JP5294301B2 - Display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a display element that is driven with a simple member construction and at a low voltage and has high display contrast and white display reflectance. <P>SOLUTION: In the display element having an electrolyte containing a compound represented by general formula (A) or general formula (B) and a white scattering material between facing electrodes, at least one of the facing electrodes is formed by solidifying a polymer compound including a bis(terpyridine) derivative, a metal ion and a counter anion. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a novel electrochemical display element.

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

  As a means for browsing such electronic information, conventional liquid crystal displays and CRTs (CRTs), and in recent years, light-emitting types 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 not necessarily human-friendly means. Generally, as a disadvantage of the light-emitting display, flickering makes the eyes tired, inconvenient to carry, read There are known problems such as the posture being restricted and the need to adjust the line of sight to the still screen, and the increased power consumption when read for a long time.

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

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

An electrochromic method is known as a method capable of full color display that can be driven at a low voltage. The electrochromic method can be driven at a low voltage of 3 V or less, but when displaying full color, it is necessary to laminate three layers of different colors, and there is a concern about high cost due to a complicated element configuration. A full-color electrochromic element using flat ground mixing (see, for example, Patent Document 1) is known. However, in this method, the contrast of color display is not sufficient because of the flat ground mixing, and a method of performing multicolor display in a single layer. Is desired.
JP 2003-270670 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a display element that has a simple member configuration, can be driven at a low voltage, and has high display contrast and white display reflectance.

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

  1. Between the counter electrodes, an electrolyte containing a compound represented by the following general formula (A) or a compound represented by the general formula (B), and a white scattering material, and at least one counter electrode is A display element, wherein a polymer material represented by the general formula (1) is fixed.

[Wherein, Ra ₁ , Ra ₂ , Rb ₁ and Rb ₂ each independently represent an aromatic hydrocarbon group, an aromatic heterocyclic group or an aliphatic hydrocarbon group which may have a substituent. Ra ₁ and Ra ₂ , Rb ₁ and Rb ₂ may be connected to each other to form a cyclic structure. ]

[The polymer compound represented by the general formula (1) is a polymer compound containing a bisterpyridine derivative, a metal ion, and a counter anion, wherein M represents a metal ion, and X represents a counter anion. R represents a spacer containing a carbon atom and a hydrogen atom or directly connecting a terpyridyl group, and R ¹ , R ² , R ³ and R ⁴ are all the same, all different or partly the same. In the formula, n represents an integer of 2 or more representing the degree of polymerization. ]
2. 2. The display element according to 1 above, wherein the metal ion M in the general formula (1) is at least one selected from iron ions, cobalt ions, ruthenium ions, nickel ions, and zinc ions.

  3. The counter anion in the general formula (1) is at least one selected from the group consisting of acetate ions, boron tetrafluoride ions, polyoxymetalates, and combinations thereof. Display element.

  4). 4. The display element according to any one of 1 to 3, wherein the spacer in the general formula (1) is an aryl group or an alkyl group.

  5. 5. The display element according to 4 above, wherein the aryl group or alkyl group further contains an oxygen atom or a sulfur atom.

  6). 6. The display element according to 4 or 5, wherein the aryl group is at least one selected from the group consisting of the following formulas [1] to [4].

  7). The polymer material represented by the general formula (1) is produced by a method including a step of refluxing a bisterpyridine derivative represented by the following general formula (2) and a metal salt in acetic acid and methanol. The display element according to any one of 1 to 6, wherein:

[In the formula, R represents a spacer containing a carbon atom and a hydrogen atom, or directly connecting a terpyridyl group, and R ¹ , R ² , R ³ and R ⁴ are all the same, all different or a part. It represents the same hydrogen atom, aryl group or alkyl group, and n is an integer of 2 or more representing the degree of polymerization. ]
8). 8. The display element according to any one of the above items 1 to 7, wherein white display and colored display of two or more colors are performed by driving the counter electrode.

  9. Between the counter electrodes, there is an electrolyte containing a compound represented by the following general formula (A) or a compound represented by the general formula (B) and a white scattering material, and at least one counter electrode has the following general A display element, wherein a polymer material represented by formula (3) is fixed.

[Wherein, Ra ₁ , Ra ₂ , Rb ₁ and Rb ₂ each independently represent an aromatic hydrocarbon group, an aromatic heterocyclic group or an aliphatic hydrocarbon group which may have a substituent. Ra ₁ and Ra ₂ , Rb ₁ and Rb ₂ may be connected to each other to form a cyclic structure. ]

[The polymer compound represented by the general formula (3) includes first to N-th (N is an integer of 2 or more) bisterpyridine derivatives and first to N-th (N is an integer of 2 or more). A polymer material containing a metal ion and first to N-th (N is an integer of 2 or more) counter anions, wherein M ¹ ,..., M ^N (N is an integer of 2 or more) ) Represent the first to Nth metal ions that are all the same, all different, or partly the same, and X ¹ ,..., X ^N (N is an integer of 2 or more) are all the same, all Represents the first to N-th counter anions which are different or partly the same, and R ¹ ,..., R ^N (N is an integer of 2 or more) are all the same, all different or partly the same Represents a spacer containing a carbon atom and a hydrogen atom, or directly connecting a terpyridyl group, R ¹ ₁ ,..., R ^{1 _{N, R 2 1, ···,}} R 2 N, R 3 1, ···, R 3 N, R 4 1, ···, R 4 N (N is an integer of 2 or more) are all identical All represent different or partially the same hydrogen atom, aryl group or alkyl group, and n ¹ ,..., ^{N N} each represents an integer of 2 or more representing the degree of polymerization. ]
10. The first to Nth metal ions in the general formula (3) are at least one selected from the group consisting of iron ions, cobalt ions, ruthenium ions, nickel ions, and zinc ions, respectively. 9. The display element according to 9.

