WO2009116354A1 - Elément d'affichage - Google Patents

Elément d'affichage Download PDF

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Publication number
WO2009116354A1
WO2009116354A1 PCT/JP2009/053174 JP2009053174W WO2009116354A1 WO 2009116354 A1 WO2009116354 A1 WO 2009116354A1 JP 2009053174 W JP2009053174 W JP 2009053174W WO 2009116354 A1 WO2009116354 A1 WO 2009116354A1
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Prior art keywords
group
compound
general formula
display element
display
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PCT/JP2009/053174
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English (en)
Japanese (ja)
Inventor
香織 大野
修 石毛
健 波木井
典之 苔口
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コニカミノルタホールディングス株式会社
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Priority to JP2010503808A priority Critical patent/JP5287849B2/ja
Publication of WO2009116354A1 publication Critical patent/WO2009116354A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1503—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions

Definitions

  • the present invention relates to a novel electrochemical display element that does not leak an organic solvent or the like and can be driven at a low voltage and has high durability.
  • a conventional liquid crystal display or CRT As a means for browsing such electronic information, a conventional liquid crystal display or CRT, and in recent years, a light emitting type such as an organic EL display is mainly used.
  • the electronic information is document information, it is relatively long time. It is necessary to pay close attention to this browsing means, and these actions are not human-friendly means.
  • eyes flicker due to flickering, inconvenient to carry, reading posture is limited, It is known that it is necessary to adjust the line of sight to a still screen, and that power consumption increases when read for a long time.
  • the method using a polarizing plate such as a reflective liquid crystal has a low reflectance of about 40%, and thus it is difficult to display white, and many of the manufacturing methods used to manufacture the constituent members are not easy.
  • 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.
  • the polymer network type liquid crystal has problems such as a high driving voltage and a complicated TFT circuit required to improve the memory performance.
  • 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.
  • EC method electrochromic display element
  • ED method electrodeposition method
  • the EC method has the advantage of being capable of full-color display at a low voltage of 3V or less, a simple cell configuration, and excellent white quality.
  • the ED method can also be driven at a low voltage of 3V or less and is a simple cell.
  • advantages such as excellent configuration, black-white contrast and black quality, and various methods have been disclosed (see, for example, Patent Documents 1 to 5).
  • liquid electrolyte in which a supporting electrolyte is dissolved in water or an organic solvent has been used as an electrolyte of many electrochemical elements.
  • the liquid electrolyte has problems in that it is difficult to leak the electrolyte due to aging or damage due to long-term storage of the electrochemical element, and to reduce the size and thickness.
  • EC-type or ED-type display elements need to be sealed with a transparent material such as glass or plastic in at least one direction for use in display applications. It is difficult to end up. For this reason, leakage and volatilization of the electrolyte become a larger problem.
  • solid thin film electrolyte materials that solidify electrolytes, are easy to handle, have high safety, and have a high ion transport number have been actively conducted.
  • a solid polymer electrolyte in which a supporting electrolyte is dissolved in a polymer having a polyether structure such as polyethylene oxide, polypropylene oxide, or a derivative or copolymer thereof.
  • a polymer having a polyether structure can dissolve one monovalent cation with four oxygen atoms in the ether structure. Since such a solid electrolyte basically does not contain a solution such as an organic solvent, the possibility of leakage is low, but its electrical conductivity is about three orders of magnitude lower than that of a normal non-aqueous electrolyte. have.
  • a gel electrolyte including a liquid electrolyte in a polymer matrix having a network structure.
  • a polymerization reaction is performed in a liquid electrolyte mixed with a monomer to produce a polymer swollen with the liquid electrolyte, and a polymer matrix that has been polymerized in advance is immersed in the liquid electrolyte to swell the polymer.
  • the polymer matrix basically has a function including a liquid electrolyte and does not contribute to ionic conduction, so that sufficient conductivity cannot be obtained.
  • an aprotic gelling agent can efficiently gel a polar organic solvent and a hydrogen bonding organic solvent, and is preferable as a gel electrolyte.
  • it only shows the gelation ability for various solvents, it does not indicate whether or not the electrolyte containing various additives can be gelled, and reflectivity when it is driven repeatedly. It has not been suggested that the stabilizing effect is obtained.
  • the present invention has been made in view of the above problems, and its object is a display element that can be driven with a simple member configuration, low voltage, high display contrast, and high white display reflectance, and can be driven repeatedly.
  • An object of the present invention is to provide a display element with little variation in reflectance.
  • An opposing electrode containing an electrolyte, a compound that changes color reversibly by an electrochemical redox reaction, and an auxiliary compound that can be redoxed to promote the electrochemical redox reaction, between at least a pair of opposing electrodes A display element that displays white and colored by the driving operation, wherein the electrolyte contains a compound represented by the following general formula (1).
  • G represents an oxygen atom or a sulfur atom
  • R 1 to R 5 each represents a hydrogen atom or a substituent.
  • L represents a divalent linking group, and n represents 0 or 1.
  • Ar represents a divalent aromatic group which may have a substituent, and R represents a substituent having 2 to 20 carbon atoms.
