃ C ^— , specifically, (CH ₃ ) _{4 PBF 4, (C 2 H 5} ) 4 PBF 4, (C 3 H 7) 4 PBF 4, include _{(C 4 H 9) 4 PBF} 4 and the like. Moreover, these mixtures can also be used suitably.

The supporting electrolyte of the present invention is preferably a quaternary ammonium salt, particularly preferably a quaternary spiro ammonium salt. The _ClO ⁴ as counter anion ^{_{-, BF 4 -, CF 3}} SO 3 -, (C 2 F 5 SO 2) 2 N -, PF 6 - are preferable, and BF ₄ ^- is preferable.

  The amount of the electrolyte salt used is arbitrary, but in general, the electrolyte salt is desirably present in the solvent as an upper limit of 20 M or less, preferably 10 M or less, more preferably 5 M or less. It is desirable that it be present at 0.01M or more, preferably 0.05M or more, more preferably 0.1M or more.

  In the case of a solid electrolyte, the following compounds showing electron conductivity and ion conductivity can be contained in the electrolyte.

Vinyl fluoride polymer containing perfluorosulfonic acid, polythiophene, polyaniline, polypyrrole, triphenylamines, polyvinylcarbazoles, polymethylphenylsilanes, Cu ₂ S, Ag ₂ S, Cu ₂ Se, AgCrSe _2, etc. Chalcogenides, CaF ₂ , PbF ₂ , SrF ₂ , LaF ₃ , Fl-containing compounds such as TlSn ₂ F ₅ , CeF ₃ , Li salts such as Li ₂ SO ₄ , Li ₄ SiO ₄ , Li ₃ PO ₄ , ZrO ₂ , CaO , Cd ₂ O ₃ , HfO ₂ , Y ₂ O ₃ , Nb ₂ O ₅ , WO ₃ , Bi ₂ O ₃ , AgBr, AgI, CuCl, CuBr, CuBr, CuI, LiI, LiBr, LiCl, LiAlCl ₄ , LiAlF4, _{AgSBr, C 5 H 5 NHAg 5} I 6, Rb 4 Cu 16 I 7 C _{13, Rb 3 Cu 7 Cl 10} , LiN, Li 5 NI 2, Li 6 NBr 3 such compounds.

(Ionic liquid)
The ionic liquid is also called a room temperature molten salt, and is a salt having a melting point of 100 ° C. or lower. This salt is composed of the same number of cations and anions, and there are many substances having a melting point below room temperature depending on the molecular structure, and these are in a liquid state at room temperature without adding any solvent. An ionic liquid has a strong characteristic that it has a strong electrostatic interaction and thus has almost no vapor pressure, and does not evaporate even at high temperatures.

  The ionic liquid used in the present invention may be any substance that is generally studied and reported. In particular, an organic ionic liquid has a molecular structure that exhibits a liquid in a wide temperature range including room temperature.

The ionic liquid used in the present invention is represented by the formula Q ⁺ A ⁻ and is 20 to 100 ° C., preferably 20 to 80 ° C., more preferably 20 to 60 ° C., further preferably 20 to 40 ° C., particularly 20 ° C. The viscosity (25 ° C.) is not particularly limited as long as it is a melt at room temperature, but is preferably 1 to 200 mPa · s. Further, the cation component represented by Q ⁺ in the formula is preferably an onium cation, more preferably an ammonium cation, an imidazolium cation, a pyridinium cation, a sulfonium cation, and a phosphonium cation.

The above ionic liquid will be specifically described in detail. As Q ⁺ in the above formula, R ₁ R ₂ R ₃ R ₄ N ⁺ , R ₁ R ₂ R ₃ S ⁺ , R ₁ R ₂ R ₃ R ₄ P ⁺ , R ₁ R ₂ N ⁺ = CR ₃ R ₄ , R ₁ R ₂ P ⁺ = CR ₃ R ₄ [where R ₁ to R ₄ are, independently of one another, hydrogen, saturated or unsaturated carbon C 1 -C 12 alkyl group, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group or an aralkyl group having a carbon number of 7-11 having 6 to 10 carbon _{atoms, R 5 -X- (R 6 -Y-} ) n - (Wherein R ₅ represents an alkyl group having 4 or less carbon atoms, R ₆ represents an alkylene group having 4 or less carbon atoms, X and Y represent an oxygen atom or a sulfur atom, and n represents an integer of 0 to 10). And the group may be substituted] ammonium selected from the group consisting of Phosphonium _{^{ion, R 1 R 2 N + =}} CR 3 -R 7 -R 3 C = N + R 1 R 2, R 1 R 2 S + -R 7 -S + R 1 R 2, R 1 R 2 P + _{= CR 3 -R 7 -R 3 C} = P + R 1 R 2 ( _wherein, R 1, _{R 2} and _{R 3} are the same as defined above, and _{R 7} is 1 to carbon atoms A quaternary ammonium and / or phosphonium ion selected from the group consisting of 6 alkylene or phenylene groups, which may have a substituent, and nitrogen represented by the following general formula: Examples thereof include nitrogen ions containing 1, 2 or 3 atoms selected from sulfur and phosphorus atoms, ammonium ions derived from sulfur and phosphorus atom-containing heterocycles, sulfonium ions, phosphonium ions, and the like.

Wherein R ₁ and R ₂ are as defined above, and Z may constitute a 4-10 membered ring including N ⁺ , N ⁺ = C, S ⁺ , P ⁺ or P ⁺ = C. It refers to an atom, and the constituent atom may have a substituent.

Specific examples of R ₁ to R _{4 in} the above are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, A linear or branched alkyl group such as nonyl, decyl, a cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, unsubstituted or halogen atom (F, Cl, Br, I), Hydroxyl group, lower alkoxy group (methoxy, ethoxy, propoxy, butoxy), carboxyl group, acetyl group, propanoyl group, thiol group, lower alkylthio group (methylthio, ethylthio, propylthio, butylthio), amino group, lower alkylamino group, di-lower Such as alkylamino groups Phenyl having one to three substituent, naphthyl may include toluyl, an aryl group xylyl, and the like aralkyl groups such as benzyl. Further, specific examples of _{R 5} include methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec- butyl, and alkyl group such as tert- butyl group, methylene as _{R 6} And alkylene groups such as ethylene, propylene and butylene groups. Specific examples of R7 include alkylene groups such as methylene, ethylene, propylene and butylene, and phenylene groups such as phenylene.

In addition, as the counter anion represented by A ⁻ ☆☆☆☆ in the formula, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, fluorosulfonate, tetrafluoroborate, Nitrate, alkyl sulfonate, fluorinated alkyl sulfonate or hydrogen sulfate.

  Furthermore, WO95 / 18456, JP-A-8-259543, JP-A-2001-243959, Electrochemical Vol.65, No.11, p.923 (1997), EP-716288, J. Org. Electrochem. Soc. , Vol. 143, no. 10, 3099 (1996), Inorg. Chem. The pyridinium salts, imidazolium salts, triazolium salts and the like described in 1996, 35, 1168 to 1178 can be selected and used in a timely manner according to the present invention.

(Solid electrolyte)
In the present invention, a solid electrolyte obtained by adding various materials to the electrolytic solution can also be used.

  In general, an intrinsic solid electrolyte to which a matrix polymer is added as a solid electrolyte and a gel electrolyte to which a chemical crosslinking agent and a gelling agent are added are known.

  Specific examples of such a matrix polymer include polysulfone, polyether sulfone, polyether ether sulfone, polyaryl ether sulfone, polyphenylene oxide, polyphenylene sulfide, polyphenylene sulfoxide, polyparaphenylene, polyarylene, polyether ketone, and polyether ether. Examples include ketones, polyether ketone ketones, polybenzoxazoles, polybenzothiazoles, polybenzimidazoles, polyimides, polyamides, polyamideimides, polymethyl methacrylates, polyvinylidene fluoride, polyvinylidene chlorides, polycarbonates, and polyacrylonitriles. There may be a resin having a chain structure or a resin having a branched structure.

The polymer solid electrolyte layer is formed by dissolving the supporting electrolyte in addition to the matrix polymer, and examples of the electrolyte include lithium salts such as LiCl, LiBr, LiI, LiBF ₄ , LiClO ₄ , LiPF ₆ , LiCF ₃ SO _{3, and the} like. And potassium salts such as KCl, KI, KBr, etc., sodium salts such as NaCl, NaI, NaBr, or tetraalkylammonium salts such as tetraethylammonium perfluoride, tetraethylammonium perchlorate, tetrabutylammonium perfluoride , Tetrabutylammonium perchlorate, tetrabutylammonium halide, and the like. The alkyl chain lengths of the quaternary ammonium salts described above may be the same or different, and only one kind may be used as necessary, or two or more kinds may be used in combination.