  11. The first to Nth counter anions in the general formula (3) are each at least one selected from the group consisting of acetate ions, boron tetrafluoride ions, polyoxymetalates, and combinations thereof. The display element according to 9 or 10 above.

12 Spacer represented by R ^1, · · ·, R ^N in the general formula (3), respectively, display of any one of the 9 to 11, characterized in that an aryl group or an alkyl group element.

  13. 13. The display element according to 12, wherein the aryl group or alkyl group further contains an oxygen atom or a sulfur atom.

  14 14. The display element according to 12 or 13, wherein the aryl group is at least one selected from the group consisting of the following formulas [1] to [4].

  15. The polymer material represented by the general formula (3) includes first to N-th (N is an integer of 2 or more) bisterpyridine derivatives represented by the following general formula (4); Each of the N (N is an integer of 2 or more) metal salts is refluxed in acetic acid and methanol, and the first to Nth (N is an integer of 2 or more) obtained in the respective refluxing steps. The display element according to any one of 9 to 14 above, wherein the display element is manufactured by a method including a step of mixing the reactants.

[Wherein, R ¹ ,..., R ^N (N is an integer of 2 or more) are all the same, all different, or partly the same, containing a carbon atom and a hydrogen atom, or a terpyridyl group Represents a directly connected spacer, R ¹ ₁ ,..., R ¹ _N , R ² ₁ ,..., R ² _N , R ³ ₁ , ..., R ³ _N , R ⁴ ₁ ,. , R ⁴ _n (n is an integer of 2 or more) are all the same, all different, or some the same hydrogen atom, an aryl group or an alkyl group, n ^1, ···, n ⁿ each polymerization It is an integer greater than or equal to 2 representing degrees. ]
16. 16. The display element according to any one of 9 to 15, wherein white display and color display of two or more colors are performed by driving the counter electrode.

  According to the present invention, it is possible to provide a display element that has a simple member configuration, can be driven at a low voltage, and has high display contrast and white display reflectance.

  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 present inventor contained at least one compound represented by the general formula (A) or the compound represented by the general formula (B) between the counter electrodes. A display element characterized by having an electrolyte and at least one counter electrode fixing the polymer material represented by the general formula (1) can be driven with a simple member configuration and low voltage Thus, it has been found that a display element having high display contrast and high white display reflectance can be realized, and as soon as the present invention has been achieved.

  Details of the present invention will be described below.

[Basic structure of display element]
In the display element of the present invention, the display portion is provided with one corresponding counter electrode. The electrode 1 which is one of the counter electrodes close to the display unit is provided with a transparent electrode such as an ITO electrode, and the other electrode 2 is provided with a conductive electrode. Between the electrode 1 and the electrode 2, an electrolyte containing the compound represented by the general formula (A) or the compound represented by the general formula (B) according to the present invention is provided. The polymer material represented by the general formula (1) according to the present invention is immobilized, and by applying a voltage of both positive and negative polarities between the counter electrodes, the high material represented by the general formula (1) according to the present invention is obtained. An oxidation-reduction reaction of the molecular material is performed, and the white display and the color display of two or more colors can be switched reversibly.

[Compounds represented by general formula (A) and general formula (B)]
In general formula (A) and general formula (B), Ra ₁ , Ra ₂ , Rb ₁ , Rb ₂ may each independently have a substituent, an aromatic group, an aromatic heterocyclic group, an aliphatic group Represents. Ra ₁ and Ra ₂ , Rb ₁ and Rb ₂ may be connected to each other to form a cyclic structure.

  Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Examples of the aromatic heterocyclic group include a pyridyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a pyrrolyl group, a pyrazinyl group, and a pyrimidinyl group. Group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, morpholino group and the like. The aliphatic hydrocarbon group includes a chain and a cyclic group, and the chain includes a linear group and a branched group. 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.

  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-hexadecanoyl Minophenyl 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, dodecyl Xy group etc.), cycloalkoxy group (eg cyclopentyloxy group, cyclohexyloxy group etc.), aryloxy group (eg 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, cyclohexylthio 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.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxy) Carbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenyl) Aminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, morpholinosulfonyl group, pyrrolidinosulfonyl group, etc.), urea Group (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 group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group, ethylcarbonyloxy group Butylcarbonyloxy 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 Group, morpholinocarbonyl group, piperazinocarbonyl group, etc.), alkanesulfinyl group or arylsulfinyl group (for example, methanesulfinyl group, ethanesulfinyl group, butanesulfinyl group, cyclohexanesulfinyl group, 2-ethylhexanesulfinyl group, dodecane) Sulfinyl 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) , Ethylamino group, dimethylamino 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, trimethylsilyloxy 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 groups (for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbo group) Ruoxy 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 (eg dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group etc.), phosphinyl group (eg phosphinyl group, dioctyloxyphosphinyl group) , Diethoxyphosphinyl group, etc.) Finyloxy 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 (A) or the general formula (B) may be a multimer such as a dimer or trimer linked by these substituents, or may be a polymer. Good.

