WO2011096298A1 - Élément d'affichage - Google Patents

Élément d'affichage Download PDF

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WO2011096298A1
WO2011096298A1 PCT/JP2011/051288 JP2011051288W WO2011096298A1 WO 2011096298 A1 WO2011096298 A1 WO 2011096298A1 JP 2011051288 W JP2011051288 W JP 2011051288W WO 2011096298 A1 WO2011096298 A1 WO 2011096298A1
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group
display element
electrode
atom
compound
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PCT/JP2011/051288
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English (en)
Japanese (ja)
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聡史 久光
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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 JP2011552732A priority Critical patent/JPWO2011096298A1/ja
Publication of WO2011096298A1 publication Critical patent/WO2011096298A1/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 
    • G02F1/13—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 liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133553—Reflecting elements
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/40—Materials having a particular birefringence, retardation

Definitions

  • the present invention relates to a display element, and more particularly to a display element with reduced power consumption.
  • the method using a polarizing plate such as a reflective liquid crystal has a low reflectance of about 40%, which makes it difficult to display white, and it is difficult to say that many of the manufacturing methods used to manufacture the constituent members are simple.
  • 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 need for a complicated TFT circuit in order to improve 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 aggregation of electrophoretic particles.
  • an electrochromic display element can be driven at a low voltage with a simple member structure, and can display a relatively bright white display or a black and white display with a high contrast, and is expected to be applied to electronic paper, electronic books, and the like.
  • Various methods are disclosed (for example, refer to Patent Documents 1 and 2).
  • the electrochromic display element like the electrophoretic display element, performs colored display by light absorption by the dye, and therefore, in order to obtain a sufficient contrast ratio, the thickness of the colored material is required.
  • the occupied volume ratio will increase. For this reason, there are problems such that the drive voltage becomes high and viewing angle dependency occurs, so that high-resolution display cannot be performed. Therefore, there has been a demand for a display element that efficiently obtains a high contrast ratio with a smaller amount of coloring material.
  • 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 can obtain a good contrast ratio with a smaller amount of coloring material, that is, a good contrast ratio with low power consumption. There is to do.
  • a display element having a color space between at least a pair of opposing electrodes, wherein the color space satisfies the following formulas (1) and (2).
  • n 2 ⁇ d 2 ⁇ 90 or n 2 ⁇ d 2 ⁇ 185 Formula (2) 100 ⁇ n 1 ⁇ d 1 ⁇ 175 [Where n 1 and d 1 are the refractive index n 1 and thickness d 1 (nm) of the coloring space when the display element is colored (or black), respectively, and n 2 and d 2 are The refractive index n 2 and the thickness d 2 (nm) of the coloring space in the white display state. ] 2.
  • an electrolyte is further contained between the pair of opposed electrodes, and the coloring space contains an electrochromic compound.
  • 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 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
  • Rl 23 represents an aromatic group or an aromatic heterocyclic 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.
  • Rg 11 -S-Rg 12 each represent a substituted or unsubstituted hydrocarbon group. Further, these hydrocarbon groups may contain one or more nitrogen atom, oxygen atom, phosphorus atom, sulfur atom or halogen atom, and Rg 11 and Rg 12 may be connected to each other to take 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 hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryl Oxy group, alkylthio group, arylthio group, alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, Re
  • the present inventors have found that in a display element having a color development space between at least a pair of opposed electrodes, the color development space satisfies the expressions (1) and (2). As a result of the present invention, it has been found that a display element capable of obtaining a good contrast ratio with a smaller amount of colorant and low power consumption can be realized.
  • the display element of the present invention is characterized in that, in a display element having a color development space between at least a pair of opposed electrodes, the color development space satisfies the following formulas (1) and (2).
  • n 1 and d 1 are the refractive index n 1 and the thickness d 1 (nm) of the coloring space when the display element is in a colored (or black) display state, respectively, and n 2 and d 2 are the white display of the display element, respectively.
  • the refractive index n 2 and the thickness d 2 (nm) of the coloring space in the state are represented.
  • FIG. 1 shows an example of the structure of the display element of the present invention.
  • a typical display element 1 of the present invention at least one pair of counter electrodes is provided.
