JP2010085570A - Electrochemical device and polymeric material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrochemical device for performing electrochromic display having contrast holding ratios and high repeating durability, and to provide a polymeric material containing a metal complex used for it. <P>SOLUTION: In the electrochemical device having the polymeric material containing metal atoms and ligands capable of being coupled with two or more metal atoms between opposite electrodes, at least one of the ligands is a ligand A capable of being coupled with three or more metal atoms. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel electrochemical device and a polymer material used therefor, and more particularly to an electrochemical device that performs electrochromic display 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, 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 an eye on this browsing means for a relatively long time, and these actions are hardly human-friendly means. Generally, as a disadvantage of light-emitting displays, eyes flicker due to flickering, inconvenient to carry, reading attitude However, it is necessary to adjust the line of sight to the still screen, and problems such as increased power consumption when read for a long time are known.

  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 display element (hereinafter abbreviated as EC method), an EC method, and an electrodeposition method (hereinafter referred to as “electrodeposition method”) using dissolution of metal or metal salt An electrochemical method such as a combination of the ED method) is known. 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 an example of such an electrochromic material, a polymer using bisterpyridine and various metals is disclosed. An electrochromic element using a material is known (for example, see Patent Document 1). Such a coordination polymer material has a problem that the repeated durability of the display element does not reach a practical level.

A coordination polymer material using a ligand capable of interacting simultaneously with three metal atoms is also known (see, for example, Non-Patent Document 1). However, in Non-Patent Document 1, use as an electrochemical device, in particular, an electrochromic display element is not assumed at all.
Special table 2007-112957 Langmuir, 2007, 12179-12184.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an electrochemical device that performs electrochromic display with high contrast retention ratio and high durability, and a polymer material including a metal complex used therein. is there.

  The above object of the present invention is achieved by the following configurations.

  1. An electrochemical device having a polymer 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 3 An electrochemical device characterized by being a ligand A capable of binding to the above metal atom.

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

  3. 3. The electrochemical device according to 1 or 2 above, wherein at least one of the ligands has a negative charge when bonded to a metal.

  4). 4. The electrochemical device according to any one of 1 to 3, wherein at least one of the ligands has a metal complex in its structure.

  5. 5. The electrochemical device according to any one of 1 to 4, wherein at least one of the ligands has a 5-membered heterocyclic monocycle.

  6). 6. The electrochemical device according to any one of 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, and n is an integer of 1 to 4. However, p, m, and n satisfy the relationship of p + m + n ≦ 4 when the ring is a 5-membered ring and p + m + n ≦ 5 when the ring is a 6-membered ring. ]
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 can bind to three or more metal atoms A polymer material characterized by being a child A.

8). At least one of the ligands includes —SH, —COOH, —P═O (OH) ₂ , —OP═O (OH) _2, and —Si (OR) ₃ (R is alkyl 8. The polymer material as described in 7 above, wherein the polymer material has at least one group selected from

  9. 9. The polymer material as described in 7 or 8 above, wherein at least one of the ligands has a negative charge when bonded to a metal.

  10. 10. The polymer material according to any one of 7 to 9, wherein at least one of the ligands has a metal complex in its structure.

  11. 11. The polymer material according to any one of 7 to 10, wherein at least one of the ligands has a 5-membered heterocyclic monocycle.

  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).

[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, and n is an integer of 1 to 4. However, p, m, and n satisfy the relationship of p + m + n ≦ 4 when the ring is a 5-membered ring and p + m + n ≦ 5 when the ring is a 6-membered ring. ]

  According to the present invention, it is possible to provide an electrochemical device that performs electrochromic display with high contrast retention and high durability and a polymer material including a metal complex used therefor.

  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 inventor of the present invention has an electrochemical having a polymer material containing a metal atom and a ligand capable of binding to two or more metal atoms between counter electrodes. An electrochemical device characterized in that it is a ligand A that can bind to three or more metal atoms, and at least one of the ligands is a highly durable electrochemical device. As a result, the present inventors have found that it can be achieved.

  Details of the present invention will be described below.

  The electrochemical device of the present invention refers to an electrochemical device that performs current drive or voltage drive, 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. A display element such as a display device is shown.

《Polymer material》
The polymer material of the present invention includes at least one metal atom and a ligand capable of binding to at least one two or more metal atoms, and at least one of the ligands includes three or more metal atoms. It is a ligand A capable of binding.

  The metal atom according to 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 from the 4th period. It is preferably a metal element in the sixth period, and more preferably a metal element in the fourth period or the fifth period from the viewpoint of cost or the like. Among these metal elements, specifically, Mn, Fe, Co, Ni, Cu, Zn, Ru, and Os are preferable, and Mn, Fe, Co, and Ru are more preferable. More preferably, Ru is selected. 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 capable of binding to a metal atom according to the present invention is a ligand capable of forming a bond with two or more metal atoms, and at least one of the ligands is three or more. It is characterized by being a ligand A capable of binding to the metal atom. 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 position is bidentate. In the case of a nickel-salen complex, the coordination position of salen is tetradentate.

  The ligand according to the present invention is characterized in that the coordination site is bidentate or more, and additionally includes a ligand A capable of binding to three or more metal atoms. 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, as a more preferable embodiment, a ligand having a tridentate or higher coordination site and a tridentate or higher ligand having a structure different from the at least one ligand are provided. Is to include. 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. In addition, when only ligands with two coordination sites are used, the polymer material has a two-dimensional extent, but a combination of two ligands and three ligands must be used. Thus, a three-dimensional structure can be introduced, and the solubility of the polymer material synthesized in the aqueous solvent or organic solvent can be adjusted.

  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, it is preferable that at least one ligand forming the polymer material of the present invention contains 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.