In the general formulas (A) and (B), Ra ₁ , Ra ₂ , Rb ₁ and Rb ₂ are preferably aromatic hydrocarbon groups or aromatic heterocyclic groups, and in particular, aromatics substituted with electron-withdrawing groups. An aromatic hydrocarbon group or an electron-deficient aromatic heterocyclic group is preferred. The electron-withdrawing group is an electron-withdrawing group having a Hammett's substituent constant σp value of 0 or more. Preferably, it is an electron withdrawing group having a σp value of 0.2 or more. The upper limit is preferably an electron withdrawing group of 1.0 or less. More preferably, it is an electron withdrawing group of 0.75 or less. Hammett's rule was found in 1935 by L. L. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values are described in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (McGraw-Hill) and “Chemical Areas Extra”, 122, 96-103, 1979 (Nan-Edo). However, it does not mean that the values known in the literature described in these documents are limited to only certain substituents, and even if the values are unknown, as long as they are included in the range when measured based on Hammett's rule Of course included.

  Specific examples of the electron withdrawing group having a σp value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group Group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy group A halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another electron-withdrawing group having a σp value of 0.20 or more, a heterocyclic group, a halogen atom, an azo group, or The selenocyanate group It is.

  The electron-deficient aromatic heterocyclic group is preferably a group derived from a nitrogen-containing 6-membered ring such as a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring.

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

  Specific examples of the compound represented by formula (B) are shown below, but the present invention is not limited to these exemplified compounds.

[Polymer material represented by general formula (1)]
The compound represented by the general formula (1) according to the present invention is a polymer material containing a bisterpyridine derivative, a metal ion, and a counter anion, wherein M represents a metal ion, and X represents a counter anion. R represents a spacer containing a carbon atom and a hydrogen atom, or directly connecting a terpyridyl group, and R ¹ , R ² , R ³ and R ⁴ are all the same, all different or partly the same A hydrogen atom, an aryl group or an alkyl group is represented, and n is an integer of 2 or more representing the degree of polymerization.

  Although the specific example of the bister pyridine derivative which comprises General formula (1) based on this invention is shown, this invention is not limited only to these illustrated compounds.

  In the general formula (1) according to the present invention, the metal ion M is not particularly limited, but is preferably at least one selected from iron ions, cobalt ions, ruthenium ions, nickel ions and zinc ions.

  In the general formula (1) according to the present invention, the counter anion is preferably at least one selected from the group consisting of acetate ions, boron tetrafluoride ions, polyoxymetalates, and combinations thereof.

  In the general formula (1) according to the present invention, the spacer is preferably an aryl group or an alkyl group, and the aryl group or alkyl group preferably contains an oxygen atom or a sulfur atom. The aryl group is preferably at least one selected from the group consisting of the formulas [1] to [4].

  As a method for producing the polymer material represented by the general formula (1) according to the present invention, it is preferable to produce the polymer material by refluxing the bisterpyridine derivative and the metal salt in acetic acid or methanol. Acetic acid and methanol can function as solvents for the bisterpyridine derivatives and metal salts, respectively. For example, the reflux is performed at a temperature of 150 ° C. for 24 hours, but is not limited thereto. The reflux conditions vary depending on the selected spacer and metal salt, but those skilled in the art can easily select optimum conditions. After the polymer formation, the mixture obtained by reflux may be heated. The solvent is evaporated by heating to a powder. The powder has, for example, a color such as purple and is in a reduced state. Since such powder is easily dissolved in methanol, it is easy to handle.

[Polymer material represented by general formula (3)]
The polymer compound represented by the general formula (3) includes first to N-th (N is an integer of 2 or more) bisterpyridine derivatives and first to N-th (N is an integer of 2 or more) metals. A polymer material containing ions and first to N-th (N is an integer of 2 or more) counter anions, wherein M ¹ ,..., M ^N (N is an integer of 2 or more) Are all the same, all different, or partly the same first to Nth metal ions, and X ¹ ,..., X ^N (N is an integer of 2 or more) are all the same and all different. Or represents the same first to N-th counter anions, and R ¹ ,..., R ^N (N is an integer of 2 or more) are all the same, all different, or partly the same. Represents a spacer containing a carbon atom and a hydrogen atom, or directly connecting a terpyridyl group, R ¹ ₁ ,..., R ¹ _N , R ² ₁ , ..., R ² _N , R ³ ₁ , ..., R ³ _N , R ⁴ ₁ , ..., R ⁴ _N (N is an integer of 2 or more) are all the same, All represent different or partly the same hydrogen atom, aryl group or alkyl group, and n ¹ ,..., ^{N N} each represents an integer of 2 or more representing the degree of polymerization.

  Specific examples of the bisterpyridine derivative constituting the general formula (3) according to the present invention include the same bisterpyridine derivatives applicable to the general formula (1).

  In the general formula (3) according to the present invention, the first to Nth metal ions are each at least one selected from the group consisting of iron ions, cobalt ions, ruthenium ions, nickel ions and zinc ions. Is preferred.