  • G in the general formula (1) is an oxygen atom.
  • Ar represents a divalent aromatic group which may have a substituent
  • R represents a substituent having 2 to 20 carbon atoms.
  • Rl 1 represents a substituted or unsubstituted aryl group
  • 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
  • Rl 4 represents a hydrogen atom or a substituent.
  • the multi-color display of three or more colors of substantially black display, white display, and colored display other than black is performed by the driving operation of the opposing electrodes, according to any one of 1 to 8 above Display element.
  • a display element that has a simple member configuration, can be driven at a low voltage, has a high display contrast, and a high white display reflectance, and has a small change in reflectance in repeated driving. It was.
  • the present inventor can be subjected to redox that promotes an electrochemical reaction between an electrolyte, an electrochromic compound, a white scatterer, and the electrochromic compound between at least a pair of opposing electrodes.
  • the electrolyte contains a compound represented by the general formula (1)
  • the present inventors have found that a display element that has a simple member configuration, can be driven at a low voltage, has a high display contrast, and a high white display reflectance, and that has a small change in reflectance in repeated driving can be realized. It depends on you.
  • ⁇ Basic configuration of display element In the display element of the present invention, a pair of opposed electrodes is provided. Of the opposing electrodes, the electrode 1 (hereinafter also referred to as display electrode) close to the display portion is provided with a transparent electrode such as an ITO electrode, and the other electrode 2 (hereinafter also referred to as counter electrode) is provided with a conductive electrode. ing. Between the electrode 1 and the electrode 2, the electrolyte which concerns on this invention and the compound which changes color reversibly by an electrochemical oxidation-reduction reaction are contained.
  • the white and various colored states can be reversibly achieved by the oxidation / reduction coloring / decoloring reaction of the compound that reversibly discolors by the electrochemical oxidation-reduction reaction. Can be switched.
  • an auxiliary compound that can be oxidized and reduced, which will be described later, is added in order to promote the electrochemical reaction of the compound that reversibly changes color due to the electrochemical oxidation-reduction reaction.
  • Examples of the compound that reversibly discolors by an electrochemical redox reaction include a metal salt compound that dissolves and precipitates reversibly by an electrochemical redox reaction with an electrochromic compound.
  • a preferred embodiment is that both an electrochromic compound and a metal salt compound are contained as a compound that reversibly changes color by an electrochemical redox reaction.
  • black and white display accompanying dissolution and precipitation of the metal salt compound is performed, combined with coloring and decoloring reactions by oxidation and reduction of the electrochromic compound, The state colored in colors other than black, white, and black can be switched reversibly.
  • a more preferred embodiment of the present invention is an embodiment in which the electrochromic compound is immobilized on the transparent electrode 1 (display electrode) on the display side.
  • Electrode In the display element of the present invention, it is preferable to use a transparent electrode as an electrode (display electrode) close to the display portion among the pair of opposed electrodes.
  • the transparent electrode is not particularly limited as long as it is transparent and conducts electricity.
  • ITO Indium Tin Oxide
  • IZO Indium Zinc Oxide
  • FTO Fluorine Doped Tin Oxide
  • ITO Indium Tin Oxide
  • Zinc Oxide Platinum, Gold, Silver, Rhodium, Copper
  • Examples thereof include chromium, carbon, aluminum, silicon, amorphous silicon, and BSO (Bismuth Silicon Oxide).
  • 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 100 ⁇ / ⁇ or less, and more preferably 10 ⁇ / ⁇ or less.
  • the thickness of the transparent electrode is not particularly limited, but is generally 0.1 to 20 ⁇ m.
  • a semiconductor nanoporous layer can be formed on the transparent electrode on the display portion side in order to fix a dye or the like.
  • the semiconductor nanoporous layer has micropores capable of supporting an EC dye or the like on the surface and inside thereof.
  • the specific surface area of the semiconductor nano-porous layer is preferably 1 ⁇ 5000m 2 / g, more preferably 10 ⁇ 2500m 2 / g.
  • the specific surface area means the BET specific surface area obtained from the adsorption amount of nitrogen gas. If the specific surface area is in the above range, a desired EC dye adsorption amount can be obtained, which is preferable.
  • the semiconductor fine particles contained in the semiconductor nanoporous layer are not particularly limited and can be appropriately selected according to the purpose.
  • single semiconductors, oxide semiconductors, compound semiconductors, organic semiconductors, composites An oxide semiconductor or a mixture thereof can be given, and these may contain impurities as a dopant.
  • the form of the semiconductor There is no particular limitation on the form of the semiconductor, and it may be single crystal, polycrystal, amorphous, or a mixed form thereof.
  • the semiconductor fine particles are preferably oxide semiconductors.
  • An oxide semiconductor is a metal oxide and has semiconductor properties. For example, TiO 2 , SnO 2 , Fe 2 O 3 , SrTiO 3 , WO 3 , ZnO, ZrO 2 , Ta 2 O 5 , Nb 2 O 5 , V 2 O 5 , In 2 O 3 , CdO, MnO, CoO, TiSrO 3 , KTiO 3 , Cu 2 O, sodium titanate, barium titanate, potassium niobate, and the like.