Moreover, 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 such a structure include polydentate chelate complexes such as salen, cyclic complexes such as porphyrin and phthalocyanine, and organometallic complexes such as ferrocene and titanocene, and the like. Is an organometallic complex, more preferably 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 preferable aspect 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.

  W represents a linking group containing a substituent or 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, W, which is a linking group containing a substituent or a coordination site, may be different or the same.

  D represents a coordination atom or a coordination atom group, and typical coordination atoms include a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Examples of the coordination atom group include a pyridine ring, a quinoline ring, and a pyrazole ring. And heterocyclic rings such as triazole ring, pyrazolone ring, thiadizole ring and benzimidazole ring, carboxyl group, hydroxyl group, alkoxy group, mercapto group, imino group, amino group, ether, sulfide (thioether), phosphine and the like.

  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, and n is an integer of 1 to 4. However, p, m, and n satisfy the relationship of p + m + n ≦ 4 when the ring is a 5-membered ring and p + m + n ≦ 5 when the ring is a 6-membered ring.

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

  First, exemplary compounds (1) to (12), which are specific examples of the ligand A capable of binding to three or more metal atoms according to the present invention, are shown below.

  Next, exemplary compounds (13) to (13) are specific examples of ligands that can be combined with other two or more metal atoms that can be used in combination with the ligand A that can be combined with three or more metal atoms according to the present invention. (69) is shown below.

  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 electrochemical device of the present invention, its usage and efficacy are not limited. Although details will be described below, it is preferably used as an electrochromic 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. preferable.

《Electrochemical device》
Next, each component of the electrochromic electrochemical device of the present invention will be described.

[Basic configuration of electrochemical device]
In the electrochemical device of the present invention, the counter unit is provided with one counter electrode on the transparent substrate. A transparent electrode such as an ITO electrode is provided on the electrode 1 which is one of the counter electrodes close to the display portion, and a conductive electrode is provided on the other non-display side electrode 2. A counter electrode composed of the electrode 1 and the electrode 2 contains an electrolyte and a compound that changes color reversibly by an electrochemical redox reaction. Reversibly switch between white and various colored states by coloring and decoloring reactions by oxidation / reduction of compounds that reversibly discolor by electrochemical oxidation-reduction reactions by applying positive and negative polarities across the counter electrode. be able to.

〔substrate〕
(Display side transparent substrate)
The 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 a transparent substrate include polyester (for example, polyethylene terephthalate), polyimide, polymethyl methacrylate, polystyrene, polypropylene, polyethylene, polyamide, nylon, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethersulfone, Silicone resin, polyacetal resin, fluororesin, cellulose derivative, polymer film such as polyolefin, plate-like substrate, glass substrate and the like are preferably used.

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

(Electrode configuration)
(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 one of the transparent electrodes, a nanoporous electrode having a nanoporous structure can be provided on the transparent electrode layer. The nanoporous electrode is substantially transparent when an electrochemical device 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 carbonaceous, graphitizable carbonaceous, composite carbon bodies, carbon compounds obtained by doping carbon with boron, nitrogen, phosphorus, and the like, and the like. 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 as 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 electrochemical device.

  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.

  In the present invention, the line width and the line interval of the auxiliary electrode pattern may be arbitrary values, but the line width needs to be increased in order to increase the conductivity. On the other hand, when the auxiliary electrode is attached to the transparent electrode, from the viewpoint of visibility, the area coverage of the auxiliary electrode viewed from the electrochemical device 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.

(Method of forming electrode)
As a method for forming the transparent electrode and the metal auxiliary electrode described above, a known method can be used. 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 methods, the following electrostatic ink jet method is capable of continuously printing a highly viscous liquid with high accuracy and is preferably used for forming a transparent electrode or a metal auxiliary electrode. The viscosity of the ink is preferably 30 mPa · s or more, and more preferably 100 mPa · s or more.

<Electrostatic inkjet method>
In the electrochemical device 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 a solution in the nozzle. It can be formed using a liquid ejecting apparatus comprising a supplying means for supplying and an ejection voltage applying means for applying an ejection voltage to the solution in the nozzle.

  Furthermore, it can form using the discharge apparatus provided with the convex-shaped meniscus formation means which forms the state which the solution in the said nozzle raised in the convex shape from the said nozzle front-end | tip part.

  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 possible 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 droplets while performing droplets.

  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.

[Application to TFT]
The polymer material of the present invention can be applied to a TFT. The TFT can be appropriately selected from materials used in known semiconductor manufacturing techniques used in liquid crystal displays and the like, and further disclosed in JP-A-10-125924, 10-135481, and 10-190001. No., Japanese Patent Application Laid-Open No. 2000-307172, etc., an organic TFT made of an organic compound 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 planar electrochemical device such as a liquid crystal display.

  FIG. 1 is a block diagram showing an example of a TFT which is an electrochemical device to which the polymer material of the present invention can be applied.

  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 110 and 110 are connected to the signal control unit 130.

〔Electrolytes〕
In the electrochemical device of the present invention, an electrolyte is contained between the counter electrodes.

  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”).

(Electrolyte solvent)
As an electrolyte solvent, it is generally used for electrochemical cells and batteries, and includes various additives such as electrochromic compounds used in the present invention, metal salt compounds that reversibly dissolve and precipitate by an electrochemical redox reaction, promoters, and the like. Any solvent that can be dissolved 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 , 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, and 20 ° C. The salt which consists of an ion pair which is liquid at the temperature over is shown. The room temperature molten salt can be used alone or in combination of two or more.

  One of these electrolyte solvents may be used alone, or a mixture of two or more may be used.

<Compounds Represented by General Formulas (S1) and (S2)>
In the electrochemical device of the present invention, the electrolyte preferably contains a compound represented by the following general formula (S1) or (S2).