  When forming the polymer solid electrolyte layer, a plasticizer may be added. As a preferable 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-butyrolactone, Acetonitrile, sulfolane, dimethoxyethane, ethyl alcohol, isopropyl alcohol, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, n-methylpyrrolidone and mixtures thereof are preferred. Furthermore, addition of a polymerizable polyalkylene oxide as a cross-linking agent is effective because it can improve the film strength of the polymer solid electrolyte and improve the ion conductivity at room temperature.

  Moreover, a gel electrolyte can also be used as the supporting electrolyte. When the electrolyte is non-aqueous, oil gelling agents described in paragraphs [0057] to [0059] of JP-A No. 11-185836 can be used.

(Electrochromic compound (hereinafter referred to as EC compound or EC dye))
There is no restriction | limiting in particular as long as the EC compound shows the effect | action which carries out color development or decoloring by at least one of an electrochemical oxidation reaction and a reduction reaction, According to the objective, it can select suitably. EC compounds include tungsten oxide, iridium oxide, nickel oxide, cobalt oxide, vanadium oxide, molybdenum oxide, titanium oxide, indium oxide, chromium oxide, manganese oxide, Prussian blue, indium nitride, tin nitride, zirconium nitride chloride, etc. In addition to compounds, organometallic complexes, conductive polymer compounds, and organic dyes are known.

  Examples of the organometallic complex exhibiting EC characteristics include metal-bipyridyl complexes, metal phenanthroline complexes, metal-phthalocyanine complexes, rare earth diphthalocyanine complexes, and ferrocene dyes.

  Examples of the conductive polymer compound exhibiting EC characteristics include polypyrrole, polythiophene, polyisothianaphthene, polyaniline, polyphenylenediamine, polybenzidine, polyaminophenol, polyvinylcarbazole, polycarbazole, and derivatives thereof.

  Organic dyes exhibiting EC characteristics include pyridinium compounds such as viologen, azine dyes such as phenothiazine, styryl dyes, anthraquinone dyes, pyrazoline dyes, fluorane dyes, donor / acceptor compounds (for example, tetracyanoquinodis Methane, tetrathiafulvalene) and the like. In addition, compounds known as redox indicators and pH indicators can be used.

In the display element of the present invention, the EC compound according to the present invention preferably has a group that chemically or physically adsorbs to the electrode surface. The chemical adsorption according to the present invention is a relatively strong adsorption state due to a chemical bond with the electrode surface, and the physical adsorption according to the present invention is a relatively strong van der Waals force acting between the electrode surface and the adsorbed substance. It is weakly adsorbed. The adsorptive group according to the present invention is preferably a chemisorbable group. Examples of the adsorptive group to be chemisorbed include —COOH, —P═O (OH) ₂ , —OP═O (OH) ₂ and -Si (OR) ₃ (R represents an alkyl group) is preferable.

EC compounds are classified into the following three classes when classified in terms of color change.
Class 1: EC compounds that change from one specific color to another by redox.
Class 2: EC compounds that are substantially colorless in the oxidized state and exhibit a specific colored state that is the reduced state.
Class 3: EC compounds that are substantially colorless in the reduced state and exhibit a particular colored state that is the oxidized state.

  In the display element of the present invention, the class 1 to class 3 EC compounds can be appropriately selected depending on the purpose and application.

[Class 1 EC compounds]
Class 1 EC compounds are EC compounds that change from a specific color to another color by oxidation-reduction, and are compounds that can display two or more colors in their possible oxidation states.

As compounds classified into class 1, for example, V ₂ O ₅ changes from orange to green by changing from an oxidized state to a reduced state, and similarly Rh ₂ O ₃ changes from yellow to dark green.

  Many of the organometallic complexes are classified as class 1, and ruthenium (II) bipyridine complexes, such as tris (5,5'-dicarboxylethyl-2,2'-bipyridine) ruthenium complexes, are between +2 and -4 valences, The color changes from orange to purple, blue, green blue, brown, red rust and red. Many of the rare earth diphthalocyanines also exhibit such multicolor characteristics. For example, in the case of lutetium diphthalocyanine, the color gradually changes from purple to blue, green, and red-orange according to oxidation. When the polymer material of the present invention is used as an EC compound, it can be classified as the organometallic complex EC compound.

  Many of the conductive polymers are also classified as class 1. For example, polythiophene changes from blue to red by changing from an oxidized state to a reduced state, and polypyrrole changes from brown to yellow. In addition, polyaniline or the like exhibits multi-color characteristics and changes from an amber color of an oxidation state to blue, green, and light yellow in order.

[Class 2 EC compounds]
Class 2 EC compounds are compounds that are colorless or extremely light in an oxidized state and exhibit a specific colored state that is a reduced state.

Examples of the inorganic compounds classified as class 2 include the following compounds, each of which shows the color shown in parentheses in the reduced state. WO ₃ (blue), MnO ₃ (blue), Nb ₂ O ₅ (blue), TiO ₂ (blue) and the like.

  As an organometallic complex classified into class 2, for example, a tris (vasophenanthroline) iron (II) complex can be mentioned, which shows red in a reduced state.

  Examples of organic dyes classified as class 2 include compounds described in JP-A-62-71934, JP-A-2006-71765, etc., such as dimethyl terephthalate (red), 4,4′-biphenylcarboxylic acid. Examples thereof include diethyl acid (yellow), 1,4-diacetylbenzene (cyan), and tetrazolium salt compounds described in JP-A-1-230026, JP-T 2000-504774, and the like.

  The most representative dyes classified into class 2 are pyridinium compounds such as viologen. Viologen compounds have the advantages of vivid display and color variations by changing the substituents, etc., so they are the most actively studied among organic dyes. ing. Color development is based on organic radicals generated by reduction.

  Examples of pyridinium-based compounds such as viologen include compounds described in the following patents, starting with, for example, JP 2000-506629A.

  JP-A-5-70455, JP-A-5-170738, JP-A-2000-235198, JP-A-2001-114769, JP-A-2001-172293, JP-A-2001-181293, JP-A-2001-181590, JP-A-2001-510590, JP-A-2001-510590 2004-101729, JP 2006-154683, JP 2006-519222, JP 2007-31708, JP 2007-171781, JP 2007-219271, JP 2007-219272, JP 2007-279659, JP 2007-. 279570, JP 2007-279571, JP 2007-279572, and the like.

  Examples of pyridinium compounds such as viologen that can be used in the present invention are shown below, but are not limited thereto.

[Class 3 EC compounds]
Class 3 EC compounds are compounds that are colorless or extremely pale in the reduced state and exhibit a specific colored state that is an oxidized state.

  Examples of inorganic compounds classified as class 3 include iridium oxide (dark blue), Prussian blue (blue), and the like (each of which shows the color shown in parentheses in the oxidized state).

  There are few examples of conductive polymers classified into class 3, but for example, phenyl ether compounds described in JP-A-6-263846 can be mentioned.

  Many dyes are known as class 3 dyes, styryl dyes, azine dyes such as phenazine, phenothiazine, phenoxazine, and acridine, azole dyes such as imidazole, oxazole, and thiazole are preferable. .

  Examples of styryl dyes, azine dyes, and azole dyes that can be used in the present invention are shown below, but are not limited thereto.

  In a preferred embodiment of the present invention, a metal salt that is reversibly dissolved and precipitated by an electrochemical oxidation-reduction reaction is used in combination with the EC dye, and at least three colors of black display, white display, and color display other than black are displayed. Perform multicolor display. In this case, since the metal salt is reduced to give a black display, the EC dye is preferably a class 3 EC compound that develops color by oxidation, and particularly an azole series in terms of color development diversity, low driving voltage, memory properties, and the like. A dye is preferred. In the present invention, the most preferred EC organic dye is a compound represented by the following general formula (L).

  Hereinafter, the electrochromic compound represented by the following general formula (L) according to the present invention will be described.

In the general formula (L), Rl ₁ represents a substituted or unsubstituted aryl group, and Rl ₂ and Rl ₃ each represent a hydrogen atom or a substituent. X represents> N—Rl ₄ , an oxygen atom or a sulfur atom, and Rl ₄ represents a hydrogen atom or a substituent.

When Rl ₁ represents an aryl group having a substituent, the substituent is not particularly limited, and examples thereof include the following substituents.