  • a transparent electrode 5 such as an ITO electrode is provided as one of the counter electrodes close to the display portion, and a conductive electrode 2 is provided on the other electrode.
  • a color development space 4 is provided between the transparent electrode 5 and the conductive electrode 2.
  • the color development space 4 is a space in which visible light transmission and absorption can be reversibly switched by a voltage applied between a pair of counter electrodes.
  • an electrochromic layer containing an electrochromic compound And a space on the electrode surface where metal ions in the electrolyte are deposited and dissolved.
  • the visible light C reflected by the upper surface A and the lower surface B of the coloring space 4 is shifted by about 1 ⁇ 2 wavelength when the display element 1 is in a colored display state, the visible light is reflected by the interference of light. It is weakened and the color density is higher. Since the optical path difference between the reflected light C ′ from the upper surface A and the reflected light C ′′ from the lower surface B of the coloring space 4 is 2n 1 ⁇ d 1 , the value of 2n 1 ⁇ d 1 is about 1 ⁇ 2 wavelength.
  • the phase of the visible light C reflected by the upper surface A and the lower surface B of the coloring space 4 is shifted by a half wavelength, since the wavelength of the visible light C is about 400 nm to 700 nm, so that 100 ⁇ n 1 ⁇ d 1 ⁇ 175.
  • the reflection of visible light is weakened by the interference of light and the coloring density in the colored display state is higher, while the reflection of visible light C is not weakened by the interference of light when the color development space 4 is in the visible light transmission absorption state.
  • the reflectance in the white display state can be increased, and the contrast ratio of the display element 1 can be increased, that is, the absorption of light due to light interference can be in the ultraviolet or infrared region.
  • N 2 ⁇ d 2 ⁇ 9 0, or n 2 ⁇ d 2 ⁇ 185.
  • the coloring space 4 contains an electrochromic compound as a colorant
  • the electrochromic compound undergoes coloring and decoloring by electrical oxidation and reduction.
  • ions in the electrolytic solution are present in the coloring space 4 to compensate for the charge.
  • the refractive index n of the coloring space changes, and at the same time, the thickness d (nm) of the coloring space also changes.
  • the type and addition amount of electrochromic dye constituting the color development space (volume ratio in the color development space), the existence form of the electrochromic dye in the color development space, and other members constituting the color development space, such as electrolysis
  • the coloring space N 1 and n 2 are determined.
  • d 1 and d 2 are set so as to satisfy the expressions (1) and (2) according to the n 1 and n 2 of the coloring space set as described above.
  • the refractive index of the coloring space changes with the deposition of the metal.
  • the thickness of the coloring space may change.
  • the effects of the present invention can be obtained by appropriately setting the refractive index and thickness of the color development space of the display element as described above.
  • an electrolyte is preferably contained between a pair of opposed electrodes.
  • electrolyte 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”).
  • 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 and the like can be used.
  • inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, cyclic quaternary ammonium salts, quaternary phosphonium salts and the like can be used.
  • 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.
  • the amount of the supporting electrolyte used is arbitrary, but in general, the supporting electrolyte 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.
  • 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 exhibiting electronic conductivity and ionic conductivity can be contained in the electrolyte.
  • Fluorine-containing compounds such as chalcogenide, CaF 2 , PbF 2 , SrF 2 , LaF 3 , TlSn 2 F 5 , CeF 3 , Li salts such as Li 2 SO 4 , Li 4 SiO 4 , Li 3 PO 4 , ZrO 2 , CaO , Cd 2 O 3 , HfO 2 , Y 2 O 3 , Nb 2 O 5 , WO 3 , Bi 2 O 3 , AgBr, AgI, CuCl, CuBr, CuBr, CuI, LiI, LiBr, LiCl, LiAlCl 4 , LiAlF 4 , AgSBr, C 5 H 5 NHAg 5 I 6 , Rb 4 Cu 16 I Examples thereof include 7 Cl 13 , Rb 3 Cu 7 Cl 10 , LiN, Li 5 NI 2 , and Li 6 NBr 3 .
  • the color space formed between a pair of opposing electrodes preferably contains an electrochromic compound.
  • the electrochromic compound is preferably an organic dye.