  • the shape of the semiconductor fine particles is not particularly limited and can be appropriately selected according to the purpose.
  • the shape may be any of a spherical shape, a nanotube shape, a rod shape, and a whisker shape, and two or more types having different shapes may be used.
  • Fine particles can also be mixed.
  • the average particle size is preferably 0.1 to 1000 nm, more preferably 1 to 100 nm.
  • Two or more kinds of fine particles having different particle size distributions may be mixed.
  • the aspect ratio is preferably 2 to 50000, more preferably 5 to 25000.
  • Counter electrode In the display element of the present invention, a metal electrode or a carbon electrode is used as an electrode (counter electrode) on the non-display portion side of the pair of opposed electrodes.
  • 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.
  • 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.
  • 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.
  • Porous carbon electrodes that can be adsorbed and supported include graphite, non-graphitizable carbon, graphitizable carbon, composite carbon, and carbon compounds obtained by doping carbon with boron, nitrogen, phosphorus, etc. Can be mentioned.
  • Examples of the shape of the carbon particles include mesophase microspheres and fibrous graphite.
  • Mesophase spherules can be obtained by firing coal tar pitch or the like at 350 to 500 ° C., and further classifying these spherules and graphitizing by high-temperature firing can provide a good porous carbon electrode.
  • fibrous graphite can be obtained from pitch-based, PAN-based, and vapor-grown fibers.
  • the electrolyte contains a compound (gelator) represented by the general formula (1), and further, the compound represented by the general formula (1) It is preferable that it is a compound represented by the said General formula (2).
  • G represents an oxygen atom or a sulfur atom
  • R 1 to R 5 each represents a hydrogen atom or a substituent
  • L represents a divalent linking group
  • n represents 0 or 1.
  • Ar represents a divalent aromatic group which may have a substituent
  • R represents a substituent having 2 or more carbon atoms.
  • G represents an oxygen atom or a sulfur atom, preferably an oxygen atom.
  • R 1 to R 5 each represent a hydrogen atom or a substituent, and the substituent is not particularly limited, but is a halogen atom (eg, fluorine, chlorine, bromine, iodine, etc.), an alkyl group (For example, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl, chloromethyl, trifluoromethyl, Trichloromethyl group, tribromomethyl group, pentafluoroethyl group, methoxyethyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group ( For example,
  • R 1 to R 5 are all hydrogen atoms.
  • L represents a divalent linking group
  • n represents 0 or 1.
  • the divalent linking group represented by L is not particularly limited and includes, for example, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a butylene group, etc.), an arylene group (for example, a phenylene group), an alkenylene.
  • R 6 represents an alkyl group, an aryl group, a hydrogen atom
  • a heterocyclic divalent group for example, triazine-2,4-diyl group, pyrimidine-2,4-diyl group, thiazole-2,4) -Diyl group, benzoxazole-2,5-diyl group, etc.
  • n represents 0 or 1, but is preferably 1.
  • Ar represents a divalent aromatic group which may have a substituent, and may be a divalent aromatic hydrocarbon group or an aromatic heterocyclic group.
  • Examples thereof include a pyridylene group and a pyrimidylene group.
  • Preferred are a phenylene group, a biphenylene group and a naphthylene group, which may have a substituent, and more preferred are a phenylene group and a biphenylene group.
  • R represents a substituent having 2 to 20 carbon atoms and is not particularly limited, but is an alkyl group (for example, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group).
  • alkyl group Preferred are an alkyl group, an alkoxy group, an alkylthio group, and a dialkylamino group, and more preferred is an alkoxy group.
  • the number of carbon atoms is preferably 14 or less, and more preferably 12 or less, from the viewpoint of easy availability of raw materials and ease of handling.
  • Ar represents a divalent aromatic group which may have a substituent.
  • Examples of the divalent aromatic group which may have a substituent include the above-described general formula (1).
  • R represents a substituent having 2 to 20 carbon atoms, and examples of the substituent include the same substituents as R in the general formula (1).
  • addition amount of the compounds represented by the general formula (1) and the general formula (2) it can be used in the range of 0.1% by mass to 30% by mass with respect to the electrolyte solvent to be used.
  • a preferable addition amount is in the range of 0.5% by mass to 10% by mass, and a range of 1% by mass to 5% by mass is particularly preferable.
  • 2,5-Dimethoxybenzaldehyde and malonic acid are led to 2,5-dimethoxycinnamic acid by Knoevenagel condensation reaction, and the terminal carboxylic acid is protected with ethyl ester, and then boron tribromide is used to deprotect the methyl ether.
  • a cyclization reaction was simultaneously performed to obtain 6-hydroxycoumarin.
  • Exemplified compound (1) can be obtained by reacting the obtained 6-hydroxycoumarin with 4-propoxybenzoic acid chloride.
  • Examples of the compound reversibly discolored by the electrochemical redox reaction according to the present invention include an electrochromic compound and a metal salt compound described below.