  Alkyl groups (eg, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, etc.), cycloalkyl groups (eg, cyclohexyl, cyclopentyl, etc.), alkenyl groups, cycloalkenyl groups , Alkynyl groups (for example, propargyl group), glycidyl groups, acrylate groups, methacrylate groups, aromatic groups (for example, phenyl group, naphthyl group, anthracenyl group, etc.), heterocyclic groups (for example, pyridyl group, thiazolyl group, oxazolyl group) Group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sriphoranyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy) Group, pliers Oxy group, cyclopentyloxy group, hexyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, etc.) , Aryloxycarbonyl group (for example, phenyloxycarbonyl group), sulfonamide group (for example, methanesulfonamide group, ethanesulfonamide group, butanesulfonamide group, hexanesulfonamide group, cyclohexanesulfonamide group, benzenesulfonamide group ), Sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylamino) Sulfonyl group, phenylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), urethane group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, phenylureido group, 2-pyridylureido group, etc.), acyl Groups (eg, acetyl, propionyl, butanoyl, hexanoyl, cyclohexanoyl, benzoyl, pyridinoyl, etc.), carbamoyl groups (eg, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylamino) Carbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), acylamino group (for example, acetylamino group, benzoyla) Mino group, methylureido group etc.), sulfonyl group (eg methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, phenylsulfonyl group, 2-pyridylsulfonyl group etc.), amino group (eg amino group, Ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, anilino group, 2-pyridylamino group, etc.), halogen atom (eg chlorine atom, bromine atom, iodine atom etc.), cyano group, nitro group, sulfo group Carboxyl group, hydroxyl group, phosphono group (for example, phosphonoethyl group, phosphonopropyl group, phosphonooxyethyl group) and the like. Further, these groups may be further substituted with these groups.

Rl ₁ is preferably a substituted or unsubstituted phenyl group, more preferably a substituted or unsubstituted 2-hydroxyphenyl group or 4-hydroxyphenyl group.

The substituent represented by R1 ₂ or Rl ₃ is not particularly limited, and examples thereof include the substituents exemplified as the substituent on the aryl group of Rl ₁ . Rl ₂ and Rl ₃ are preferably an alkyl group, a cycloalkyl group, an aromatic group, or a heterocyclic group, which may have a substituent. Rl ₂ and Rl ₃ may be connected to each other to form a ring structure. As a combination of Rl ₂ and Rl ₃ , both of them may be a phenyl group or a heterocyclic group which may have a substituent, or one of them may be a phenyl group or a heterocyclic group which may have a substituent. Yes, the other is a combination of alkyl groups which may have a substituent.

X is preferably> N—R ₁₄ . R ₁₄ is preferably a hydrogen atom, an alkyl group, an aromatic group, a heterocyclic group, or an acyl group, more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms, or acyl. It is a group.

In the display element of the present invention, it is preferable that the compound represented by the general formula (L) according to the present invention has a group that chemically or physically adsorbs on the electrode surface. The chemical adsorption according to the present invention is a relatively strong adsorption state due to a chemical bond with the electrode surface, and the physical adsorption according to the present invention is a relatively strong van der Waals force acting between the electrode surface and the adsorbed substance. It is weakly adsorbed. The adsorptive group according to the present invention is preferably a chemisorbable group. Examples of the adsorptive group to be chemisorbed include —COOH, —P═O (OH) ₂ , —OP═O (OH) ₂ and -Si (OR) ₃ (R represents an alkyl group) is preferable.

  Among the azole dyes represented by the general formula (L), an imidazole dye represented by the following general formula (L2) is particularly preferable.

In the general formula (L2), Rl ₂₁ and Rl ₂₂ represent an aliphatic group, an aliphatic oxy group, an acylamino group, a carbamoyl group, an acyl group, a sulfonamide group, and a sulfamoyl group, and R1 ₂₃ represents an aromatic group or an aromatic group. Rl ₂₄ represents a hydrogen atom, an aliphatic group, an aromatic group or an aromatic heterocyclic group, and RL ₂₅ represents a hydrogen atom, an aliphatic group, an aromatic group or an acyl group.

These groups represented by Rl ₂₁ to Rl ₂₅ may be further substituted with an arbitrary substituent. However, at least one of the groups represented by Rl ₂₁ to Rl ₂₅ has —COOH, —P═O (OH) ₂ , —OP═O (OH) ₂ and —Si (OR) ₃ (R Represents an alkyl group).

The group represented by the general formulas Rl ₂₁ and Rl ₂₂ is preferably an alkyl group (particularly a branched alkyl group), a cycloalkyl group, an alkyloxy group, or a cycloalkyloxy group. Rl ₂₃ is preferably a substituted or unsubstituted phenyl group, a 5-membered or 6-membered heterocyclic group (for example, thienyl group, furyl group, pyrrolyl group, pyridyl group, etc.). Rl ₂₄ is preferably a substituted or unsubstituted phenyl group, a 5-membered or 6-membered heterocyclic group, or an alkyl group. Rl25 is particularly preferably a hydrogen atom or an aryl group.

When fixing the general formula (L2) on the electrode, at least one of the groups represented by Rl ₂₁ to Rl ₂₅ has a partial structure of —P═O (OH) ₂ , —Si (OR) ₃ (R Preferably represents an alkyl group), and particularly preferably has —Si (OR) ₃ (R represents an alkyl group) as a partial structure of the group represented by Rl ₂₃ or Rl ₂₄ .

  Specific examples of the EC dye represented by the general formula (L2) and specific examples of the EC dye contained in the general formula (L) that do not correspond to the general formula (L2) are shown below. The invention is not limited to these exemplified compounds.

(Metal salt compound)
The metal salt compound according to the present invention may be any compound as long as it contains a metal species that can be dissolved and precipitated by driving operation on at least one of the electrodes. It can also be used. Preferred metal species are silver, bismuth, copper, nickel, iron, chromium, zinc and the like, and particularly preferred are silver and bismuth.

(Silver salt compound)
The silver salt compound according to the present invention is silver or a compound containing silver in the chemical structure, such as silver oxide, silver sulfide, metallic silver, silver colloidal particles, silver halide, silver complex compound, silver ion and the like. There are no particular restrictions on the phase state species such as the solid state, the solubilized state in liquid, and the gas state, and the charged state species such as neutral, anionic, and cationic.

  In the display element of the present invention, silver iodide, silver chloride, silver bromide, silver oxide, silver sulfide, silver citrate, silver acetate, silver behenate, silver p-toluenesulfonate, silver trifluoromethanesulfonate, mercapto A known silver salt compound such as a silver salt with an acid or a silver complex with iminodiacetic acid can be used. Among these, it is preferable to use, as a silver salt, a compound that does not have a nitrogen atom having coordination properties with halogen, carboxylic acid, or silver, and for example, silver p-toluenesulfonate is preferable.

  The metal ion concentration contained in the electrolyte according to the present invention is preferably 0.2 mol / kg ≦ [Metal] ≦ 2.0 mol / kg. If the metal ion concentration is 0.2 mol / kg or more, a silver solution having a sufficient concentration can be obtained, and a desired driving speed can be obtained. If the metal ion concentration is 2 mol / kg or less, precipitation is prevented, and storage at low temperature is possible. The stability of the electrolyte solution is improved.

(Halogen ion, metal ion concentration ratio)
In the display element of the present invention, the molar concentration of halogen ions or halogen atoms contained in the electrolyte is [X] (mol / kg), and silver contained in the electrolyte or the total silver of the compound containing silver in the chemical structure. When the molar concentration is [Metal] (mol / kg), it is preferable to satisfy the condition defined by the following formula (1).

Formula (1): 0 ≦ [X] / [Metal] ≦ 0.1
The halogen atom as used in the field of this invention means an iodine atom, a chlorine atom, a bromine atom, and a fluorine atom. When [X] / [Metal] is larger than 0.1, X− → X ₂ is generated during the oxidation-reduction reaction of the metal, and X ₂ easily cross-oxidizes with the deposited metal to dissolve the deposited metal. Therefore, the molar concentration of halogen atoms is preferably as low as possible relative to the molar concentration of metallic silver. In the present invention, 0 ≦ [X] / [Metal] ≦ 0.001 is more preferable. In the case of adding halogen ions, the halogen species preferably have a total molar concentration of [I] <[Br] <[Cl] <[F] from the viewpoint of improving memory properties.

(Silver salt solvent)
In the present invention, a silver salt solvent can be used to promote dissolution and precipitation of metal salts (particularly silver salts). The silver salt solvent may be any compound that can solubilize silver in the electrolyte. For example, silver or a compound containing silver coexisting with a compound containing a chemical structural species that interacts with silver, such as a coordinate bond with silver or a weak supply bond with silver. It is common to use a means for converting to a solubilizate. As the chemical species, a halogen atom, a mercapto group, a carboxyl group, an imino group, and the like are known. It is characterized by low influence on coexisting compounds and high solubility in solvents.

  In particular, it is preferable to contain at least one compound represented by the following general formula (G-1) or general formula (G-2).

[Compound represented by General Formula (G-1) or General Formula (G-2)]
Formula _{(G-1) Rg 11 -S} -Rg 12
In the formula, Rg ₁₁ and Rg ₁₂ each represent a substituted or unsubstituted hydrocarbon group. These hydrocarbon groups may contain one or more nitrogen atoms, oxygen atoms, phosphorus atoms, sulfur atoms, and halogen atoms, and Rg ₁₁ and Rg ₁₂ may be linked to each other to form a cyclic structure.