  • Examples of the conductive polymer compound exhibiting electrochromic properties include polypyrrole, polythiophene, polyisothianaphthene, polyaniline, polyphenylenediamine, polybenzidine, polyaminophenol, polyvinylcarbazole, polycarbazole, and derivatives thereof.
  • 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.
  • electrochromic compounds When the electrochromic compounds are classified according to color change, they can be divided into the following three classes.
  • Class 1 An electrochromic compound that changes from one specific color to another by redox
  • Class 2 An electrochromic compound that is substantially colorless in an oxidized state and exhibits a specific colored state that is a reduced state
  • Class 3 An electrochromic compound that is substantially colorless in the reduced state and exhibits a specific colored state that is an oxidized state.
  • the class 1 to class 3 electrochromic compounds can be appropriately selected depending on the purpose and application.
  • a class 1 electrochromic compound is an electrochromic compound that changes from a specific color to another color by oxidation-reduction, and is a compound that can display two or more colors in its possible oxidation state.
  • V 2 O 5 changes from orange to green by changing from an oxidation state to a reduction state
  • Ru 2 O 3 changes from yellow to dark green
  • 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 multi-color characteristics, and changes from an amber color in an oxidation state to blue, green, and light yellow.
  • Class 2 electrochromic 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.
  • organic dyes classified as class 2 include compounds described in JP-A Nos. 62-71934 and 2006-71765, such as dimethyl terephthalate (red) and 4,4′-biphenyl. Examples thereof include diethyl carboxylate (yellow), 1,4-diacetylbenzene (cyan), and tetrazolium salt compounds described in JP-A-1-230026, JP-T 2000-504774, and the like.
  • the most representative dyes classified in class 2 are pyridinium compounds such as viologen.
  • Viologen compounds have the advantages of vivid display images and the ability to change colors by changing substituents, so they are the most actively studied among organic dyes. Has been. Color development is based on organic radicals generated by reduction.
  • pyridinium compounds such as viologen include compounds described in each of the following patent documents starting with 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.
  • 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, but styryl dyes, azine dyes such as phenazine, phenothiazine, phenoxazine, and acridine, azole dyes such as imidazole, oxazole, and thiazole, etc. preferable.
  • styryl dyes, azine dyes, and azole dyes that can be used in the present invention are exemplified, 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 electrochromic dye, and a plurality of three or more colors of black display, white display, and color display other than black are used. Perform color display.
  • the electrochromic dye is preferably a class 3 electrochromic compound that develops color by oxidation.
  • an electrochromic compound represented by the following general formula (L) according to the present invention is preferable as the electrochromic compound.
  • 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 eg, propargyl group, etc.
  • glycidyl groups acrylate groups, methacrylate groups, aromatic groups (eg, phenyl group, naphthyl group, anthracenyl group, etc.), heterocyclic groups (eg, pyridyl group, thiazolyl group, oxazolyl group) Group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sriphoranyl
  • Rl 1 is preferably a substituted or unsubstituted phenyl group, more preferably a substituted or unsubstituted 2-hydroxyphenyl group or 4-hydroxyphenyl group.
  • R1 2 or Rl 3 is not particularly limited, and examples thereof include the substituents exemplified as the substituent on the aryl group of Rl 1 .
  • Rl 2 and Rl 3 are each an alkyl group, a cycloalkyl group, an aromatic group, or a heterocyclic group, which may have a substituent.
  • Rl 2 and Rl 3 may be connected to each other to form a ring structure.
  • both of them may be a phenyl group or a heterocyclic group which may have a substituent, or one of them may be a phenyl group or a heterocyclic group which may have a substituent.
  • the other is a combination of alkyl groups 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) according to the present invention has a 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 according to the present invention is preferably a chemisorbable group.
  • Examples of the adsorptive group to be chemisorbed include —COOH, —P ⁇ O (OH) 2 , —OP ⁇ O (OH) 2 , Or -Si (OR) 3 (R represents an alkyl group) is preferable.
  • 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 sulfonamido group, or a sulfamoyl group
  • Rl 23 represents an aromatic group or Represents an aromatic heterocyclic 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 a partial structure of —COOH, —P ⁇ O (OH) 2 , —OP ⁇ O (OH) 2 , or —Si (OR) 3. (R represents 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 , —Si It is preferable to have (OR) 3 (R represents an alkyl group), and in particular, —Si (OR) 3 (R represents an alkyl group) as a partial structure of the group represented by Rl 23 or Rl 24 It is preferable to have.