  • 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 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.
  • organometallic complexes, conductive polymer compounds, and organic dyes are known.
  • organometallic complexes 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.
  • a polymer material composed of a bisterpyridine derivative and a metal ion as described in JP-A-2007-112957 also exhibits electrochromic properties.
  • organic dyes exhibiting 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.
  • 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.
  • redox indicators and pH indicators can also be used.
  • 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 compound that changes from one specific color to another by redox.
  • Class 2 EC compound that is substantially colorless in an oxidized state and exhibits a specific colored state in a reduced state.
  • Class 3 EC compound that is substantially colorless in the reduced state and exhibits a specific colored state in the oxidized state.
  • the above class 1 to class 3 EC compounds can be appropriately selected depending on the purpose and application.
  • 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.
  • V 2 O 5 changes from an orange state to a green color by changing from an oxidation state to a reduction state
  • Rh 2 O 3 changes from a yellow color to a dark green color
  • 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.
  • polythiophene changes from blue to red by changing from an oxidized state to a reduced state
  • polypyrrole changes from brown to yellow
  • 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 they are a single compound and can be displayed in multiple colors, but have the disadvantage that they cannot be made virtually colorless.
  • 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.
  • organometallic complexes classified as class 2 include tris (vasophenanthroline) iron (II) complexes, which show red in the reduced state.
  • 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′-biphenyl. Examples thereof include diethyl carboxylate (yellow), 1,4-diacetylbenzene (cyan), and tetrazolium salt compounds described in JP-A-1-230026 and JP-T-2000-504964.
  • 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.
  • pyridinium-based compounds such as viologen
  • examples of pyridinium-based compounds such as viologen include compounds described in the following patents, including JP-T 2000-506629.
  • pyridinium compounds such as viologen that can be used in the present invention are shown below, but are not limited thereto.
  • EC compounds belonging to class 3 are compounds that are colorless or extremely light in a reduced state and exhibit a specific colored state that is an oxidized state.
  • inorganic compounds classified as class 3 include iridium oxide (dark blue), Prussian blue (blue), etc. (each exhibiting the color shown in parentheses in the oxidized state).
  • conductive polymers classified into class 3 There are few examples of conductive polymers classified into class 3, but examples include phenyl ether compounds described in JP-A-6-263846.
  • 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. .
  • styryl dyes examples include styryl dyes, azine dyes, and azole dyes that can be used in the present invention are shown below, but the invention is not limited thereto.
  • 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.
  • 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.
  • the most preferable dye is a compound represented by the general formula (L).
  • Rl 1 represents a substituted or unsubstituted aryl group
  • 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
  • Rl 4 represents a hydrogen atom or a substituent.
  • 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, cycloalkenyl , 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, piperid
  • Rl 1 is preferably a substituted or unsubstituted phenyl group, more preferably a substituted or unsubstituted 2-hydroxyphenyl group or 4-hydroxyphenyl group.
  • 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.
  • 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.
  • 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, an acyl group It is a group.
  • the compound represented by the general formula (L) has an adsorptive group that chemically or physically adsorbs 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
  • 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.
  • the adsorptive group is preferably a chemisorbable group
  • the chemisorbable adsorptive groups include —COOH, —P ⁇ O (OH) 2 , —OP ⁇ O (OH) 2 and —Si (OR) 3 (R represents an alkyl group) is preferred.
  • an imidazole dye represented by the following general formula (L2) is particularly preferable.
  • Rl 21 and Rl 22 each represents an aliphatic group, an aliphatic oxy group, an acylamino group, a carbamoyl group, an acyl group, a sulfonamide group, or a sulfamoyl group
  • R1 23 represents an aromatic group or an aromatic group
  • Rl 24 represents a hydrogen atom, an aliphatic group, an aromatic group or an aromatic heterocyclic group
  • RL 25 represents a hydrogen atom, an aliphatic group, an aromatic group or an acyl group.
  • Rl 21 to Rl 25 may be further substituted with an arbitrary substituent. However, at least one of the groups represented by Rl 21 to Rl 25 has —COOH, —P ⁇ O (OH) 2 , —OP ⁇ O (OH) 2 and —Si (OR) 3 ( R represents at least one selected from an alkyl group.
  • 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.
  • At least one of the groups represented by Rl 21 to Rl 25 has a partial structure of —P ⁇ O (OH) 2 or —Si. It is preferable to have (OR) 3 (R represents an alkyl group), and in particular, as a partial structure of the group represented by Rl 23 or Rl 24 , —Si (OR) 3 (R represents an alkyl group) It is preferable to have.
  • an auxiliary compound that can be oxidized and reduced is added in order to promote the electrochemical reaction of the compound that reversibly discolors due to the electrochemical redox reaction.
  • 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 fixed on the electrode, or may be added to the electrolyte.
  • These promoters can be used, for example, as counter electrode reactants or as redox mediators.
  • 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.
  • a promoter 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. .
  • the promoter does not change the optical density in the visible region (400 to 700 nm) as a result of the redox reaction.
  • 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.
  • the mediator 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.