In the formula, M represents a hydrogen atom, a metal atom or quaternary ammonium. Z represents an atomic group necessary for constituting a nitrogen-containing heterocyclic ring. n represents an integer of 0 to 5, Rg ₂₁ represents a substituent, and when n is 2 or more, each Rg ₂₁ may be the same or different, and may be connected to each other to form a condensed ring. It may be formed.

In the general formula (G-1), Rg ₁₁ and Rg ₁₂ each represent a substituted or unsubstituted hydrocarbon group, which includes an aromatic straight chain group or a branched group. Further, these hydrocarbon groups may contain one or more nitrogen atoms, oxygen atoms, phosphorus atoms, and sulfur atoms, and Rg ₁₁ and Rg ₁₂ may be connected to each other to take a cyclic structure. However, when a ring containing an S atom is formed, an aromatic group is not taken.

  Examples of groups that can be substituted for the hydrocarbon group include amino groups, guanidino groups, quaternary ammonium groups, hydroxyl groups, halogen compounds, carboxylic acid groups, carboxylate groups, amide groups, sulfinic acid groups, sulfonic acid groups, and sulfates. Groups, phosphonic acid groups, phosphate groups, nitro groups, cyano groups and the like.

  Hereinafter, although the specific example of a compound represented by general formula (G-1) which concerns on this invention is shown, in this invention, it is not limited only to these illustrated compounds.

G1-1: CH ₃ SCH ₂ CH ₂ OH
G1-2: HOCH ₂ CH ₂ SCH ₂ CH ₂ OH
G1-3: HOCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OH
G1-4: HOCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OH
G1-5: HOCH ₂ CH ₂ SCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ SCH ₂ CH ₂ OH
_{G1-6: HOCH 2 CH 2 OCH 2} CH 2 SCH 2 CH 2 SCH 2 CH 2 OCH 2 CH 2 OH
_{G1-7: H 3 CSCH 2 CH 2} COOH
G1-8: HOOCCH ₂ SCH ₂ COOH
G1-9: HOOCCH ₂ CH ₂ SCH ₂ CH ₂ COOH
G1-10: HOOCCH ₂ SCH ₂ CH ₂ SCH ₂ COOH
G1-11: HOOCCH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ COOH
G1-12: HOOCCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH (OH) CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ COOH
G1-13: HOOCCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH (OH) CH (OH) CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ COOH
G1-14: H ₃ CSCH ₂ CH ₂ CH ₂ NH ₂
G1-15: H ₂ NCH ₂ CH ₂ SCH ₂ CH ₂ NH ₂
G1-16: H ₂ NCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ NH _{2
G1-17: H 3 CSCH 2 CH 2} CH (NH 2) COOH
G1-18: H ₂ NCH ₂ CH ₂ OCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OCH ₂ CH ₂ NH _{2
G1-19: H 2 NCH 2 CH 2} SCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 SCH 2 CH 2 NH 2
G1-20: H ₂ NCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ NH ₂
G1-21: HOOC (NH ₂ ) CHCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ CH (NH ₂ ) COOH
G1-22: HOOC (NH ₂ ) CHCH ₂ SCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ SCH ₂ CH (NH ₂ ) COOH
G1-23: HOOC (NH ₂ ) CHCH ₂ OCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OCH ₂ CH (NH ₂ ) COOH
_{G1-24: H 2 N (O =} ) CCH 2 SCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 SCH 2 C (= O) NH 2
_{G1-25: H 2 N (O =} ) CCH 2 SCH 2 CH 2 SCH 2 C (= O) NH 2
_{G1-26: H 2 NHN (O =} ) CCH 2 SCH 2 CH 2 SCH 2 C (= O) NHNH 2
_{G1-27: H 3 C (O =} ) NHCH 2 CH 2 SCH 2 CH 2 SCH 2 CH 2 NHC (= O) CH 3
_{G1-28: H 2 NO 2 SCH 2} CH 2 SCH 2 CH 2 SCH 2 CH 2 SO 2 NH 2
_{G1-29: NaO 3 SCH 2 CH 2} CH 2 SCH 2 CH 2 SCH 2 CH 2 CH 2 SO 3 Na
_{G1-30: H 3 CSO 2 NHCH 2} CH 2 SCH 2 CH 2 SCH 2 CH 2 NHSO 2 CH 3
G1-31: H ₂ N (NH) CSCH ₂ CH ₂ SC (NH) NH ₂ .2HBr
_{G1-32: H 2 N (NH)} CSCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 SC (NH) NH 2 · 2HCl
_{G1-33: H 2 N (NH)} CNHCH 2 CH 2 SCH 2 CH 2 SCH 2 CH 2 NHC (NH) NH 2 · 2HBr
G1-34: [(CH ₃ ) ₃ NCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ N (CH ₃ ) ₃ ] 2 ⁺ · 2Cl ⁻

  Among the above-exemplified compounds, Exemplified Compound G1-2 is particularly preferable from the viewpoint that the object and effects of the present invention can be exhibited.

  Next, the compound represented by formula (G2) according to the present invention will be described.

In the general formula (G2), M represents a hydrogen atom, a metal atom, or quaternary ammonium. Z represents a nitrogen-containing heterocyclic ring excluding imidazole rings. n represents an integer of 0 to 5, Rg ₂₁ represents a substituent, and when n is 2 or more, each Rg ₂₁ may be the same or different, and may be connected to each other to form a condensed ring. It may be formed.

Examples of the metal atom represented by M in the general formula (G2) include Li, Na, K, Mg, Ca, Zn, and Ag. Examples of the quaternary ammonium include NH ₄ , N (CH ₃ ) ₄ , N (C ₄ H ₉ ) ₄ , N (CH ₃ ) ₃ C ₁₂ H ₂₅ , N (CH ₃ ) ₃ C ₁₆ H ₃₃ , N (CH ₃ ) ₃ CH ₂ C ₆ H _{5 and the} like It is done.

  Examples of the nitrogen-containing heterocycle having Z as a constituent in general formula (G2) include, for example, a tetrazole ring, a triazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, an indole ring, an oxazole ring, a benzoxazole ring, and a benzimidazole Ring, benzothiazole ring, benzoselenazole ring, naphthoxazole ring and the like.

The substituents represented by Rg ₂₁ of the general formula (G2), not particularly limited, but include for example substituents such as the following.

  Hydrogen atom, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (eg, methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl) Octyl, dodecyl, hydroxyethyl, methoxyethyl, trifluoromethyl, benzyl, etc.), aryl groups (eg, phenyl, naphthyl, etc.), alkylcarbonamide groups (eg, acetylamino, propionylamino, butyroylamino, etc.), aryl Carboxamide groups (eg, benzoylamino), alkylsulfonamide groups (eg, methanesulfonylamino group, ethanesulfonylamino group, etc.), arylsulfonamide groups (eg, benzenesulfonylamino group, toluenesulfonylamino) Group), alkoxy group, aryloxy group (for example, phenoxy), alkylthio group (for example, methylthio, ethylthio, butylthio, etc.), arylthio group (for example, phenylthio group, tolylthio group, etc.), alkylcarbamoyl group (for example, methylcarbamoyl group) Dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, piperidylcarbamoyl, morpholylcarbamoyl, etc.), arylcarbamoyl groups (eg, phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl, etc.), carbamoyl groups, alkylsulfurates Famoyl groups (eg methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibu Sulfamoyl, piperidylsulfamoyl, morpholylsulfamoyl, etc.), arylsulfamoyl groups (eg, phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl, etc.), sulfamoyl groups , Cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group, etc.), arylsulfonyl group (for example, phenylsulfonyl, 4-chlorophenylsulfonyl, p-toluenesulfonyl, etc.), alkoxycarbonyl group (for example, methoxycarbonyl, Ethoxycarbonyl, butoxycarbonyl etc.), aryloxycarbonyl group (eg phenoxycarbonyl etc.), alkylcarbonyl group (eg acetyl, propionyl, butyroyl etc.), a A reelcarbonyl group (for example, benzoyl group, alkylbenzoyl group, etc.), an acyloxy group (for example, acetyloxy, propionyloxy, butyroyloxy, etc.), a carboxyl group, a carbonyl group, a sulfonyl group, an amino group, a hydroxy group, or a heterocyclic group (for example, , Oxazole ring, thiazole ring, triazole ring, selenazole ring, tetrazole ring, oxadiazole ring, thiadiazole ring, thiazine ring, triazine ring, benzoxazole ring, benzthiazole ring, indolenine ring, benzselenazole ring, naphthothiazole ring , Triazaindolizine ring, diazaindolizine ring, tetraazaindolizine ring group, etc.). These substituents further include those having a substituent.