In the general formula (S1), L represents an oxygen atom or an alkylene group, and Rs _{11 to} Rs ₁₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxyalkyl group, or an alkoxy group.

In the general formula (S2), 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 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, 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.

  Subsequently, the detail of the compound represented by general formula (S2) is demonstrated.

In the general formula (S2), 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.

  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).

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

Further, 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 - 4 quaternary ammonium salt having a counter anion selected from, 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,
Furthermore,

Etc.

Further, 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 - phosphonium salt having a counter anion selected from, specifically, _(CH 3) ₄ PBF ₄ , (C ₂ H ₅ ) ₄ PBF ₄ , (C ₃ H ₇ ) ₄ PBF ₄ , (C ₄ H ₉ ) ₄ PBF _{4 and the} like. Moreover, these mixtures can also be used suitably.

As the supporting electrolyte of the present invention, a cyclic quaternary ammonium salt is preferable, and a quaternary spiro ammonium salt is particularly preferable. 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 generally, the electrolyte salt is present in the solvent as an upper limit of 20 mol / L or less, preferably 10 mol / L or less, more preferably 5 mol / L or less. Desirably, the lower limit is usually 0.01 mol / L or more, preferably 0.05 mol / L or more, more preferably 0.1 mol / L or more.

  In the case of a solid electrolyte, the following compounds exhibiting electronic conductivity and ionic conductivity can be contained in the electrolyte.

Vinyl fluoride-based polymers containing perfluorosulfonic acid, polythiophene, polyaniline, polypyrrole, triphenylamines, polyvinylcarbazoles, polymethylphenylsilanes, Cu ₂ S, Ag ₂ S, Cu ₂ Se, AgCrSeR _2, etc. Chalcogenide, CaF ₂ , PbF ₂ , SrF ₂ , LaF ₃ , TlSn ₂ F ₅ , CeF _{3 and} other F-containing compounds, Li ₂ SO ₄ , Li ₄ SiO ₄ , Li ₃ PO _{4 and} other Li salts, 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 , LiAlF _{4 , AgSBr, C 5 H 5 NHAg} 5 I 6, Rb 4 Cu 16 I 7 Examples of the compound include Cl ₁₃ , Rb ₃ Cu ₇ Cl ₁₀ , LiN, Li ₅ NI ₂ , and Li ₆ NBr ₃ .

(Ionic liquid)
The ionic liquid referred to in the present invention 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 that can be suitably 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., and still more preferably 20 to 40 ° C. In particular, it refers to a salt that exists as a liquid at 20 ° C., and the viscosity (25 ° C.) is not particularly limited as long as it is a melt at normal temperature, but it is preferably 1 to 200 mPa · s. Further, the cation component represented by Q + in the formula is preferably an onium cation, and 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 and / or 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 is an atom capable of constituting a 4-10 membered ring containing N ⁺ , N ⁺ = C, S ⁺ , P ⁺ or P ⁺ = C And the constituent atoms 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 and decyl; a cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; unsubstituted or halogen atoms (eg, F, Cl, Br, I ), Hydroxyl group, lower alkoxy group (eg, methoxy, ethoxy, propoxy, butoxy, etc.), carboxyl group, acetyl group, propanoyl group, thiol group, lower alkylthio group (eg, methylthio, ethylthio, propylthio, butylthio, etc.) Each group), amino group, lower alkyl Amino group include phenyl having one to three substituents, such as di-lower alkyl amino group, naphthyl, tolyl, 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. Furthermore, specific examples of R ₇ include alkylene groups such as methylene, ethylene, propylene, and butylene, and phenylene groups such as phenylene.

Further, A in the formula ^- Examples of the counter anion represented by, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, fluorosulfonate salts, tetrafluoroborate, nitrate, alkyl sulfonate Represents a fluorinated alkyl sulfonate or a hydrogen sulfate.

  Furthermore, WO95 / 18456, JP-A-8-259543, JP-A-2001-243959, Electrochemistry 65, 11, 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, tetrafluoroborate Examples thereof include butylammonium, tetrabutylammonium perchlorate, and tetrabutylammonium halide. 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.

  In the present invention, the following compounds may be added to the electrolyte in addition to the electrolyte solvent and the supporting electrolyte.

(Metal salt compound)
The metal salt compound in the present invention is any compound as long as it contains a metal species that can be dissolved and precipitated by driving the counter electrode on at least one electrode on the counter electrode. May be. 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 electrochemical device 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, Known silver salt compounds such as silver salts with mercaptos and silver complexes with iminodiacetic acids 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 electrochemical device of the present invention, the molar concentration of halogen ions or halogen atoms contained in the electrolyte is [X] (mol / kg), and the silver or silver contained in the electrolyte is contained in the chemical structure. When the total 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 greater 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.

<Compound Represented by General Formula (G-1) or General Formula (G-2)>
In the electrochemical device of the present invention, the electrolyte preferably contains at least one compound represented by the following general formula (G-1) or general formula (G-2). The compounds represented by the general formulas (G-1) and (G-2) are compounds that promote the solubilization of silver in the electrolyte in order to cause dissolution and precipitation of silver in the present invention.

General formula (G-1)
_{Rg 11} -S-Rg ₁₂
In the general formula (G-1), 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 above general formula (G-2), 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 Rg21 may be the same or different, and are connected to each other to form a condensed ring. May be.

In the general formula (G-1), Rg ₁₁ and Rg ₁₂ each represent a substituted or unsubstituted hydrocarbon group. In these hydrocarbon groups, one or more nitrogen atoms, oxygen atoms, phosphorus atoms, sulfur An atom may be included, and Rg ₁₁ and Rg ₁₂ may be connected to each other to take a cyclic structure.

  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.