  In the general formula (3) according to the present invention, the first to N-th counter anions are each selected from the group consisting of acetate ions, boron tetrafluoride ions, polyoxymetalates, and combinations thereof. One type is preferable.

In the general formula (3) according to the present invention, each of the spacers represented by R ¹ ,..., R ^N is preferably an aryl group or an alkyl group, and more preferably an aryl group or an alkyl group. Preferably further contains an oxygen atom or a sulfur atom, and in particular, the aryl group is preferably at least one selected from the group consisting of the formulas [1] to [4].

  Examples of the method for producing the polymer material represented by the general formula (3) according to the present invention include, for example, first to Nth (N is an integer of 2 or more) bisters represented by the general formula (4). Each of the pyridine derivatives and each of the first to N-th (N is an integer of 2 or more) metal salts are refluxed in acetic acid and methanol, and the first to first obtained in the respective refluxing steps. The method of manufacturing by the method of mixing the Nth (N is an integer greater than or equal to 2) reactant is preferable.

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

[Electrolyte solvent]
The organic solvent applicable in the electrolyte according to the present invention is not particularly limited as long as the organic solvent has 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, propionitri , Acetonitrile, acetylacetone, 4-methyl-2-pentanone, 2-butanol, 1-butanol, 2-propanol, 1-propanol, acetic anhydride, ethyl acetate, ethyl propionate, dimethoxyethane, diethoxyfuran, tetrahydrofuran, ethylene glycol , Diethylene glycol, triethylene glycol monobutyl ether, tricresyl phosphate, 2-ethylhexyl phosphate, dioctyl phthalate, dioctyl sebacate and the like.

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

  As other solvents that 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).

[Ionic liquid]
An ionic liquid can be applied to the display element of the present invention. 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, more preferably an ammonium cation, an imidazolium cation, a pyridinium cation, a sulfonium cation, and a phosphonium cation.

The above-mentioned ionic fluid 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 each other hydrogen, saturated or unsaturated carbon, An alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 11 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). groups ammonium is selected from the group consisting of which may have a substituent] and / or phosphonium ^{_{ion, R 1 R 2 N + =}} CR 3 - ^{_{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 represents an alkylene or phenylene group having 1 to 6 carbon atoms, and these groups are substituted) A quaternary ammonium and / or phosphonium ion selected from the group consisting of (which may have a group), an atom selected from nitrogen, sulfur and phosphorus atoms represented by the following general formula: An ammonium ion, a sulfonium ion, a phosphonium ion, or the like derived from a nitrogen-containing, sulfur-containing, and phosphorus-containing heterocyclic ring containing three atoms can be given.

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 are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, A linear or branched alkyl group such as nonyl, decyl, a cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, unsubstituted or halogen atom (F, Cl, Br, I), Hydroxyl group, lower alkoxy group (methoxy, ethoxy, propoxy, butoxy), carboxyl group, acetyl group, propanoyl group, thiol group, lower alkylthio group (methylthio, ethylthio, propylthio, butylthio), amino group, lower alkylamino group, di-lower Substitution such as alkylamino group An aryl group such as phenyl, naphthyl, toluyl and xylyl having 1 to 3 groups, and an aralkyl group such as benzyl can be exemplified. Specific examples of R ₅ include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups, and R ₆ represents methylene. 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.

The counter anion represented by A ⁻ in the formula includes hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, fluorosulfonate, tetrafluoroborate, nitrate, alkylsulfonate. Represents a fluorinated alkyl sulfonate or a hydrogen sulfate.

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

[Solid electrolyte, gel electrolyte]
The electrolyte according to the present invention includes, in addition to a solution electrolyte composed of a solvent and an ionic liquid, a high-viscosity electrolyte or a gel electrolyte (hereinafter referred to as a solid electrolyte or a polymer compound substantially free of a solvent). , Gel electrolyte).

[White scattered matter]
In the display element of the present invention, it is preferable to contain a white scatterer from the viewpoint of further increasing the display contrast and white display reflectance, and a porous white scattering layer may be formed and present.

  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.

  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, zinc oxide, and zinc hydroxide are preferably used. In addition, titanium dioxide surface-treated with inorganic oxides (Al ₂ O ₃ , AlO (OH), SiO _2, etc.), in addition to these surface treatments, trimethylolethane, triethanolamine acetate, trimethylcyclosilane, etc. Titanium dioxide subjected to organic treatment can be 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, 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, cellulose derivatives, natural compounds such as starch, gum arabic, dextran, pullulan and carrageenan, and other natural compounds, polyvinyl alcohol, polyvinyl pyrrolidone, acrylamide polymers and their Examples include synthetic polymer compounds such as derivatives. Examples of gelatin derivatives include acetylated gelatin, phthalated gelatin, polyvinyl alcohol derivatives include 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 of the vinyl monomer having a (e.g., sodium methacrylate, Copolymers with ammonium acid, potassium acrylate, etc.) are also used. Two or more of these binders can be used in combination.

  In the present invention, gelatin and gelatin derivatives, or polyvinyl alcohol or derivatives thereof can be preferably used.

  Polymers dispersed in an aqueous solvent include natural rubber latex, styrene butadiene rubber, butadiene rubber, nitrile rubber, chloroprene rubber, isoprene rubber and other latexes, polyisocyanate, epoxy, acrylic, silicone, 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.