  Next, although the preferable specific example of a compound represented by general formula (G2) is shown, this invention is not limited to these compounds.

  Among the compounds exemplified above, the exemplified compounds G2-12, G2-19, and G2-20 are particularly preferable.

(promoter)
In the display device of the present invention, in order to promote the electrochemical reaction of the electrochromic material, an auxiliary compound (hereinafter referred to as a promoter) that can be oxidized and reduced may be added in addition to the EC compound. The promoter may be one that does not change the optical density in the visible region (400 to 700 nm) as a result of the oxidation-reduction reaction, or may be one that changes, that is, the EC compound, and is immobilized on the electrode. Or may be added to the electrolyte. These promoters can be used, for example, as counter electrode reactants or as redox mediators.

  For example, when an EC compound is oxidized (or reduced) in color on the display electrode side, a high color density can be obtained with a low driving voltage by utilizing a reduction (or oxidation) reaction of a promoter on the counter electrode side. . Thus, when using a promoter as a counter electrode reactive substance, it is preferable to fix an EC compound on a display electrode, and to fix and use a promoter having redox activity opposite to that of the EC compound on a counter electrode. When a promoter is used as a counter electrode material, it is preferable that the promoter does not change the optical density in the visible region (400 to 700 nm) as a result of the redox reaction. However, as described in the preferred embodiment of the present invention, the optical density in the visible region (400 to 700 nm) changes in the case of using a white scatterer in the display element to shield the color development by the promoter. Promoters, ie EC compounds may be used. Such a configuration is preferable because it facilitates selection of a promoter. As another embodiment, it is one of preferred embodiments to use a promoter that exhibits the same color as the EC compound on the display electrode side.

  On the other hand, the redox mediator is a material generally used in the field of organic electrolytic synthesis. Each organic compound has an oxidation overvoltage that depends on the electrolysis method and electrolysis conditions, in addition to its own oxidation potential, and when the anode potential is higher than the combined oxidation potential, an oxidation reaction actually occurs. Due to experimental limitations on the anodic potential, it is not possible to oxidize all substrates by direct methods. When a substrate having a high oxidation potential is oxidized, no electron transfer from the substrate to the anode occurs. When a mediator that causes electron transfer (oxidation) to the anode at a low potential coexists in this reaction system, the mediator is first oxidized, and the substrate is oxidized by the oxidized mediator to obtain a product. The advantage of this reaction system is that the substrate can be oxidized at an anode potential lower than the oxidation potential of the substrate, and the oxidized mediator returns to the original mediator when the substrate is oxidized. Is to act as a catalytic amount. In addition, since oxidation at a low potential is possible, decomposition of the substrate and product can be suppressed.

  In the present invention, for example, when an EC compound that oxidizes and colors is used as the substrate, the display element can be driven with a low driving voltage by coexisting a catalytic amount of an oxidation mediator, and the durability of the display element is increased. Will increase. In addition, there are advantages such as an improvement in display switching speed and high coloring efficiency. Similarly, the above effect can be obtained by a combination of a reducing mediator and an EC compound that produces a reducing color.

  In the display element of the present invention, as shown in the field of organic electrolytic synthesis, a single mediator may be used, or a plurality of mediators may be used in combination. In the present invention, when a promoter is used as a mediator, it is preferable to fix the EC compound on the display electrode and localize the promoter in the vicinity thereof.

  In the present invention, a promoter may be used as a counter electrode reaction substance or a mediator. For both purposes, a plurality of promoters may be used in combination at the same time. There is no restriction | limiting in particular as a promoter, According to the objective, it can select suitably. In particular, when used as a counter electrode reactant, a known EC compound can be used. In addition, when used as a redox mediator, according to the properties of EC compounds used as display dyes, Journal of Synthetic Organic Chemistry, Vol. 43, No. 6 (Special Issue on Organic Synthesis Using Electric Energy) (1985) etc. The known mediators described can be appropriately selected and used.

Examples of preferred promoters that can be used in the present invention include the following compounds.
1) Compounds having an N—O bond, such as N-oxyl derivatives such as TEMPO, N-hydroxyphthalimide derivatives, and hydroxamic acid derivatives.
2) A compound having an allyloxy free radical having a bulky substituent introduced at the 0-position, such as galvinoxyl.
3) Metallocene derivatives such as ferrocene.
4) A benzyl (diphenylethanedione) derivative.
5) Tetrazolium salt / formazan derivative.
6) Azine compounds such as phenazine, phenothiazine, phenoxazine, and acridine.
7) Pyridinium compounds such as viologen.

  In addition, a benzoquinone derivative, a hydrazyl free radical compound such as verdazil, a thiazyl free radical compound, a hydrazone derivative, a phenylenediamine derivative, a triallylamine derivative, a tetrathiafulvalene derivative, a tetracyanoquinodimethane derivative, a thianthrene derivative, etc. can also be used as a promoter. .

  In the display element of the present invention, promoters in the categories 1) to 7) are preferable, and 1) is particularly preferable.

  Hereinafter, compounds in the category 1) will be described in detail.

  N-oxyl (also called nitroxide radical) is an oxygen-centered radical generated by radically cleaving the oxygen-hydrogen bond of hydroxylamine. The nitroxide radical is known to have two reversible redox pairs as shown in the following scheme. The nitroxide radical becomes an oxoammonium cation by one-electron oxidation, which is reduced to regenerate the radical. The nitroxide radical is converted into an aminoxy anion by one-electron reduction, which is oxidized to regenerate the radical. Therefore, the nitroxide radical can function as a p-type counter electrode reactant or an n-type counter electrode reactant. In addition, oxoammonium cation has a high oxidation ability and can function as a mediator because it can oxidize leuco dyes and the like.

  The N-oxyl derivative may be contained in the electrolyte or may be immobilized on the electrode surface. Examples of the method of immobilizing on the electrode surface include a method of introducing a group that chemically or physically adsorbs with the electrode surface into the N-oxyl derivative, a method of polymerizing the N-oxyl derivative to form a thin film on the electrode surface, and the like. It is done. The N-oxyl derivative may be added in the form of an N-oxyl radical, or may be added in the form of an N-hydroxy compound, and further in the form of an oxoammonium cation.

  As N-oxyl derivatives, derivatives substituted with various substituents such as TEMPO (2,2,6,6-tetramethylpiperidinyl-N-oxyl) are commercially available. In addition, various derivatives including polymers can be easily synthesized according to known literature.

  In general, when hydrogen is substituted on the α-position carbon of the nitroxide radical, it is known that it easily disproportionates to hydroxyamine and nitrone. For this reason, the four methyl groups at the N-oxyl group α-position of TEMPO can be said to be indispensable structures for existing as stable radicals, but conversely, the reactivity may decrease due to steric hindrance of these four methyl groups. is there. Azaadamantane N-oxyl derivatives or azabicyclo N-oxyl derivatives are preferred in that they do not cause a decrease in activity.

  Next, N-hydroxyphthalimide derivatives, hydroxamic acid derivatives and the like will be described. As shown in the following scheme, phthalimide N-oxyl (PINO) generated by electrode oxidation of N-hydroxyphthalimide (NHPI) oxidizes a secondary alcohol to produce a ketone. That is, it has been reported that NHPI functions as an oxidation mediator (Chem. Commun., 1983, 479). As can be seen from this example, it is understood that the redox couple of NHPI / PINO functions as a counter electrode reactant or mediator even in the display element of the present invention. As with NHPI, hydroxamic acid derivatives and trihydroxyimino cyanuric acid (THICA) can also be used as promoters.

  When producing the display element of this invention using these compounds, it is preferable to add in the state of N-OH. After producing a display element in the state of N—OH, radicals are generated by driving the display element to oxidize.

  The promoter represented by the category of 1) can be represented by the following general formula (M1), and promoters represented by the following general formulas (M2) to (M5) are preferable. In particular, a polycyclic N-oxyl derivative represented by the general formula (M6) is preferable.

  Various promoters represented by the general formulas (M1) to (M5) are commercially available and can be easily obtained. In addition, various derivatives can be easily synthesized according to known literature. The promoter represented by the general formula (M6) is J.P. Am. Chem. Soc. , 128, 8412 (2006) and Tetrahedron Letters 49 (2008) 48-52.

  Further, promoters obtained by polymerizing these are, for example, JP-A Nos. 2004-227946, 2004-228008, 2006-73240, 2007-35375, 2007-70384, and 2007-184227. Can be synthesized with reference to Japanese Patent Publication No. 2007-298713.

In the formula, Rm ₁₁ and Rm ₁₂ are each independently an optionally substituted aliphatic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, or>C═O,>C═S,> C═N. A group bonded to a nitrogen atom via —Rm ₁₃ ; Rm ₁₃ represents a hydrogen atom or an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group which may have a substituent. Rm ₁₁ and Rm ₁₂ may be connected to each other to form a cyclic structure.