  Specific examples of the compound represented by General Formula (G-1) that can be applied in the present invention are shown below, but the present invention is not limited to these exemplified 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 NH 2 SOCH 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 objective effect 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 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 (G2), examples of the metal atom represented by M include Li, Na, K, Mg, Ca, Zn, Ag, and the like. 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 etc. Can be mentioned.

  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.

In the general formula (G2), the substituent represented by Rg ₂₁ is not particularly limited, and examples thereof include the following substituents.

  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.), arylcarbonamide groups ( For example, benzoylamino etc.), alkylsulfonamide groups (eg methanesulfonylamino group, ethanesulfonylamino group etc.), arylsulfonamide groups (eg benzenesulfonylamino group, toluenesulfonylamino group etc.), Alkyloxy group (eg, phenoxy), alkylthio group (eg, methylthio, ethylthio, butylthio, etc.), arylthio group (eg, phenylthio group, tolylthio group, etc.), alkylcarbamoyl group (eg, methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethyl) Carbamoyl, dibutylcarbamoyl, piperidylcarbamoyl, morpholylcarbamoyl, etc.), arylcarbamoyl groups (eg, phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl, etc.), alkylsulfamoyl groups (eg, methylsulfamoyl, Dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl, piperidylsulfamoy , Morpholylsulfamoyl, etc.), arylsulfamoyl groups (eg, phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl, etc.), alkylsulfonyl groups (eg, 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 ( For example, phenoxycarbonyl etc.), alkylcarbonyl groups (eg acetyl, propionyl, butyroyl etc.), arylcarbonyl groups (eg benzoyl group, alkylbenzoyl groups etc.), acyl Ruoxy group (for example, acetyloxy, propionyloxy, butyroyloxy, etc.), 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). 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 above-exemplified compounds, Exemplified Compounds G2-12 and G2-18 are particularly preferable from the viewpoint that the object and effects of the present invention can be exhibited.

(Thickener added with electrolyte)
In the electrochemical device 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 (Vinyl pyrrolidone), 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 Vinylidene chloride), 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.

[Electrochromic compound]
An electrochromic compound having electrochromic characteristics can be used for the electrolyte solution according to the present invention.

  The electrochromic compound (EC compound) according to the present invention is not particularly limited as long as it exhibits an action of coloring or decoloring by at least one of an electrochemical oxidation reaction and a reduction reaction, and may be appropriately selected according to the purpose. it can. EC compounds include inorganic oxides such as 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 electrochromic properties include metal-bipyridyl complexes, metal phenanthroline complexes, metal-phthalocyanine complexes, rare earth diphthalocyanine complexes, and ferrocene dyes.

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

  For example, a polymer material composed of a bisterpyridine derivative and a metal ion as described in JP-A-2007-112957 also exhibits electrochromic properties.

  Examples of organic dyes that exhibit electrochromic properties include pyridinium compounds such as viologen, azine dyes such as phenothiazine, styryl dyes, anthraquinone dyes, pyrazoline dyes, fluorane dyes, donor / acceptor compounds (for example, tetracyanoquino compounds) Dimethane, tetrathiafulvalene) and the like. In addition, compounds known as redox indicators and pH indicators can also be used.

(Classification of EC compounds by color tone)
The EC compounds according to the present invention 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 electrochemical device 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 capable of displaying two or more colors in their possible oxidation states.

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

  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.

  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 multicolor characteristics and changes from an amber color in an oxidation state to blue, green, and light yellow in order.

  EC compounds classified as class 1 have a merit that multicolor display is possible with a single compound, but on the other hand, they have a drawback that a state that can be said to be substantially colorless cannot be made.

<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 Nos. 62-71934 and 2006-71765, such as dimethyl terephthalate (red), 4,4'-biphenylcarboxylic acid. Examples thereof include diethyl (yellow), 1,4-diacetylbenzene (cyan), and tetrazolium salt compounds described in JP-A-1-230026, JP-T 2000-504964, and the like.

  The most typical compounds classified as class 2 are pyridinium compounds such as viologen. Viologen compounds have the advantages of vivid display and the ability to have color variations by changing substituents. Therefore, 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 JP 2000-506629 A.

  JP-A-5-70455, JP-A-5-170738, JP-A-2000-235198, JP-A-2001-114769, JP-A-2001-172293, JP-A-2001-181292, JP-A-2001-181293, Table 2001-510590, JP-A-2004-101729, JP-A-2006-154683, JP-T-2006-519222, JP-A-2007-31708, 2007-171817, 2007-219271, 2007-219272, JP-T 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 exhibiting the color shown in parentheses in the oxidized state).

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

  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 reversibly dissolves and precipitates by an electrochemical redox reaction is used in combination with the EC dye, and a multicolor of three or more colors of black display, white display, and non-black color display. 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 in particular, azoles in terms of color development diversity, low driving voltage, memory properties, and the like. System dyes are preferred.

[Compound represented by formula (L)]
In the present invention, the most preferred dye is a compound represented by the following general formula (L).

  Hereinafter, the electrochromic compound represented by the 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 linked to each other to form a ring structure. The combination of Rl ₂ and Rl ₃ may be a phenyl group or a heterocyclic group, both of which may have a substituent, or Either one is a phenyl group or a heterocyclic group which may have a substituent, and the other is a combination of an alkyl group which may have a substituent.

X is preferably a> N-Rl _4. Rl ₄ 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 electrochemical device of the present invention, the compound represented by the general formula (L) preferably has an adsorptive group that is chemically or physically adsorbed on the electrode surface. The chemical adsorption referred to in the present invention is a relatively strong adsorption state due to a chemical bond with the electrode surface, and the physical adsorption referred to in the present invention is a relatively strong van der Waals force acting between the electrode surface and the adsorbed substance. It is weakly adsorbed.