  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, 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.

  In the present invention, the medium for applying the water mixture of the water-based compound and the white pigment may be at any position as long as it is on the component between the counter electrodes of the display element, but on the electrode surface of at least one of the counter electrodes. It is preferable to give to. As a method for applying to a medium, for example, a coating method, a liquid spraying method, a spraying method via a gas phase, a method of flying droplets using vibration of a piezoelectric element, for example, a piezoelectric inkjet head, Examples thereof include a bubble jet (registered trademark) type ink jet head that causes droplets to fly using a thermal head that uses bumping, and a spray type that sprays liquid by air pressure or liquid pressure.

  The coating method can be appropriately selected from known coating methods. For example, an air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnation coater, reverse roller coater, transfer roller coater, curtain coater, double coater Examples include roller coaters, slide hopper coaters, gravure coaters, kiss roll coaters, bead coaters, cast coaters, spray coaters, calendar coaters, and extrusion coaters.

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

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

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

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

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

(Electronic insulation layer)
In the display element of the present invention, an electrical insulating layer can be provided.

  The electronic insulating layer applicable to the present invention may be a layer having both ionic conductivity and electronic insulating properties. For example, a solid electrolyte membrane in which a polymer or salt having a polar group is formed into a film, electronic insulating properties And a porous solid body having a low relative dielectric constant, such as a silicon-containing compound, and the like.

  As a method for forming a porous film, a sintering method (fusion method) (using fine pores formed between particles by adding polymer fine particles or inorganic particles to a binder or the like and partially fusing them), an extraction method ( After forming a constituent layer with a solvent-soluble organic substance or inorganic substance and a binder that does not dissolve in the solvent, the organic substance or inorganic substance is dissolved with the solvent to obtain pores), and the polymer is heated or degassed Known forming methods such as a foaming method in which foaming is performed, a phase change method in which a mixture of polymers is phase-separated by operating a good solvent and a poor solvent, and a radiation irradiation method in which pores are formed by radiating various types of radiation Can be used. Specifically, JP-A-10-30181, JP-A-2003-107626, JP-B-7-95403, JP-A-2635715, JP-A-2894523, JP-A-2987474, JP-A-3066426, and JP-A-3464513. No. 3,483,464, No. 3535942, No. 30622203, and the like.

[Thickener added with electrolyte]
In the display element of the present invention, a thickener can be used for the electrolyte. For example, gelatin, gum arabic, poly (vinyl alcohol), hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate, cellulose acetate butyrate, poly ( Vinylpyrrolidone), poly (alkylene glycol), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly ( Styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (PVC Redene), poly (epoxide) s, poly (carbonates), poly (vinyl acetate), cellulose esters, poly (amides), hydrophobic transparent binders such as polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, Examples include polycarbonate, polyacrylic acid, polyurethane 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.

[Other additives]
Examples of the constituent layers of the display element of the present invention include auxiliary layers such as a protective layer, a filter layer, an antihalation layer, a crossover light cut layer, and a backing layer. Sensitizer, noble metal sensitizer, photosensitive dye, supersensitizer, coupler, high boiling point solvent, antifoggant, stabilizer, development inhibitor, bleach accelerator, fixing accelerator, color mixing inhibitor, formalin scavenger, Toning agents, hardeners, surfactants, thickeners, plasticizers, slip agents, UV absorbers, anti-irradiation dyes, filter light absorbing dyes, anti-bacterial agents, polymer latex, heavy metals, antistatic agents, matting agents Etc. can be contained as required.

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

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

Additive RD17643 RD18716 RD308119
Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 96 III
Sensitizing dye 23 IV 648-649 996-8 IV
Desensitizing dye 23 IV 998 IV
Dye 25-26 VIII 649-650 1003 VIII
Development accelerator 29 XXI 648 Upper right Anti-fogging agent / stabilizer
24 IV 649 Upper right 1006-7 VI
Brightener 24 V 998 V
Hardener 26 X 651 Left 1004-5 X
Surfactant 26-7 XI 650 Right 1005-6 XI
Antistatic agent 27 XII 650 Right 1006-7 XIII
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
〔substrate〕
Examples of the substrate that can be used in the present invention include polyolefins such as polyethylene and polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylene dinaphthalene dicarboxylate, polyethylene naphthalates, polyvinyl chloride, polyimide, and polyvinyl acetal. Synthetic plastic films such as polystyrene can also be preferably used. Syndiotactic polystyrenes are also preferred. These can be obtained, for example, by the methods described in JP-A Nos. 62-117708, 1-46912 and 1-178505. Further, a metal substrate such as stainless steel, a paper support such as baryta paper and resin coated paper, and a support provided with a reflective layer on the plastic film, supported by JP-A-62-253195 (pages 29-31) The thing described as a body is mentioned. RDNo. 17643, page 28, ibid. No. 18716, page 647, right column to page 648, left column, and No. 307105, page 879 can also be preferably used. As these supports, those having resistance to curling due to heat treatment of Tg or less as in US Pat. No. 4,141,735 can be used. Further, the surface of these supports may be subjected to surface treatment for the purpose of improving the adhesion between the support and other constituent layers. In the present invention, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, and flame treatment can be used as the surface treatment. Furthermore, the support body described in pages 44 to 149 of publicly known technology No. 5 (issued by Aztec Co., Ltd. on March 22, 1991) can also be used. Furthermore, RDNo. 308119, page 1009, Product Licensing Index, Volume 92, P108, “Supports”, and the like. In addition, a glass substrate or an epoxy resin kneaded with glass can be used.