  • the display element when a compound that reversibly changes color by an electrochemical redox reaction that oxidizes and develops as the substrate, the display element is driven at a low driving voltage by coexisting a catalytic amount of an oxidation mediator.
  • This makes it possible to increase the durability of the display element.
  • there are advantages such as an improvement in display switching speed and high color development efficiency.
  • 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.
  • a single mediator may be used, or a plurality of mediators may be used in combination.
  • a promoter 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.
  • a promoter may be used as a counter electrode reactant or a mediator.
  • a plurality of promoters may be used in combination at the same time.
  • the promoter is not particularly limited and may be appropriately selected depending on the purpose.
  • when used as a counter electrode reactant it is possible to use a compound that reversibly discolors by a known electrochemical redox reaction.
  • 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.
  • Examples of preferred promoters that can be used in the present invention include the following compounds.
  • 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
  • a compound having an allyloxy free radical having a bulky substituent introduced at the 0-position, such as galvinoxyl such as galvinoxyl
  • metallocene derivatives such as ferrocene
  • benzyl (diphenylethanedione) derivative 5) Tetrazolium salt / formazan derivative
  • Azine compounds such as phenazine, phenothiazine, phenoxazine, acridine
  • pyridinium compounds such as viologen
  • hydrazyl free radical compounds such as benzoquinone derivatives, verdazyl, thiazyl free radical compounds, hydrazone derivatives, phenylenediamine derivatives, triallylamine derivatives, te
  • promoters in the categories 1) to 7) are preferable, and 1) is particularly preferable.
  • N-oxyl also called nitroxide radical
  • nitroxide radical is an oxygen-centered radical generated by radically cleaving the oxygen-hydrogen bond of hydroxylamine.
  • the nitroxide radical is known to have two reversible redox pairs as shown in the following scheme.
  • the nitroxide radical becomes an oxoammonium cation by one-electron oxidation, and this is reduced to regenerate the radical.
  • the nitroxide radical becomes 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.
  • oxoammonium cation has a high oxidation ability and can function as a mediator because it can oxidize leuco dyes and the like.
  • the N-oxyl derivative may be contained in the electrolyte or may be immobilized on the electrode surface.
  • Examples of the method of immobilizing on the electrode surface include a method of introducing a group that chemically or physically adsorbs with the electrode surface into the N-oxyl derivative, and a method of polymerizing the N-oxyl derivative to form a thin film on the electrode surface. It is done.
  • the N-oxyl derivative may be added in the form of an N-oxyl radical, or in the form of an N-hydroxy compound, and further in the form of an oxoammonium cation.
  • N-oxyl derivatives derivatives substituted with various substituents such as TEMPO (2,2,6,6-tetramethylpiperidinyl-N-oxyl) are commercially available.
  • various derivatives including polymers can be easily synthesized according to known literature.
  • N-hydroxyphthalimide derivatives N-hydroxyphthalimide derivatives, hydroxamic acid derivatives, etc.
  • PINO phthalimide N-oxyl
  • NHPI N-hydroxyphthalimide
  • the display element of the present invention is produced using these compounds, it is preferably added in the state of N—OH. After the display element is manufactured in the N—OH state, radicals are generated by driving the display element 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.
  • M1 general formula
  • M2 general formulas
  • M6 polycyclic N-oxyl derivative represented by the general formula (M6)
  • 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.
  • 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 can be referred to for synthesis.
  • 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.
  • substituents may further have a substituent.
  • 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, trimethylsilyleth
  • the compound represented by the general formula (M1) may be a multimer such as a dimer or a trimer linked by these substituents, or may be a polymer.
  • 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.
  • a polycyclic structure such as an azanorbornene structure or an azaadamantane structure is taken together with a nitrogen atom. Also good.
  • a piperidine ring, a pyrrolidine ring, or an azaadamantane ring is preferable.
  • the N-oxyl derivative according to the present invention is a compound represented by 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.
  • 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. Note that the compound represented by the general formula (M3) is preferably added in the state of N—OH to manufacture a display element.
  • the N-oxyl derivative according to the present invention is a compound represented by 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 manufacture a display element.
  • the N-oxyl derivative according to the present invention is a compound represented by the above 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).
  • 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.
  • Rm 52 to Rm 55 are preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.
  • 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 0 or 1
  • 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 in which other metals, compounds, etc., regardless of whether it is an electrolyte or a non-electrolyte, is referred to as an electrolyte ("broadly defined electrolyte").
  • the electrolyte solvent is not particularly limited, and specifically includes tetramethylurea, sulfolane, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, 2- (N-methyl) -2-pyrrolidinone.
  • examples of the solvent that can be used in the present invention include J. 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 Electrolytes Handbook”, Vol. 1, Academic Press (1972).
  • the boiling point of the solvent used in the electrolyte is not particularly limited, but is preferably a high boiling point from the viewpoint of preventing volatilization and production, and a solvent having a boiling point of 200 ° C. or higher is preferable.
  • particularly preferably used solvents are compounds represented by the following general formulas (S1) and (S2).