In the general formula (M1), Rm ₁₁ and Rm ₁₂ are each independently an optionally substituted aliphatic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, or>C═O,> C═S. ,> C═N—Rm represents a group bonded to a nitrogen atom via ₁₃ . Rm ₁₃ represents a hydrogen atom or an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group which may have a substituent. Rm ₁₁ and Rm ₁₂ may be connected to each other to form a cyclic structure.

  The aliphatic hydrocarbon group includes chain and cyclic groups, and the chain group includes linear and branched groups. Such aliphatic hydrocarbon groups include methyl, ethyl, vinyl, propyl, isopropyl, propenyl, butyl, iso-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, iso-hexyl, cyclohexyl, cyclohexenyl, Examples include octyl, iso-octyl, cyclooctyl, 2,3-dimethyl-2-butyl and the like.

  Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Examples of the heterocyclic group include a pyridyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a pyrrolyl group, a pyrazinyl group, a pyrimidinyl group, and a pyridazinyl group. , Serenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, morpholino group and the like.

  These substituents may further have a substituent. These substituents are not particularly limited, and examples thereof include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, Tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopropyl group, cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group, butenyl group, octenyl group etc.), cycloalkenyl group (eg , 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, etc.), alkynyl group (eg, propargyl group, ethynyl group, trimethylsilylethynyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p) -Tolyl group, m-chlorophenyl group, o-hexadecanoylamino Phenyl group, etc.), heterocyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, Tetrazolyl group, morpholino group, etc.), heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group, pyridyloxy group, thiazolyloxy group, oxazolyloxy group, imidazolyloxy group, etc.) ), Halogen atoms (for example, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.), alkoxy groups (for example, methoxy group, ethoxy group, propyloxy group, tert-butoxy group, pentyloxy group, hexyloxy group, octyl) Oxy group, dodecyloxy Group), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (for example, phenoxy group, 2-naphthyloxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3 -Nitrophenoxy group, 2-tetradecanoylaminophenoxy group, etc.), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, Cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, phenylthio group, 1-naphthylthio group, etc.), heterocyclic thio group (for example, pyridylthio group, thiazolylthio group, oxazolylthio group, imidazolylthio group, furylthio group, pinyl) Rorylthio group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl) Group), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylamino) Sulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, morpholinosulfonyl group, pyrrolidinosulfonyl group, etc.), ureido (For example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), acyl group (for example, acetyl group Ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, Formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy, ethylcarbonyloxy, Rucarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), acylamino group (for example, acetylamino group, benzoylamino group, formylamino group, pivaloylamino group, lauroylamino group, 3, 4, 5-tri-n-octyloxyphenylcarbonylamino group), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octyl) Aminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group , Morpholinocarbonyl group, piperazinocarbonyl group, etc.), alkanesulfinyl group or arylsulfinyl group (for example, methanesulfinyl group, ethanesulfinyl group, butanesulfinyl group, cyclohexanesulfinyl group, 2-ethylhexanesulfinyl group, dodecanesulfinyl group) , Phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkanesulfonyl group or arylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, cyclohexanesulfonyl group, 2-ethylhexanesulfonyl group, Dodecanesulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, methylamino group, Tilamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, N-methylanilino group, diphenylamino group, naphthylamino group, 2-pyridylamino group), silyloxy group (Eg, trimethylsilyloxy group, tert-butyldimethylsilyloxy group, etc.), aminocarbonyloxy group (eg, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N -Di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group, etc.), alkoxycarbonyloxy group (for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyl) Oxy group, n-octylcarbonyloxy group, etc.), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group, etc.), alkoxycarbonylamino Groups (for example, methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group, etc.), aryloxycarbonylamino groups (for example, phenoxycarbonyl) Amino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group, etc.), sulfamoylamino group (for example, sulfamoylamino group, N, N -Dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group, etc.), mercapto group, arylazo group (eg, phenylazo group, naphthylazo group, p-chlorophenylazo group, etc.), heterocyclic azo group (eg, pyridylazo group) , Thiazolylazo group, oxazolylazo group, imidazolylazo group, furylazo group, pyrrolylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group, etc., imino group (for example, N-succinimido-1-yl group, N-phthalimido-1-yl group, etc.), phosphino group (for example, dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group, etc.), phosphinyl group (for example, phosphinyl group, dioctyloxyphosphinyl group, di) Ethoxyphosphinyl group, etc.), phosphine Nyloxy group (for example, diphenoxyphosphinyloxy group, dioctyloxyphosphinyloxy group, etc.), phosphinylamino group (for example, dimethoxyphosphinylamino group, dimethylaminophosphinylamino group, etc.), silyl group (For example, trimethylsilyl group, tert-butyldimethylsilyl group, phenyldimethylsilyl group, etc.), cyano group, nitro group, hydroxyl group, sulfo group, carboxyl group and the like can be mentioned.

  The compound represented by the general formula (M1) may be a multimer such as a dimer or trimer linked by these substituents, or may be a polymer.

In the formula, Rm ₂₁ , Rm ₂₂ , Rm ₂₃ , and Rm ₂₄ each independently represent an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group that may have a hydrogen atom or a substituent. The atoms constituting Rm ₂₁ to Rm ₂₄ and Z1 may be connected to each other to form a cyclic structure, and Z ₁ may further have a substituent.

In the general formula (M2), Rm ₂₁ , Rm ₂₂ , Rm ₂₃ and Rm ₂₄ are each independently an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group which may have a hydrogen atom or a substituent. Represents. These aliphatic hydrocarbon group, aromatic hydrocarbon group, and heterocyclic group have the same meanings as those in formula (M1).

Z ₁ represents an atomic group necessary for forming a cyclic structure, and preferably forms a 5-membered ring or a 6-membered ring. Z ₁ may further have a substituent, and examples of the substituent include the same substituents as exemplified in the general formula (M1). The atoms constituting Rm _{21 to} Rm ₂₄ and Z ₁ may be linked to each other to form a cyclic structure. For example, together with the nitrogen atom, a polycyclic structure such as an azanorbornene structure or an azaadamantane structure is taken. Also good.

  The ring structure of the compound represented by the general formula (M2) is preferably a piperidine ring, a pyrrolidine ring, or an azaadamantane ring.

In the formula, Rm ₃₁ is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group which may have a substituent, which is substituted directly or through an oxygen atom, a nitrogen atom, or a sulfur atom with a carbonyl carbon atom. Rm ₃₂ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group which may have a substituent. Rm ₃₁ and Rm ₃₂ may be connected to each other to form a ring structure.

  In the present invention, it is one of the preferred embodiments that the N-oxyl derivative according to the present invention is a compound represented by the general formula (M3).

In the general formula (M3), Rm ₃₁ may be substituted with a carbonyl carbon atom directly or through an oxygen atom, a nitrogen atom, or a sulfur atom, and may have an aliphatic hydrocarbon group or aromatic hydrocarbon which may have a substituent. Rm ₃₂ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group which may have a substituent. These aliphatic hydrocarbon group, aromatic hydrocarbon group, and heterocyclic group have the same meanings as those in formula (M1). Rm ₃₁ and Rm ₃₂ may be connected to each other to form a cyclic structure. In the general formula (M3), Rm ₃₂ is preferably an aromatic hydrocarbon group, particularly preferably a phenyl group which may have a substituent. The substituent on the phenyl group is preferably an electron-withdrawing group such as a cyano group, an alkoxycarbonyl group, or a trifluoromethyl group. Rm ₃₁ is preferably a phenyl group or an aliphatic hydrocarbon group directly bonded to a carbonyl carbon atom, particularly preferably a branched alkyl group or a cycloalkyl group.

  In addition, it is preferable to add the compound represented by general formula (M3) in the state of N-OH to produce a display element.

In the formula, Z ₂ represents an atomic group necessary for forming a cyclic structure, and may further have a substituent.

  In this invention, it is one of the preferable aspects that the N-oxyl derivative which concerns on this invention is a compound represented by the said general formula (M4).

In the general formula (M4), Z ₂ represents an atomic group necessary for forming a cyclic structure, and preferably forms a 5-membered ring or a 6-membered ring. Z ₂ may further have a substituent, and examples of the substituent include the substituents exemplified in Formula (M1). Z ₂ may be a condensed ring.

  Note that the compound represented by the general formula (M4) is preferably added in the state of N—OH to produce a display element.

In the formula, Rm ₅₁ to Rm ₅₅ each independently represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group which may have a substituent.

  In this invention, it is one of the preferable aspects that the N-oxyl derivative which concerns on this invention is a compound represented by the said general formula (M5).

In the general formula (M5), Rm ₅₁ to Rm ₅₅ each independently represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group which may have a substituent. These aliphatic hydrocarbon group, aromatic hydrocarbon group, and heterocyclic group have the same meanings as those in formula (M1).