〔electrode〕
In the display element of the present invention, it is preferable that at least one of the counter electrodes is a metal electrode. As the metal electrode, for example, known metal species such as platinum, gold, silver, copper, aluminum, zinc, nickel, titanium, bismuth, and alloys thereof can be used. The metal electrode is preferably a metal having a work function close to the redox potential of silver in the electrolyte. Above all, silver or a silver electrode having a silver content of 80% or more is advantageous for maintaining the reduced state of silver. Excellent in preventing dirt. As an electrode manufacturing method, an existing method such as an evaporation method, a printing method, an ink jet method, a spin coating method, or a CVD method can be used.

  In the display element of the present invention, it is preferable that at least one of the counter electrodes is a 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 order to form the electrode in this manner, for example, an ITO film may be vapor-deposited on the substrate by a sputtering method or the like, or an ITO film may be formed on the entire surface and then patterned by a photolithography method. 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.

[Other components of the display element]
In the display element of the present invention, a sealant, a columnar structure, and spacer particles can be used as necessary.

  Sealing agent is for sealing so that it does not leak outside and is also called sealing agent. Epoxy resin, urethane resin, acrylic resin, vinyl acetate resin, ene-thiol resin, silicon resin, modified resin A curing type such as a polymer resin, such as a thermosetting type, a photocurable type, a moisture curable type, and an anaerobic curable type can be used.

  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 area of the display element is 1 to 40%, a practically sufficient strength as a display element can be obtained.

  A spacer may be provided between the pair of substrates for uniformly holding a gap between the substrates. Examples of the spacer include a sphere made of resin or inorganic oxide. Further, a fixed spacer whose surface is 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 a space holding member. May be used. When the columnar structure is formed, the diameter of the spacer is equal to or less than the height, 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.

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

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

Example 1
《Synthesis of polymer material》
(Synthesis of polymer material 1)
A schematic structure of the polymer material 1 according to the present invention is shown below. The polymer material 1 according to the present invention has a configuration including a bisterpyridine derivative 110 that is a ligand, a metal ion M, and a counter anion. The plurality of repeating units of the polymer material 1 shown below is 110.

  Next, the manufacturing method of the polymeric material 1 which concerns on this invention is demonstrated for every process.

  Step S110: The polymer material 1 was obtained by refluxing the bisterpyridine derivative represented by the exemplified compound 1 and the iron salt in acetic acid and methanol.

  In step S110, acetic acid and methanol function as a solvent for bisterpyridine derivative 110 and metal salt M (iron salt), respectively. The reflux was performed at a temperature of 150 ° C. for 24 hours.

(Synthesis of polymer material 2)
A schematic structure of the polymer material 2 according to the present invention is shown below. The polymer material 2 according to the present invention has a configuration including bisterpyridine derivatives 210 and 220 which are ligands, first to Nth metal ions, and first to Nth counter anions. Here, N is an integer of 2 or more.

  Next, the manufacturing method of the polymeric material 2 which concerns on this invention is demonstrated for every process.

  Step S210: The bisterpyridine derivative and iron salt represented by Exemplary Compound 1 were refluxed in acetic acid and methanol, respectively, to obtain a polymer compound 2a. Next, the bister pyridine derivative represented by the exemplified compound 1 and the ruthenium salt were refluxed in acetic acid and methanol, respectively, to obtain a polymer compound 2b.

  In step S210, as in step S110, acetic acid and methanol function as a solvent for the bisterpyridine derivative and the metal salt. The reflux was performed at a temperature of 150 ° C. over 24 hours.

  Step S220: Polymer compound 2a and polymer compound 2b respectively obtained in step S210 were mixed. The mixing was performed by stirring for 2 hours at room temperature, to obtain a polymer material 2 in which a plurality of elements 210 and a plurality of elements 220 as shown below were bonded in a self-aligning manner.

  It can also obtain by heating the obtained mixture after process S220. The solvent is evaporated by heating to a powder. At this time, the powder has a color in which a plurality of colors are mixed, and the contained metal ions are in a reduced state.

(Synthesis of polymer material 3)
In the synthesis of the polymer material 1, the polymer material 3 was obtained in the same manner except that the bisterpyridine derivative was changed from the exemplified compound 1 to the exemplified compound 8.

(Synthesis of polymer material 4)
In the synthesis of the polymer material 1, the polymer material 4 was obtained in the same manner except that the bisterpyridine derivative was changed from the exemplified compound 1 to the exemplified compound 6.

<Adjustment 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.

(Preparation of electrolyte 2)
0.05 g of Exemplified Compound (A) -24 and 0.05 g of tetrabutylammonium perchlorate were dissolved in 2.5 g of acetonitrile to obtain an electrolytic solution 2.

(Preparation of electrolytes 3-7)
In the preparation of the electrolytic solution 2, electrolytic solutions 3 to 7 were obtained in the same manner except that the exemplary compound (A) -24 was changed to each exemplary compound shown in Table 1.