In the present invention, the adsorptive group is preferably a chemisorbable group, and as the adsorptive group to be chemisorbed, —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. R1 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, as its partial structure, —COOH, —P═O (OH) ₂ , —OP═O (OH) ₂ and —Si (OR) ₃ ( R represents an alkyl group.

In the general formula (L2), the group represented by Rl ₂₁ or 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. Rl ₂₅ is particularly preferably a hydrogen atom or an aryl group.

In addition, when the compound represented by the general formula (L2) is fixed on the electrode, at least one of the groups represented by Rl _{21 to} Rl ₂₅ includes —P═O (OH) ₂ , —Si as a partial structure. It is preferable to have (OR) ₃ (R represents an alkyl group), and in particular, —Si (OR) ₃ (R represents an alkyl group) as a partial structure of the group represented by Rl ₂₃ or Rl _24. It is preferable to have.

  Specific examples of the EC dye represented by the general formula (L2) and specific examples of the EC dye included in the general formula (L) are shown below, although they do not correspond to the general formula (L2). Is not limited to these exemplified compounds.

  These electrochromic compounds are preferably immobilized on electrodes, particularly on the viewing side (display side). By fixing to the viewing side electrode, the viewing density can be improved.

〔promoter〕
In the electrochemical device of the present invention, an auxiliary compound (hereinafter referred to as a promoter) that can be oxidized / reduced is added in order to promote the electrochemical reaction of the compound that is reversibly discolored by the electrochemical oxidation-reduction reaction. Is preferred. 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 one that changes, that is, a compound that reversibly discolors due to the electrochemical oxidation-reduction reaction. Alternatively, it may be immobilized on the electrode, or may be added to the electrolyte solution. These promoters can be used, for example, as counter electrode reactants or as redox mediators.

  For example, when a compound that reversibly changes color due to an electrochemical redox reaction on the display electrode side is oxidized (or reduced), a low drive is achieved by utilizing the reduction (or oxidation) reaction of the promoter on the counter electrode side. It is possible to obtain a high color density with voltage. Thus, when a promoter is used as a counter electrode reactant, it is preferable to use a promoter having a redox activity opposite to that of a compound reversibly discolored by an electrochemical redox reaction, immobilized 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 embodiment in which white scatterers are used in the electrochemical device to block the color development by the promoter. A promoter, that is, a compound that changes color reversibly by an electrochemical redox reaction 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 a compound that reversibly changes color by an electrochemical redox reaction 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 it is possible to oxidize the substrate at an anodic potential lower than the oxidation potential of the substrate, and that the oxidized mediator returns to the original mediator when the substrate is oxidized. It acts as a catalytic amount. Further, since oxidation at a low potential is possible, decomposition of the substrate and product can be suppressed.

  In the present invention, for example, when a compound that reversibly changes color by an electrochemical redox reaction that oxidizes and develops as the substrate, the electrochemical device is driven at a low driving voltage by coexisting a catalytic amount of an oxidation mediator. This increases the durability of the electrochemical device. 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 a compound that reversibly discolors by an electrochemical redox reaction that produces a reduction color.

  In the electrochemical device of the present invention, as shown in the field of organic electrosynthesis, a single mediator may be used, or a plurality of mediators may be used in combination. When a promoter is used as a mediator in the present invention, it is preferable to fix a compound that changes color reversibly by an electrochemical redox reaction on a display electrode and to localize the promoter in the vicinity thereof.

  In the present invention, a promoter may be used as a counter electrode reactant 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, it is possible to use a compound that reversibly discolors by a known electrochemical redox reaction. In addition, when used as a redox mediator, in accordance with the properties of a compound that reversibly changes color by an electrochemical redox reaction, Journal of Synthetic Organic Chemistry, Vol. 43, No. 6 (“Organic synthesis using electric energy”). The known mediators described in “Special Issue” (1985) and the like can be appropriately selected and used.

  Preferred promoters that can be used in the present invention include, for example, the following compounds.

1) N-oxyl derivatives such as TEMPO (2,2,6,6-tetramethylpiperidinyl-N-oxyl), N-hydroxyphthalimide derivatives, hydroxamic acid derivatives, etc., compounds having an N—O bond ,
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) benzyl (diphenylethanedione) derivative,
5) Tetrazolium salt / formazan derivative,
6) Azine compounds such as phenazine, phenothiazine, phenoxazine, acridine,
7) pyridinium compounds such as viologen,
In addition, hydrazyl free radical compounds such as benzoquinone derivatives, verdazyl, thiazyl free radical compounds, hydrazone derivatives, phenylenediamine derivatives, triallylamine derivatives, tetrathiafulvalene derivatives, tetracyanoquinodimethane derivatives, thianthrene derivatives, etc. can also be used as promoters. .

  In the electrochemical device 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. Nitroxide radicals are known to have two reversible redox pairs as shown in the scheme below. 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 solution 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, it is known that when hydrogen is substituted on the α-position carbon of the nitroxide radical, it is easily disproportionated 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 when present as stable radicals, but conversely, when the reactivity falls due to the steric hindrance of these four methyl groups. There is. An azaadamantane N-oxyl derivative or an azabicyclo N-oxyl derivative is preferred in that it does 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 also functions as a counter electrode reactant or mediator in the electrochemical device of the present invention. As with NHPI, hydroxamic acid derivatives and trihydroxyimino cyanuric acid (THICA) can also be used as promoters.

  When the electrochemical device of the present invention is produced using these compounds, it is preferably added in the state of N—OH. After producing an electrochemical device in the state of N—OH, radicals are generated by driving the electrochemical device to oxidize.

  The promoter shown in the category of 1) can be represented by the following general formula (M1), and promoters represented by the following general formulas (M2) to (M6) 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. 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 disclosed in, for example, JP-A Nos. 2004-227946, 2004-228008, 2006-73240, 2007-35375, 2007-70384, and 2007. -184227, 2007-298713, and the like.