In the general formula (M5), Rm ₅₁ is preferably an aromatic hydrocarbon group, particularly preferably a phenyl group which may have a substituent. The substituent on the phenyl group is preferably an electron-withdrawing group such as a cyano group, an alkoxycarbonyl group, or a trifluoromethyl group. As Rm ₅₂ to Rm ₅₅ , an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is particularly preferable.

[Wherein, Rm ₆₁ and Rm ₆₂ each independently represent a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent, and Z ₃ , Z ₄ and Z ₅ are atoms necessary for forming a cyclic structure. Represents a group, and n represents 0 or 1. ]
In the general formula (M6), Rm ₆₁ and Rm ₆₂ each independently represent a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. Rm ₆₁ and Rm ₆₂ are preferably a hydrogen atom or a linear alkyl group having 4 or less carbon atoms, and at least one of Rm ₆₁ and Rm ₆₂ is preferably a hydrogen atom.

Z ₃ , Z ₄ and Z ₅ each represent an atomic group necessary for forming a cyclic structure (for example, carbon, nitrogen, oxygen, sulfur, etc.), and each preferably forms a 5-membered ring or a 6-membered ring. Z ₃ , Z ₄ and Z ₅ may further have a substituent.

  n represents 0 or 1, but when n = 0, the general formula (6) represents a bicyclo compound, and when n = 1, a tricyclo compound.

As the compound represented by the general formula (M6), n = 1 is preferable, and an azaadamantane derivative is particularly preferable.
Specific examples of promoters that can be used in the present invention are shown below, but are not limited thereto.

(Other additives)
In the electrolyte layer of the display element of the present invention, other additives for the purpose of improving various performances can be used. They are selected according to the purpose and are not particularly limited.

  Various chemical sensitizers, noble metal sensitizers, photosensitive dyes, supersensitizers, couplers, high boiling point solvents, antifoggants, stabilizers, development inhibitors, bleach accelerators, fixing accelerators, color mixing inhibitors, Formalin scavengers, toning agents, hardeners, surfactants, thickeners, plasticizers, slip agents, UV absorbers, anti-irradiation dyes, filter light absorbing dyes, polymer latex, heavy metals, antistatic agents, matting agents, etc. Can be contained as required.

  These additives mentioned above are more specifically described in Research Disclosure (hereinafter abbreviated as RD), Volume 176 Item / 17643 (December 1978), Volume 184, Item / 18431 (August 1979), 187. Volume Item / 18716 (November 1979) and Volume 308 Item / 308119 (December 1989).

  The types of compounds and their descriptions shown in these three research disclosures are listed below.

Additive RD17643 RD18716 RD308119
Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 96 III
Sensitizing dye 23 IV 648-649 996-8 IV
Desensitizing dye 23 IV 998 IV
Dye 25-26 VIII 649-650 1003 VIII
Development accelerator 29 XXI 648 Upper right Anti-fogging agent / stabilizer
24 IV 649 Upper right 1006-7 VI
Brightener 24 V 998 V
Hardener 26 X 651 Left 1004-5 X
Surfactant 26-7 XI 650 Right 1005-6 XI
Antistatic agent 27 XII 650 Right 1006-7XIII
Plasticizer 27 XII 650 Right 1006 XII
Slipper 27 XII
Matting agent 28 XVI 650 Right 1008-9 XVI
Binder 26 XXII 1003-4 IX
Support 28 XVII 1009 XVII
The above additives may be provided in auxiliary layers such as a protective layer, a filter layer, an antihalation layer, a crossover light cut layer, and a backing layer, and may be contained in these auxiliary layers.

[Product application]
The display element of the present invention can be used in an electronic book field, an ID card field, a public field, a traffic field, a broadcast field, a payment field, a distribution logistics field, and the like. Specifically, keys for doors, student ID cards, employee ID cards, various membership cards, convenience store cards, department store cards, vending machine cards, gas station cards, subway and railway cards, bus cards, Cash cards, credit cards, highway cards, driver's licenses, hospital examination cards, electronic medical records, health insurance cards, Basic Resident Registers, passports, electronic books, etc.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1 Synthesis of Polymer Material Synthesis Example 1 (Synthesis of Polymer Material 1 of the Present Invention)
Ligand A-9, 0.42 g, was dissolved in 10 ml of methanol (MeOH), and a solution of 0.17 g of iron (III) chloride dissolved in 3 ml of water was added dropwise thereto, and reacted at room temperature for 24 hours. The solvent was removed under reduced pressure to obtain the polymer material 1 of the present invention.

Synthesis Example 2 (Synthesis of polymer material 2 of the present invention)
0.18 g of sodium trifluoromethanesulfonate was added to the solution obtained in the same manner as in Example 1, and the mixture was heated to reflux for 12 hours. After concentration of this solution under reduced pressure, 0.60 g of silver trifluoromethanesulfonate was added to a solution in which the solvent was acetonitrile, and the mixture was heated under reflux for 5 hours. The precipitated solid was filtered off, and the filtrate was concentrated under reduced pressure. Thus, the polymer material 2 of the present invention was obtained by substituting chloromethane sulfonate ions with chloride ions.

Synthesis Example 3 (Synthesis of polymer material 3 of the present invention)
Ligand C-12, 0.39 g, Ligand 32, 0.77 g, Ligand 50, 0.20 g were dissolved in 10 ml of dimethylformamide (DMF), and iron (II) chloride tetrahydrate was dissolved therein. 0.40 g was added and the mixture was heated and stirred at 100 ° C. for 5 hours to synthesize the polymer material 3 of the present invention.

Synthesis Example 4 (Synthesis of polymer material 4 of the present invention)
Ligand A-2, 0.25 g, Ligand 57, 0.12 g, Ligand 66, 0.54 g are dissolved in 10 ml of dimethylformamide (DMF), and then iron (II) chloride tetrahydrate is dissolved therein. 0.40 g was added, heated and stirred at 100 ° C. for 5 hours, water was added, and the precipitate was collected by filtration to synthesize the polymer material 4 of the present invention.

Synthesis Example 5 (Synthesis of Comparative Polymer Material A)
A comparative polymer material A was obtained in the same manner as in Synthesis Example 1 except that the ligand was changed to 0.70 g of the comparative ligand shown below.

Example 2: Production of display element (use as electrochromic material)
<Production of electrode>
(Production of electrode 1)
An ITO (Indium Tin Oxide) film having a pitch of 145 μm and an electrode width of 130 μm is formed on a glass substrate having a thickness of 1.5 mm and 2 cm × 4 cm according to a known method to obtain a transparent electrode (electrode 1). It was.

(Preparation of electrode 2)
On electrode 1, a titanium dioxide film having a thickness of 5 μm (about 10 particles having an average particle diameter of 20 nm had been necked) was formed, and electrode 2 was obtained.

(Formation of electrode 3)
A solution obtained by dissolving 3% by mass of the polymer material 1 of the present invention obtained above in ethanol is applied onto the electrode 1 by spin coating, heated at 85 ° C. for 1 minute, the solvent is evaporated, and the electrode A polymer film was formed on 1 to obtain an electrode 3.

(Formation of electrode 4)
A polymer film was formed on the electrode 1 in the same manner as in the formation of the electrode 3 except that the comparative polymer material A was used, and an electrode 4 was obtained.

(Formation of electrode 5)
A polymer film was formed on the electrode 2 in the same manner as in the formation of the electrode 3 except that the electrode 2 was used, whereby an electrode 5 was obtained.

(Formation of electrode 6)
An ethanol solution containing 3% by mass of ligand A-20 was prepared, and the electrode 1 was immersed in this solution at 60 ° C. for 3 hours, washed and dried to produce an electrode 6.

(Formation of electrode 7)
Ligand C-12, 0.19 g, Ligand A-9, 0.42 g and Ligand C-36, 0.20 g and iron (III) chloride 0.20 g were mixed in 30 ml of methanol. After the electrode 6 was immersed in the solution and reacted for 24 hours, it was washed with ethanol and dried to form a polymer film on the electrode 6 via a modifying group, whereby an electrode 7 was obtained.

(Formation of electrode 8)
Ligand C-12, 0.19 g, Ligand A-9, 0.42 g and Ligand C-36, 0.20 g and iron (III) chloride 0.20 g were mixed in 30 ml of methanol. The electrode 2 was immersed in the solution and reacted for 24 hours, then washed with ethanol and dried to form a polymer film on the electrode 2 to obtain an electrode 8.

(Preparation of electrolyte 1)
An electrolytic solution 1 was obtained by dissolving 0.05 g of tetrabutylammonium perchlorate in 2.5 g of acetonitrile.