<Production of electrode>
(Production of electrode 1)
An ITO (Indium Tin Oxide) film was formed on a 2 cm × 4 cm glass substrate having a thickness of 1.5 mm according to a known method to obtain a transparent electrode (electrode 1).

(Preparation of electrode 2)
Using a known method, a nickel electrode having an electrode thickness of 0.1 μm is formed on a glass substrate having a thickness of 1.5 mm and 2 cm × 4 cm, and the obtained electrode is further immersed in a displacement gold plating bath. A gold-nickel electrode (electrode 2) having a depth of 0.05 μm replaced with gold was obtained.

(Preparation of electrode 3)
A solution obtained by dissolving the polymer material 1 obtained above in ethanol is applied onto the electrode 1 by the blade method, heated at 85 ° C. for 1 minute to evaporate the ethanol, and a polymer film is formed on the electrode 1. As a result, an electrode 3 was obtained.

(Production of electrodes 4 to 6)
Electrodes 4 to 6 were produced in the same manner as in the production of the electrode 3 except that the polymer material 1 was changed to each polymer material shown in Table 1.

<< Production of display element >>
(Preparation of display element 1)
The periphery of the electrode 2 is edged with an olefin-based sealant containing 10% glass spherical beads having an average particle diameter of 40 μm as a volume fraction, and then bonded so that the electrode 3 and the electrode 2 are orthogonal to each other, and further heated and pressed Thus, an empty cell was produced. 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.

(Production of display elements 2 to 7)
Display elements 2 to 7 were produced in the same manner as in the production of the display element 1 except that the electrolytic solution 1 was changed to the electrolytic solutions 2 to 7.

(Preparation of display element 8)
The periphery of the electrode 2 is edged with an olefin-based sealant containing glass spherical beads having an average particle size of 40 μm as a volume fraction of 10%, and then bonded so that the electrode 4 and the electrode 2 are orthogonal to each other, and further heated and pressed Thus, an empty cell was produced. 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 8.

(Preparation of display elements 9 and 10)
Display elements 9 and 10 were produced in the same manner as in the production of the display element 8 except that the electrolytic solution 1 was changed to the electrolytic solutions 3 and 5, respectively.

(Preparation of display element 11)
The periphery of the electrode 2 is bordered with an olefin-based sealant containing 10% glass spherical beads having an average particle diameter of 40 μm as a volume fraction, and then bonded so that the electrode 5 and the electrode 2 are orthogonal to each other, and further heated and pressed Thus, an empty cell was produced. 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 11.

(Production of display elements 12 and 13)
Display elements 12 and 13 were produced in the same manner as in the production of the display element 11 except that the electrolytic solution 1 was changed to the electrolytic solutions 3 and 5, respectively.

(Preparation of display element 14)
The periphery of the electrode 2 is bordered with an olefin-based sealant containing 10% glass spherical beads having an average particle diameter of 40 μm as a volume fraction, and then bonded so that the electrode 6 and the electrode 2 are orthogonal, and further heated and pressed. Thus, an empty cell was produced. The electrolytic solution 1 was vacuum-injected into the empty cell, and the injection port was sealed with an epoxy-based ultraviolet curable resin, whereby a display element 14 was produced.

(Preparation of display elements 15 and 16)
Display elements 15 and 16 were produced in the same manner as in the production of the display element 14 except that the electrolytic solution 1 was changed to the electrolytic solutions 3 and 5, respectively.

<< Evaluation of display element >>
[Observation of color change]
The undriven state of each display element and the color tone after application were visually observed.

[Evaluation of contrast]
(Evaluation of display elements 1 to 7)
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 manufactured are connected to both terminals of the constant voltage power source, and the reflectance after applying a voltage of +1.8 V for 3 seconds is similarly used, and the reflectance at the wavelength at which R ₀ is obtained. R ₁ . _{It was set to 8} . CR = R ₁ . ₈ / _R0, and CR was used as an index of contrast of the display element. Here, the greater the CR value, the higher the contrast. The obtained results are shown in Table 1.

(Evaluation of display elements 8 to 10)
Contrast was evaluated in the same manner as display elements 1-7. The obtained results are shown in Table 1.

(Evaluation of display elements 11-13)
The contrast was evaluated in the same manner as the display elements 1 to 7 except that the applied voltage was changed to + 1.6V. The obtained results are shown in Table 1.

(Evaluation of display elements 14 to 16)
The contrast was evaluated in the same manner as the display elements 11 to 13. The obtained results are shown in Table 1.

  As is apparent from the results shown in Table 1, it can be seen that the display element according to the present invention has a higher contrast when the same voltage is applied than the comparative display element.

Claims (16)

Between the counter electrodes, an electrolyte containing a compound represented by the following general formula (A) or a compound represented by the general formula (B), and a white scattering material, and at least one counter electrode is A display element, wherein a polymer material represented by the general formula (1) is fixed.