  First, the compound represented by general formula (M1) is demonstrated.

In the general formula (M1), Rm ₁₁ and Rm ₁₂ are each independently an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group or>C═O,> C═S, which may have a substituent. ,> 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.

  Next, the compound represented by formula (M2) will be described.

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 ring that may have a hydrogen atom or a substituent. Represents a group. 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.

  Next, the compound represented by formula (M3) will be described.

  In this invention, it is one of the preferable aspects that the N-oxyl derivative based on this invention is a compound represented by general formula (M3).

In the general formula (M3), Rm ₃₁ is an aliphatic hydrocarbon group or aromatic hydrocarbon which may be substituted directly or substituted with a carbonyl carbon atom via an oxygen atom, a nitrogen atom or a sulfur atom. 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, and produce an electrochemical device.

  Next, the compound represented by formula (M4) will be described.

  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 above 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 an electrochemical device.

  Next, the compound represented by formula (M5) will be described.

  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. The Rm ₅₂ ~Rm _55, preferably an alkyl group having 1 to 6 carbon atoms, a methyl group is particularly preferred.

  Next, the compound represented by formula (M6) will be described.

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 form a 5-membered ring or a 6-membered ring. preferable. Z ₃ , Z ₄ and Z ₅ may further have a substituent.

  n represents 0 or 1, but when n = 0, the general formula (M6) 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.

(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 a component between the counter electrodes of the electrochemical device, but at least one electrode surface of the counter electrode. It is preferable to apply on top.

  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 electrochemical device of the present invention, it is desirable to carry out a curing reaction of the aqueous compound with a curing agent during or after application and drying of 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.

[Other additives]
Various additives can be used for the electrolyte solution of the electrochemical device produced by the method for producing an electrochemical device of the present invention for the purpose of improving various other performances. 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 Scavenger, Toning Agent, Hardener, Surfactant, Thickener, Plasticizer, Slipper, UV Absorber, Irradiation Dye, Filter Light Absorber Dye, Antibacterial Agent, Polymer Latex, Heavy Metal, Antistatic Agent Further, a matting agent and the like can be contained as necessary.

  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.

[Other components]
In the electrochemical device of the present invention, a sealant, a columnar structure, and spacer particles are used as necessary.

(Sealant)
The sealing agent is for sealing so as not to leak outside, and is also called a sealing agent, and is an epoxy resin, urethane resin, acrylic resin, vinyl acetate resin, ene-thiol resin, silicon resin, Curing types such as a thermosetting type, a photo-curing type, a moisture-curing type, and an anaerobic curing type such as a modified polymer resin can be used.

(Columnar structure)
The columnar structure provides strong self-holding (strength) between the substrates, for example, a columnar body, a quadrangular columnar body, an elliptical columnar body, a trapezoidal array arranged in a predetermined pattern such as a lattice arrangement. A columnar structure such as a columnar body can be given. Alternatively, stripes arranged at predetermined intervals may be used. This columnar structure is not a random array, but can be properly maintained at intervals of the substrate, such as an evenly spaced array, an array in which the interval gradually changes, and an array in which a predetermined arrangement pattern is repeated at a constant period. The arrangement is preferably considered so as not to disturb the display. If the ratio of the area occupied by the columnar structure in the display region of the electrochemical device is 1 to 40%, a practically sufficient strength as an electrochemical device can be obtained.

(spacer)
A spacer may be provided between the pair of substrates for uniformly maintaining a gap between the substrates. Examples of the spacer include a sphere made of resin or inorganic oxide. Further, a fixed spacer having a surface coated with a thermoplastic resin is also preferably used. In order to hold the gap between the substrates uniformly, only the columnar structure may be provided, but both the spacer and the columnar structure may be provided, or instead of the columnar structure, only the spacer is used as the space holding member. May be used. The diameter of the spacer is equal to or less than the height of the columnar structure, preferably equal to the height. When the columnar structure is not formed, the diameter of the spacer corresponds to the thickness of the cell gap.

[Method of applying electrolyte solution]
In the present invention, the electrolyte solution can be applied on the substrate by a coating method, a printing method, or a dispenser method. As the coating method, an extrusion coating method, a dip coating method, a spray method, a spin coating method and the like are known. As the printing method, a gravure printing method, a screen printing method, an offset printing method, a relief printing method, an ink jet method, or the like can be used.

(Screen printing)
Among the printing methods, screen printing can be used not only for imparting high-viscosity components but also for forming sealing agents and the various structures.

  In the screen printing method, a printing material (a composition for forming a columnar structure, such as a photocurable resin) is placed through a screen on which a predetermined pattern is formed. Then, the squeegee is moved at a predetermined pressure, angle, and speed. Thereby, the printing material is transferred onto the substrate through the pattern of the screen.

  When the columnar structure is formed by the screen printing method, the resin material is not limited to a photocurable resin, and for example, a thermosetting resin such as an epoxy resin or an acrylic resin or a thermoplastic resin can also be used. As thermoplastic resins, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polymethacrylate resin, polyacrylate resin, polystyrene resin, polyamide resin, polyethylene resin, polypropylene resin, fluororesin, polyurethane resin , Polyacrylonitrile resin, polyvinyl ether resin, polyvinyl ketone resin, polyether resin, polyvinyl pyrrolidone resin, saturated polyester resin, polycarbonate resin, chlorinated polyether resin and the like. The resin material is preferably used in the form of a paste by dissolving the resin in an appropriate solvent.

  After the columnar structure or the like is formed on the substrate as described above, a spacer is provided on at least one of the substrates as desired, and the pair of substrates are overlapped with the electrode formation surfaces facing each other to form an empty cell. . A pair of stacked substrates is heated while being pressed from both sides, whereby the display cells are obtained.