  • the electrolyte preferably contains a compound represented by the following general formula (S1) or (S2).
  • L represents an oxygen atom or an alkylene group
  • 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.
  • 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.
  • L represents an oxygen atom or an alkylene group
  • 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.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group.
  • cycloalkyl group such as phenyl group, naphthyl group, etc.
  • cyclopentyl group examples include, for example, cyclopentyl group, cyclohexyl group, etc., alkoxyalkyl groups, such as ⁇ -methoxyethyl group, ⁇ -methoxypropyl group, etc. 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.
  • 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.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group.
  • cycloalkyl group such as phenyl group, naphthyl group, etc.
  • cyclopentyl group examples include, for example, cyclopentyl group, cyclohexyl group, etc., alkoxyalkyl groups, such as ⁇ -methoxyethyl group, ⁇ -methoxypropyl group, etc. 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.
  • the exemplary compounds (S1-1), (S1-2), and (S2-3) are particularly preferable.
  • the electrolyte solvent may be a single kind or a mixture of solvents, but a mixed solvent containing ethylene carbonate is preferred.
  • the addition amount of ethylene carbonate is preferably 10% by mass or more and 90% by mass or less of the total electrolyte solvent mass.
  • a particularly preferable electrolyte solvent is a mixed solvent having a mass ratio of propylene carbonate / ethylene carbonate of 7/3 to 3/7. When the propylene carbonate ratio is larger than 7/3, the ionic conductivity is inferior and the response speed is lowered. When the propylene carbonate ratio is smaller than 3/7, the electrolyte tends to be deposited at a low temperature.
  • the compound represented by the general formula (1) and the general formula (2) is included in the electrolyte, and is represented by the general formula (1) and the general formula (2) according to the present invention.
  • the resulting compound functions as a gelling agent in the electrolyte solvent.
  • the compounds represented by the general formula (1) and the general formula (2) according to the present invention form a three-dimensionally entangled fibrous network structure using ⁇ - ⁇ interaction as a driving force, It is considered that an organic gel is formed by forming a structure in which an electrolyte solvent is included in these voids.
  • Supporting electrolyte As the supporting electrolyte that can be used in the display element of the present invention, salts, acids, and alkalis that are usually used in the field of electrochemistry or the field of batteries can be used.
  • the salts are not particularly limited, 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 can be used.
  • 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 Li salt, Na salt having a counter anion selected from 6 ⁇ , AsF 6 ⁇ , CH 3 COO ⁇ , CH 3 (C 6 H 4 ) SO 3 ⁇ , and (C 2 F 5 SO 2 ) 3 C ⁇ K salt is mentioned.
  • 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
  • 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.
  • a cyclic quaternary ammonium salt is preferable, and a quaternary spiro ammonium salt is particularly preferable.
  • a counter anion ClO 4 ⁇ , BF 4 ⁇ , CF 3 SO 3 ⁇ , (C 2 F 5 SO 2 ) 2 N ⁇ and PF 6 — are preferable, and BF 4 ⁇ is particularly 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.
  • the following compounds may be added to the electrolyte in addition to the electrolyte solvent and the supporting electrolyte.
  • the metal salt compound according to the present invention is a salt containing a metal species that can be dissolved and precipitated by driving the opposing electrode on at least one electrode on a pair of opposing electrodes. Any compound may be used.
  • Preferred metal species are silver, bismuth, copper, nickel, iron, chromium, zinc and the like, and particularly preferred are silver and bismuth.
  • 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.
  • 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.
  • 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.
  • the molar concentration of halogen ions or halogen atoms contained in the electrolyte is [X] (mol / kg), and the concentration of metal ions contained in the electrolyte is [Metal] (mol / kg).
  • 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.
  • [X] / [Metal] is greater than 0.1, X ⁇ ⁇ X 2 is generated during the oxidation-reduction reaction of the metal ion, and X 2 easily cross-oxidizes with the deposited metal to form the deposited metal. Since it is one of the factors that cause dissolution and a decrease in memory properties, the molar concentration of halogen atoms is preferably as low as possible relative to the molar concentration of metal 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] it is preferable to contain a compound represented by the following general formula (G1) or general formula (G2) in order to promote dissolution and precipitation of metal salts (particularly silver salts).
  • the electrolyte preferably contains at least one compound represented by the following general formula (G1) or general formula (G2).
  • the compounds represented by the general formulas (G1) and (G2) are compounds that promote the solubilization of silver in the electrolyte in order to cause dissolution and precipitation of silver in the present invention.
  • Rg 11 -S-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.
  • 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.
  • Rg 11 and Rg 12 each represent a substituted or unsubstituted hydrocarbon group.
  • these hydrocarbon groups one or more nitrogen atoms, oxygen atoms, phosphorus atoms, and sulfur atoms are substituted.
  • Rg 11 and Rg 12 may be connected to each other to take a cyclic structure.
  • 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.
  • 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 COOH G1-12: HOOCCH 2 CH 2 SCH 2 CH 2 SCH 2 CH (OH)
  • Exemplified Compound G1-2 is particularly preferable from the viewpoint that the objective effect of the present invention can be exhibited.