[Wherein, Ra ₁ , Ra ₂ , Rb ₁ and Rb ₂ each independently represent an aromatic hydrocarbon group, an aromatic heterocyclic group or an aliphatic hydrocarbon group which may have a substituent. Ra ₁ and Ra ₂ , Rb ₁ and Rb ₂ may be connected to each other to form a cyclic structure. ]

[The polymer compound represented by the general formula (1) is a polymer compound containing a bisterpyridine derivative, a metal ion, and a counter anion, wherein M represents a metal ion, and X represents a counter anion. R represents a spacer containing a carbon atom and a hydrogen atom or directly connecting a terpyridyl group, and R ¹ , R ² , R ³ and R ⁴ are all the same, all different or partly the same. In the formula, n represents an integer of 2 or more representing the degree of polymerization. ] 2. The display element according to claim 1, wherein the metal ion M in the general formula (1) is at least one selected from iron ion, cobalt ion, ruthenium ion, nickel ion, and zinc ion. The counter anion in the general formula (1) is at least one selected from the group consisting of acetate ions, boron tetrafluoride ions, polyoxymetalates, and combinations thereof. The display element as described. The display element according to claim 1, wherein the spacer in the general formula (1) is an aryl group or an alkyl group. The display element according to claim 4, wherein the aryl group or the alkyl group further contains an oxygen atom or a sulfur atom. The display element according to claim 4, wherein the aryl group is at least one selected from the group consisting of the following formulas [1] to [4].

The polymer material represented by the general formula (1) is produced by a method including a step of refluxing a bisterpyridine derivative represented by the following general formula (2) and a metal salt in acetic acid and methanol. The display element according to claim 1, wherein the display element is a display element.

[In the formula, R represents a spacer containing a carbon atom and a hydrogen atom, or directly connecting a terpyridyl group, and R ¹ , R ² , R ³ and R ⁴ are all the same, all different or a part. It represents the same hydrogen atom, aryl group or alkyl group, and n is an integer of 2 or more representing the degree of polymerization. ] The display element according to claim 1, wherein white display and color display of two or more colors are performed by driving the counter electrode. Between the counter electrodes, there is an electrolyte containing a compound represented by the following general formula (A) or a compound represented by the general formula (B) and a white scattering material, and at least one counter electrode has the following general A display element, wherein a polymer material represented by formula (3) is fixed.

[Wherein, Ra ₁ , Ra ₂ , Rb ₁ and Rb ₂ each independently represent an aromatic hydrocarbon group, an aromatic heterocyclic group or an aliphatic hydrocarbon group which may have a substituent. Ra ₁ and Ra ₂ , Rb ₁ and Rb ₂ may be connected to each other to form a cyclic structure. ]

[The polymer compound represented by the general formula (3) includes first to N-th (N is an integer of 2 or more) bisterpyridine derivatives and first to N-th (N is an integer of 2 or more). A polymer material containing a metal ion and first to N-th (N is an integer of 2 or more) counter anions, wherein M ¹ ,..., M ^N (N is an integer of 2 or more) ) Represent the first to Nth metal ions that are all the same, all different, or partly the same, and X ¹ ,..., X ^N (N is an integer of 2 or more) are all the same, all Represents the first to N-th counter anions which are different or partly the same, and R ¹ ,..., R ^N (N is an integer of 2 or more) are all the same, all different or partly the same Represents a spacer containing a carbon atom and a hydrogen atom, or directly connecting a terpyridyl group, R ¹ ₁ ,..., R ^{1 _{N, R 2 1, ···,}} R 2 N, R 3 1, ···, R 3 N, R 4 1, ···, R 4 N (N is an integer of 2 or more) are all identical All represent different or partially the same hydrogen atom, aryl group or alkyl group, and n ¹ ,..., ^{N N} each represents an integer of 2 or more representing the degree of polymerization. ] The first to Nth metal ions in the general formula (3) are each at least one selected from the group consisting of iron ions, cobalt ions, ruthenium ions, nickel ions, and zinc ions. Item 10. The display element according to Item 9. The first to Nth counter anions in the general formula (3) are each at least one selected from the group consisting of acetate ions, boron tetrafluoride ions, polyoxymetalates, and combinations thereof. The display element according to claim 9 or 10. R ¹ in the general formula (3), ..., a spacer represented by R ^N are each according to any one of claims 9 to 11, characterized in that an aryl group or an alkyl group Display element. The display element according to claim 12, wherein the aryl group or the alkyl group further contains an oxygen atom or a sulfur atom. The display element according to claim 12 or 13, wherein the aryl group is at least one selected from the group consisting of the following formulas [1] to [4].

The polymer material represented by the general formula (3) includes first to N-th (N is an integer of 2 or more) bisterpyridine derivatives represented by the following general formula (4); Each of the N (N is an integer of 2 or more) metal salts is refluxed in acetic acid and methanol, and the first to Nth (N is an integer of 2 or more) obtained in the respective refluxing steps. The display element according to claim 9, wherein the display element is manufactured by a method including a step of mixing the reactants.

[Wherein, R ¹ ,..., R ^N (N is an integer of 2 or more) are all the same, all different, or partly the same, containing a carbon atom and a hydrogen atom, or a terpyridyl group Represents a directly connected spacer, R ¹ ₁ ,..., R ¹ _N , R ² ₁ ,..., R ² _N , R ³ ₁ , ..., R ³ _N , R ⁴ ₁ ,. , R ⁴ _n (n is an integer of 2 or more) are all the same, all different, or some the same hydrogen atom, an aryl group or an alkyl group, n ^1, ···, n ⁿ each polymerization It is an integer greater than or equal to 2 representing degrees. ] The display element according to any one of claims 9 to 15, wherein white display and color display of two or more colors are performed by driving the counter electrode.