[Driving method of electrochemical device]
In the electrochemical device of the present invention, it is preferable to perform a driving operation in which silver black is precipitated by applying a voltage equal to or higher than the precipitation overvoltage and silver black is continuously precipitated by applying a voltage lower than the precipitation overvoltage. By performing this driving operation, the writing energy can be reduced, the driving circuit load can be reduced, and the writing speed as a screen can be improved. It is generally known that overvoltage exists in electrode reactions in the electrochemical field. For example, overvoltage is described in detail on page 121 of “Introduction to Chemistry of Electron Transfer—Introduction to Electrochemistry” (published by Asakura Shoten in 1996). Since the electrochemical device of the present invention can also be regarded as an electrode reaction between the electrode and silver in the electrolyte, it can be easily understood that overvoltage exists even in silver dissolution precipitation. Since the magnitude of the overvoltage is governed by the exchange current density, it is possible to continue silver black precipitation by applying a voltage equal to or lower than the precipitation overvoltage after the formation of silver black as in the present invention. However, it is estimated that electron injection can be easily performed with little extra electric energy.

  The driving operation of the electrochemical device of the present invention may be simple matrix driving or active matrix driving. The simple matrix driving in the present invention is a driving method in which a current is sequentially applied to a circuit in which a positive line including a plurality of positive electrodes and a negative electrode line including a plurality of negative electrodes are opposed to each other in a vertical direction. Say that. By using simple matrix driving, there is an advantage that the circuit configuration and driving IC can be simplified and manufactured at low cost. The active matrix drive is a system in which scanning lines, data lines, and current supply lines are formed in a grid pattern, and are driven by TFT circuits provided in each grid pattern. Since switching can be performed for each pixel, there are merits such as gradation and memory function. For example, a circuit described in FIG. 5 of JP-A-2004-29327 can be used.

[Product application]
The electrochemical device of the present invention can be used in an electronic book field, an ID card related field, a public related field, a transportation related field, a broadcasting related field, a settlement related field, a distribution logistics related 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, Case decoration of various equipment such as cash card, credit card, highway card, driver's license, hospital examination card, electronic medical record, health insurance card, basic resident register, passport, one-time password, electronic book, mobile phone cover, etc. Examples include a keyboard display, an electronic shelf label, an electronic POP, and an electronic advertisement. In particular, it is effective for manufacturing electronic books, electronic advertisements, electronic POPs, and the like that require display on a large screen.

  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]
0.62 g of the exemplified ligand (15) and 0.56 g of the exemplified ligand (4) are dissolved in 10 ml of methanol, and 0.17 g of iron (III) chloride is dissolved in 3 ml of water. The dissolved solution was dropped and reacted at room temperature for 24 hours, and then 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]
To a solution obtained in the same manner as in the synthesis of the polymer material 1, 0.18 g of sodium trifluoromethanesulfonate was added and heated to reflux for 12 hours. After concentrating this solution under reduced pressure, 0.60 g of silver trifluoromethanesulfonate was added to a solution containing acetonitrile as a solvent, and the mixture was heated to reflux for 5 hours. The precipitated solid was filtered off, the filtrate was evaporated, 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]
0.39 g of the exemplified ligand (19), 0.39 g of the exemplified ligand (1), and 0.68 g of the exemplified ligand (54) were dissolved in 10 ml of dimethylformamide. 0.40 g of acetylacetonate iron (III) 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]
0.38 g of the exemplified ligand (1), 0.57 g of the exemplified ligand (27), and 0.22 g of the exemplified ligand (49) were dissolved in 10 ml of dimethylformamide. 0.40 g of iron (II) chloride tetrahydrate was added, the mixture was heated and stirred at 100 ° C. for 5 hours, water was added, and the precipitate was filtered off to synthesize the polymer material 4 of the present invention.

[Synthesis Example 5: Synthesis of Comparative Polymer Material 5]
Similar to the method described in Japanese Patent Application Laid-Open No. 2007-112957, a comparative example having 0.62 g of exemplified ligand (15) and 0.18 g of iron (II) acetate and having acetate ions as counter ions. A polymer material 5 was obtained.

Example 2
<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 a size of 2 cm × 4 cm according to a known method, thereby obtaining an electrode 1 that is a transparent electrode. It was.

(Preparation of electrode 2)
On the 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 an electrode 2 was obtained.

(Preparation of electrode 3)
A solution in which 3% by mass of the polymer material 1 of the present invention synthesized in Example 1 was dissolved in ethanol was applied onto the electrode 1 by spin coating, heated at 85 ° C. for 1 minute, and the solvent was evaporated. Electrode 3 in which a polymer film was formed on electrode 1 was obtained.

(Preparation of electrode 4)
In the production of the electrode 3, an electrode 4 having a polymer film formed on the electrode 1 was obtained in the same manner except that the polymer material 1 of the present invention was changed to a comparative polymer material 5 of the same amount.

(Preparation of electrode 5)
In the production of the electrode 3, an electrode 5 having a polymer film formed on the electrode 2 was obtained in the same manner except that the electrode 2 was used instead of the electrode 1.

(Preparation of electrode 6)
The electrode 2 was immersed in a solution in which 3-aminopropyltrimethoxysilane was dissolved in ethanol at a concentration of 2% by mass for 24 hours, and then washed with ethanol. Next, an ethanol solution containing 5% by mass of the exemplified ligand (61) was prepared, and the electrode 2 was immersed in this solution at 60 ° C. for 3 hours, washed and dried to produce an electrode 6.