  • 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.
  • 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 the 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.
  • Rg 21 is not particularly limited, and examples thereof include the following substituents.
  • Halogen atom eg, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
  • Alkyl group eg, methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl
  • aryl groups eg, phenyl, naphthyl, etc.
  • alkylcarbonamide groups eg, acetylamino, propionylamino, butyroylamino, etc.
  • arylcarbonamide groups for example, benzoylamino etc.
  • alkylsulfonamide groups eg methanesulfonylamino group, ethanesulfon
  • Exemplified Compounds G2-12, G2-18, and G2-20 are particularly preferable from the viewpoint that the objective effects of the present invention can be exhibited.
  • a white scattering material from the viewpoint of further increasing the display contrast and the white display reflectance, it is preferable to contain a white scattering material, 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 a water mixture of a water-based 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, acid 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.
  • 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
  • titanium dioxide zinc oxide, and zinc hydroxide are preferably used.
  • titanium dioxide surface-treated with inorganic oxides Al 2 O 3 , AlO (OH), SiO 2, etc.
  • trimethylolethane triethanolamine acetate, trimethylcyclosilane, etc.
  • titanium dioxide subjected to organic treatment can be used.
  • 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.
  • examples of the water-based polymer that is substantially insoluble in the electrolyte solvent include a water-soluble polymer and a polymer dispersed in the water-based solvent.
  • water-soluble polymers include proteins such as gelatin and gelatin derivatives, or cellulose derivatives, natural compounds such as starch, gum arabic, dextran, pullulan, and carrageenan, and the like, polyvinyl alcohol, polyvinyl pyrrolidone, acrylamide polymers, and the like. And synthetic polymer compounds such as derivatives thereof.
  • 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.
  • gelatin and gelatin derivatives, or polyvinyl alcohol or derivatives thereof can be preferably used.
  • Polymers dispersed in water-based solvents include natural rubber latex, styrene butadiene rubber, butadiene rubber, nitrile rubber, chloroprene rubber, isoprene rubber and other latexes, 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, the water-based polyurethane resin described in JP-A-10-76621 is preferably used.
  • substantially insoluble in the electrolyte solvent is defined as a state where 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.
  • the water mixture of the water-based polymer and the white pigment preferably has a form in which the white pigment is dispersed in water according to a known dispersion method.
  • the mixing ratio of the water-based polymer / white pigment is preferably 1 to 0.01 by volume, more preferably 0.3 to 0.05.
  • the medium for applying the water mixture of the water-based polymer and the white pigment may be at any position as long as it is on the constituent element between the electrodes facing each other in the display element, but at least one of the electrodes facing each other. It is preferable to apply on the electrode surface.
  • 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.
  • 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.
  • the drying of the water mixture of the water-based polymer and the white pigment applied on the medium may be performed by any method that can evaporate water. 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 a water mixture of the water-based polymer and white pigment applied on one electrode and dried to form a porous white scattering material, and then silver or silver on the scattering material. After applying an electrolyte solution containing a compound containing silver in the chemical structure, it can be sandwiched between opposing electrodes, giving a potential difference between the opposing electrodes, and causing a silver dissolution precipitation reaction. It means the penetrating state that can be moved by.
  • the display element of the present invention it is desirable to perform a curing reaction of the water-based polymer 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, US Pat. No. 4,678,739, column 41, US Pat. No. 4,791,042, JP-A-59-116655. And the hardening agents described in JP-A-62-245261, JP-A-61-18942, JP-A-61-249054, JP-A-61-245153, JP-A-4-218044, and the like.
  • 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).
  • gelatin it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination.
  • boron-containing compounds such as boric acid and metaboric acid.
  • hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of water-based polymer.
  • 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.
  • 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.
  • auxiliary layers such as a protective layer, a filter layer, an antihalation layer, a crossover light cut layer, and a backing layer.
  • Table 1 below shows the types of compounds and their locations shown in these three research disclosures.
  • 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.
  • 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
  • Japanese Patent Application Laid-Open No. Sho 62-253195 pages 29 to 31. What was described as a support 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.
  • 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.
  • 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.
  • glow discharge treatment ultraviolet irradiation treatment, corona treatment, and flame treatment can be used as the surface treatment.
  • the support described on pages 44 to 149 of publicly known technology No. 5 (issued by Aztec Co., Ltd. on March 22, 1991) can also be used.
  • a glass substrate or an epoxy resin kneaded with glass can be used.
  • Sealing agent is for sealing so that it does not leak to the outside and is also called sealing agent.
  • 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 to 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 maintaining a gap between the substrates.
  • the spacer include a sphere made of resin or inorganic oxide.
  • a fixed spacer having a surface coated with a thermoplastic resin is also preferably 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.
  • the method for controlling the transparent state and the colored state of the display element of the present invention is preferably determined based on the oxidation-reduction potential of the electrochromic dye and the precipitation overvoltage of silver ions.
  • a colored state other than black is shown on the oxidation side and a black state is shown on the reduction side.