(Preparation of electrolyte 2)
In a mixed solution of 2.0 g of propylene carbonate and 0.5 g of ethylene carbonate, 0.1 g of silver trifluoromethanesulfonate, 0.2 g of (G2-19) and 0.05 g of tetrabutylammonium perchlorate are dissolved. 0.3 g of pyrrolidone (PVP, Mw 100,000) and 1.0 g of titanium dioxide having a particle diameter of 200 nm were added, and vacuum deaeration was performed while stirring to obtain an electrolytic solution 2.

(Preparation of display element 1-1)
On the periphery of the electrode 1 bordered with an olefin-based sealant containing 10% glass spherical bead spacers having an average particle size of 40 μm as a volume fraction, polyvinyl alcohol (average polymerization degree 3500, saponification degree 87% ) Add 20% by mass of Titanium Dioxide CR-90 manufactured by Ishihara Sangyo Co., Ltd. into an isopropanol solution containing 2% by mass, and apply the mixed liquid dispersed with an ultrasonic disperser so that the film thickness after drying is 20 μm. Then, after drying at 15 ° C. for 30 minutes to evaporate the solvent, it was dried in an atmosphere at 45 ° C. for 1 hour. After spraying glass spherical bead-shaped spacers having an average particle diameter of 20 μm on the obtained titanium dioxide layer, this electrode 1 and electrode 3 were bonded together and heated and pressed to produce an empty cell. The electrolyte solution 1 was vacuum-injected into the empty cell, and the inlet was sealed with an epoxy-based ultraviolet curable resin to produce a display element 1-1.

(Production of display elements 1-2 to 1-5)
In the production of the display element 1, display elements 1-2 to 1-5 were obtained in the same manner except that the configuration of the display-side electrode was changed to the configuration described in Table 1.

<< Evaluation of display element >>
[Evaluation of contrast retention]
The reflectance of the display element in an undriven state is measured with a spectrocolorimeter CM-3700d manufactured by Konica Minolta Sensing Co., Ltd., and the reflectance value at a wavelength at which the obtained reflectance takes a minimum value is R ₀ . did. Next, both electrodes of the display element fabricated were connected to both terminals of the constant voltage power source, and the reflectance after applying a voltage of +1.5 V for 3 seconds was measured in the same manner, and R ₀ was obtained at the wavelength obtained. The reflectivity was R _1.5 . CR = R _1.5 / R ₀ , CR is used as an index of contrast of the display element, and after the voltage application of + 1.5V, the repetition of 0V voltage application and + 1.5V voltage application is driven once and the first time The contrast index CR ₁ at the time of driving and the contrast index CR ₁₀₀ at the time of driving 100 times were compared according to the following formulas, and each numerical value was evaluated according to the following six levels.

(Contrast retention,%) = CR ₁₀₀ / CR ₁ × 100
◎: Contrast retention is 80% or more ◎; Contrast retention is 65% or more and less than 80% ○: Contrast retention is less than 65% Δ: Contrast change can be confirmed, but contrast retention is less than 65% ×: Table 1 below shows the results obtained when the contrast change cannot be observed visually.

  As mentioned above, the electrochromic display element which has the polymer material of this invention in the display electrode was excellent in contrast retention, and has provided the display element with high repetition resistance.

Example 3: Synthesis of display element (utilization as a promoter substance)
(Preparation of display element 2-1)
The periphery of the electrode 1 is bordered with an olefin-based sealant containing glass spherical beads having an average particle diameter of 40 μm as a volume fraction of 10%, the electrode 3 is used as a counter electrode, and the striped electrodes are orthogonal to each other. And then heated and pressed to produce an empty cell. The electrolytic solution 2 was vacuum-injected into the empty cell, and the injection port was sealed with an epoxy-based ultraviolet curable resin to produce a display element 2-1.

(Preparation of display elements 2-2 to 2-5)
Display elements 2-2 to 2-5 were obtained in the same manner as in the production of the display element 1 except that the configuration of the display-side electrode was changed to the configuration described in Table 2.

<< Evaluation of display element >>
[Evaluation of repeated durability]
The reflectance of the display element in the undriven state was measured with a spectrocolorimeter CM-3700d manufactured by Konica Minolta Sensing Co., Ltd., and the reflectance value at a wavelength of 550 nm was defined as _R0 . Next, both electrodes of the display element produced were connected to both terminals of a constant voltage power source, and the reflectance after applying a voltage of -1.3 V for 3 seconds was measured in the same manner, and the reflectance at a wavelength of 550 nm was measured. R- _1.3 . CR = R _−1.3 / R ₀ , CR is used as an index of contrast of the display element, and after the voltage application of −1.3V, the repetition of voltage application of + 1.3V is driven once and the driving is performed 50 times. The contrast index was measured every time, and the number of times of repeated driving when the CR index was 80% or less compared with the first CR index was obtained. The CR is measured up to 2000 times of repeated driving, and the higher the number of times of driving when the CR index is 80% or less of the initial value, the higher the durability as an element.

  From the above, it was found that a display element using the polymer material of the present invention as a mediator, more specifically, a counter electrode reactant, has high durability.

Example 4: Confirmation of conductivity Coating on a polyethylene terephthalate substrate (thickness: 200 μm) by 10% by mass MEK of the polymer material 2 of the present invention and a bar coater (No. 9, wet film thickness: 20 μm) by a bar coating method. After forming the film, the polymer material thin film of the present invention was formed by drying under reduced pressure in an environment of 120 ° C. Furthermore, when this board | substrate was arrange | positioned in series with an AA dry cell and a miniature light bulb using the alligator clip, it turned out that a miniature light bulb emits light and the polymer material of this invention has electroconductivity.

It is a block diagram of a display apparatus.

Explanation of symbols

12 Transparent pixel electrode 13 TFT
100, 110 Data line driving circuit 120 Gate line driving circuit 130 Signal control unit 140 Gate line (scanning line wiring)
150 Data line (signal line wiring)

Claims (12)

An electrochemical device comprising a polymeric material containing a metal atom and a ligand capable of binding to two or more metal atoms between opposing electrodes, wherein at least one of the ligands is a five-membered An electrochemical device comprising a heterocyclic monocycle. The electrochemical device according to claim 1, wherein at least one of the ligands can bind to three or more metal atoms. At least one of the ligands includes —SH, —COOH, —P═O (OH) ₂ , —OP═O (OH) _2, and —Si (OR) ₃ (R is an alkyl group) in the molecule. The electrochemical device according to claim 1, wherein the electrochemical device has at least one group selected from: The electrochemical device according to claim 1, wherein at least one of the ligands has a negative charge when bonded to a metal. The electrochemical device according to any one of claims 1 to 4, wherein at least one of the ligands has a metal complex in its structure. The electrochemical device according to any one of claims 1 to 5, wherein at least one of the ligands is a compound represented by the following general formula (1).

[Wherein A is a nitrogen, oxygen, sulfur, phosphorus or carbon atom and is part of a ring component and together with other components forms a 5-membered or 6-membered ring. W represents a substituent or a linking group containing a coordination site, p is an integer of 1 to 4, and when p is 2 or more, W may be different from each other. D represents a coordination atom or a coordination atom group, L represents a linking group between a ring containing A and D, m is an integer of 0 to 4, n is an integer of 1 to 4, p , M and n satisfy the relationship of p + m + n ≦ 4 when the ring containing A is a 5-membered ring, and p + m + n ≦ 5 when the ring is a 6-membered ring. However, at least one of the ring containing A and D is a 5-membered heterocyclic monocycle. ] A polymer material containing a metal atom and two or more ligands capable of binding to the metal atom, wherein at least one of the ligands contains a 5-membered heterocyclic monocycle, High polymer material. The polymer material according to claim 7, wherein at least one of the ligands can be bonded to three or more metal atoms. At least one of the ligands includes —SH, —COOH, —P═O (OH) ₂ , —OP═O (OH) ₂ and —Si (OR) ₃ (R is alkyl The polymer material according to claim 7, wherein the polymer material has at least one group selected from The polymer material according to claim 7, wherein at least one of the ligands has a negative charge when bonded to a metal. The polymer material according to claim 7, wherein at least one of the ligands has a metal complex in its structure. 12. The polymer material according to claim 7, wherein at least one of the ligands is a compound represented by the following general formula (1).

[Wherein A is a nitrogen, oxygen, sulfur, phosphorus or carbon atom and is part of a ring component and together with other components forms a 5-membered or 6-membered ring. W represents a substituent or a linking group containing a coordination site, p is an integer of 1 to 4, and when p is 2 or more, W may be different from each other. D represents a coordination atom or a coordination atom group, L represents a linking group between a ring containing A and D, m is an integer of 0 to 4, n is an integer of 1 to 4, p , M and n satisfy the relationship of p + m + n ≦ 4 when the ring containing A is a 5-membered ring, and p + m + n ≦ 5 when the ring is a 6-membered ring. However, at least one of the ring containing A and D is a 5-membered heterocyclic monocycle. ]

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