(Preparation of electrode 7)
In 30 ml of methanol, 0.19 g of exemplary ligand (1), 0.42 g of exemplary ligand (38), 0.20 g of exemplary ligand (60), and iron (III) chloride 0.20 g was mixed, the electrode 6 was immersed in this solution and reacted for 24 hours, then washed with ethanol and dried to form a polymer film via the modifying group on the electrode 6 to form the electrode 7. Obtained.

(Preparation of electrode 8)
In 30 ml of methanol, 0.19 g of exemplary ligand (1), 0.42 g of exemplary ligand (38), 0.20 g of exemplary ligand (60), and iron (III) chloride 0.20 g was mixed and the electrode 2 was immersed in this solution and reacted for 24 hours, then washed with ethanol and dried to form a polymer film via the modifying group on the electrode 2 to form the electrode 8. Obtained.

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

<< Production of display element >>
(Preparation of display element 1-1)
On the periphery of the electrode 2 bordered with an olefin-based sealant containing a glass spherical bead spacer having an average particle diameter of 40 μm as a volume fraction of 10%, polyvinyl alcohol (average polymerization degree 3500, saponification degree 87% ) Is added to an isopropanol solution containing 2% by mass of titanium dioxide CR-90 manufactured by Ishihara Sangyo Co., Ltd., and the mixed liquid dispersed with an ultrasonic disperser has a thickness of 20 μm after drying. It was applied, then dried at 15 ° C. for 30 minutes to evaporate the solvent, and then dried in an atmosphere at 45 ° C. for 1 hour. After sprinkling glass spherical bead spacers having an average particle diameter of 20 μm on the obtained titanium dioxide layer, electrodes 1 and 4 were bonded together and heated and pressed to prepare empty cells. The electrolytic solution 1 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 1-1.

(Production of display elements 1-2 to 1-5)
Display elements 1-2 to 1-5 were obtained in the same manner as in the manufacture of the display element 1-1 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 is R ₁ . _{It was set to 5} . CR = R ₁ . ₅ / R ₀ , CR is used as an index of contrast of the display element, and after applying a voltage of + 1.5V, a repetition of a voltage application of 0V and a voltage application of + 1.5V is driven once and a contrast index at the time of the first driving CR ₁ and contrast index CR ₁₀₀ at the time of driving 100 times were compared according to the following formula, and each numerical value was evaluated according to the following five 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 40% or more and less than 65% X: Contrast change can be confirmed, but contrast retention is 40% Less than xx: Contrast change cannot be observed visually Table 1 shows the results obtained as described above.

  As is clear from the results shown in Table 1, it can be seen that the display element having the polymer material of the present invention in the display electrode is excellent in contrast retention.

Example 3
<< Preparation of electrolyte >>
(Preparation of electrolyte 2)
In 2.5 g of dimethyl sulfoxide, 0.1 g of silver p-toluenesulfonate, 0.2 g of exemplified compound (G2-19) and 0.05 g of tetrabutylammonium perchlorate are dissolved, and polyvinylpyrrolidone (Mw 100,000) is further dissolved. 0.3 g and 1.0 g of titanium dioxide having an average particle diameter of 200 nm were added, and vacuum deaeration was performed with stirring to obtain an electrolytic solution 2.

<< Production of display element >>
(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%, and the electrode 3 is used as the opposite electrode, and the striped electrodes are orthogonal to each other. Then, the cells were bonded together and further 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 manufacture of the display element 2-1, except that the configuration of the counter 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 above-described voltage application of −1.3V, the voltage application of + 1.3V is repeated once and the driving is performed 100 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 a display element.

  As is apparent from the results shown in Table 2, it can be seen that a display element using the polymer material of the present invention as a promoter, more specifically, a counter electrode reactant as a counter electrode has high durability.

Example 4
After a 10% by mass methyl ethyl ketone solution of the polymer material 3 of the present invention is applied on a polyethylene terephthalate substrate (thickness: 200 μm) using a bar coater (No. 9, wet film thickness: 20 μm) and formed into a film. The polymer material 1 thin film of the present invention was formed by drying under reduced pressure in an environment of 120 ° C. Next, using a crocodile clip on this substrate and arranging it in series with AA batteries and miniature bulbs, the miniature bulbs emit light and it is confirmed that the polymer material 3 of the present invention has conductivity. We were able to.

It is a block diagram which shows an example of TFT which is an electrochemical device which can apply the polymer material of this invention.

Explanation of symbols

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 having a polymer 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 3 An electrochemical device characterized by being a ligand A capable of binding to the above metal atom. 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 electrochemical device according to claim 1, wherein the electrochemical device has at least one group selected from The electrochemical device according to claim 1 or 2, wherein at least one of the ligands has a negative charge when bonded to a metal. The electrochemical device according to claim 1, wherein at least one of the ligands has a metal complex in the structure. The electrochemical device according to any one of claims 1 to 4, wherein at least one of the ligands has a 5-membered heterocyclic monocycle. The electrochemical device according to claim 1, 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, and n is an integer of 1 to 4. However, p, m, and n satisfy the relationship of p + m + n ≦ 4 when the ring is a 5-membered ring and p + m + n ≦ 5 when the ring is a 6-membered ring. ] 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 is capable of binding to three or more metal atoms A polymer material characterized by being a child A. 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, comprising at least one group selected from: The polymer material according to claim 7 or 8, wherein at least one of the ligands has a negative charge when bonded to a metal. The polymer material according to any one of claims 7 to 9, wherein at least one of the ligands has a metal complex in its structure. The polymer material according to any one of claims 7 to 10, wherein at least one of the ligands has a 5-membered heterocyclic monocycle. 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, and n is an integer of 1 to 4. However, p, m, and n satisfy the relationship of p + m + n ≦ 4 when the ring is a 5-membered ring and p + m + n ≦ 5 when the ring is a 6-membered ring. ]

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