  • the control method in this case by applying a noble voltage from the oxidation-reduction potential of the compound represented by the general formula (L), the compound represented by the general formula (L) is oxidized and blackened.
  • the compound represented by the general formula (L) is applied by applying a voltage between the oxidation-reduction potential of the compound represented by the general formula (L) and the deposition overvoltage of the silver compound.
  • silver is deposited on the electrode to show a black state, and is expressed by the oxidation potential of the deposited silver and the general formula (L).
  • a method of dissolving and decoloring the precipitated silver by applying a voltage between the oxidation-reduction potentials of the compound is mentioned.
  • 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.
  • 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 advantages such as gradation and memory function. For example, a circuit described in FIG. 5 of Japanese Patent Application Laid-Open No. 2004-29327 can be used.
  • 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.
  • 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.
  • Example 1 Production of display element >> [Production of display electrode] (Preparation of electrode A1) An ITO (Indium Tin Oxide) film having a pitch of 145 ⁇ m and an electrode width of 130 ⁇ m is 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 A1). It was.
  • ITO Indium Tin Oxide
  • Electrode A2 On the electrode A1, a titanium dioxide film having a thickness of 5 ⁇ m (about 4 to 10 particles having an average particle diameter of 17 nm was necked) was formed to obtain an electrode A2.
  • Electrode B1 A nickel electrode having an electrode thickness of 0.1 ⁇ m, a pitch of 145 ⁇ m, and an electrode interval of 130 ⁇ m is formed on a glass substrate having a thickness of 1.5 mm and a size of 2 cm ⁇ 4 cm by using a known method. To obtain a gold-nickel electrode (electrode B1) having a depth of 0.05 ⁇ m substituted with gold from the electrode surface.
  • the electrolyte solution 1-1 kept at 50 ° C. was injected under reduced pressure, and the injection port was sealed with an epoxy-based ultraviolet curable resin to produce a display element 1-1.
  • Display elements 1-2 to 1-15 were obtained in the same manner as in the production of the display element 1-1 except that the electrolytic solution 1-1 was changed to electrolytic solutions 1-2 to 1-15, respectively.
  • R ave2 was obtained by the same method.
  • ⁇ R COLOR1
  • the smaller the value of ⁇ R COLOR1 the better the stability of the reflectance when it is repeatedly driven.
  • Display element 1-2 to display element 1-15 were evaluated in the same manner as display element 1-1 except that the voltage applied to the display element was changed to the values shown in Table 3.
  • the display element 1-15 of the comparative example that does not use the gelling agent was driven at a low voltage and had a favorable performance with a small change in reflectance except that it was in a liquid state.
  • the driving speed gradually decreased and eventually the element stopped driving.
  • the display elements satisfying the configuration of the present invention have improved reflectance stability, display unevenness, and the like even when driven repeatedly.
  • Example 2 Production of display element >> As the display electrode and the counter electrode, the electrode A3 and the electrode B1 prepared in Example 1 were used, respectively.
  • the display element 2-1 was similarly performed except that the electrolytic solutions 2-1 to 2-12 prepared above were used instead of the electrolytic solution 1-1. ⁇ 2-12 were prepared.
  • Table 5 shows the evaluation results of each electrolytic solution and display element obtained as described above.
  • the display element satisfying the configuration of the present invention has improved reflectance stability, display unevenness, and the like when it is repeatedly driven as compared with the comparative example. .

Abstract

L'invention concerne un élément d'affichage qui peut être entraîné à une basse tension, tout en ayant une simple configuration d'organe, un haut contraste d'affichage et un haut facteur de réflexion d'affichage du blanc. L'élément d'affichage est supprimé dans des changements de facteur de réflexion pendant des opérations répétées. L'élément d'affichage contient, entre au moins une paire d'électrodes opposées, un électrolyte, un composé dont la couleur est changée de façon réversible par une réaction redox électrochimique, et un composé auxiliaire pouvant faire l'objet d'une réaction redox qui accélère la réaction redox électrochimique. L'élément d'affichage présente un affichage blanc ou coloré par entraînement de la paire d'électrodes opposées, et est caractérisé en ce que l'électrolyte contient un composé représenté par la formule générale (1).
PCT/JP2009/053174 2008-03-18 2009-02-23 Elément d'affichage WO2009116354A1 (fr)

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JP2008-069144 2008-03-18
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JP2008-167116 2008-06-26

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0762594A (ja) * 1993-08-27 1995-03-07 Dainichiseika Color & Chem Mfg Co Ltd 薄膜及びその製造方法並びにその薄膜を用いる機能素子
JP2002524762A (ja) * 1998-09-08 2002-08-06 バイエル アクチェンゲゼルシャフト 黄色フィルター付きのエレクトロクロミック装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0762594A (ja) * 1993-08-27 1995-03-07 Dainichiseika Color & Chem Mfg Co Ltd 薄膜及びその製造方法並びにその薄膜を用いる機能素子
JP2002524762A (ja) * 1998-09-08 2002-08-06 バイエル アクチェンゲゼルシャフト 黄色フィルター付きのエレクトロクロミック装置

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