  • electrochromic dye represented by the general formula (L2) and specific examples of the electrochromic dye contained in the general formula (L) are shown below, although they do not correspond to the general formula (L2).
  • the present invention is not limited only to these exemplified compounds.
  • the metal salt compound according to the present invention is any compound as long as it contains a metal species that can be dissolved and precipitated by driving the counter electrode on at least one electrode on the counter electrode.
  • a metal species that can be dissolved and precipitated by driving the counter electrode on at least one electrode on the counter electrode.
  • 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.
  • a known silver salt compound such as a silver salt with an acid or a silver complex with iminodiacetic acid can be used.
  • the silver salt a compound which does not have a nitrogen atom having a coordination property with halogen, carboxylic acid or silver, and for example, silver p-toluenesulfonate is preferable.
  • the metal ion concentration contained in the electrolyte solution 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.
  • a silver salt solvent can be used to promote dissolution and precipitation of metal salts (particularly silver salts).
  • the silver salt solvent may be any compound that can solubilize silver in the electrolyte.
  • a halogen atom, a mercapto group, a carboxyl group, an imino group, and the like are known. It is characterized by low influence on coexisting compounds and high solubility in solvents.
  • the electrolyte preferably contains a compound represented by the general formula (G-1) or (G-2) as a silver salt solvent.
  • Rg 11 and Rg 12 each represents 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 hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryl Oxy group, alkylthio group, arylthio group, alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl
  • Rg 11 and Rg 12 each represent a substituted or unsubstituted hydrocarbon group, and in these hydrocarbon groups, one or more nitrogen atoms, oxygen atoms, phosphorus atoms, sulfur An atom may be included, and Rg 11 and Rg 12 may be connected to each other to take a cyclic structure.
  • 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 Compounds G1-2 and G1-3 are particularly preferable from the viewpoint that the object and effects 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 hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryl Oxy group, alkylthio group, arylthio group, alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl
  • 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.
  • Examples of the nitrogen-containing heterocycle having Z as a constituent in the general formula (G-2) 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, Examples include a benzimidazole ring, a benzothiazole ring, a benzoselenazole ring, and a naphthoxazole ring.
  • the specific group represented by Rg 21 is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom) alkyl group (eg, methyl, ethyl, propyl) I-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl, hydroxyethyl, methoxyethyl, trifluoromethyl, benzyl, etc.), aryl group (eg, phenyl, naphthyl, etc.), alkylcarboxylic Amido group (eg, acetylamino, propionylamino, butyroylamino, etc.), arylcarbonamide group (eg, benzoylamino, etc.), alkylsulfonamide group (eg, methane
  • halogen atom
  • 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.
  • an auxiliary compound that can be oxidized and reduced may be added in addition to the electrochromic compound.
  • the promoter may be one that does not change the optical density in the visible region (400 to 700 nm) as a result of the oxidation-reduction reaction, or one that changes, that is, the electrochromic compound, and is immobilized on the electrode. It may be added to the electrolyte.
  • These promoters can be used, for example, as counter electrode reactants or as redox mediators.
  • 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.
  • an oxidation reaction actually occurs. Due to experimental limitations on the anodic potential, it is not possible to oxidize all substrates by direct methods.
  • a substrate having a high oxidation potential is oxidized, no electron transfer from the substrate to the anode occurs.
  • 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 present invention for example, when an electrochromic compound that oxidizes and colors is used as the substrate, it is possible to drive the display element with a low driving voltage by coexisting an oxidation mediator of the catalyst, and the durability of the display element is improved. Rise. In addition, there are advantages such as an improvement in display switching speed and high coloring efficiency. Similarly, the above-described effect can be obtained by a combination of a reducing mediator and an electrochromic compound that produces a reducing color.
  • 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.
  • a known electrochromic compound can be used.
  • a redox mediator according to the characteristics of the electrochromic compound used as the display dye, Journal of Organic Synthetic Chemistry, Vol. 43, No. 6 (Special Issue on “Organic Synthesis Using Electric Energy”) (1985), etc.
  • the known mediators described in 1) can be appropriately selected and used.
  • N-oxyl also called nitroxide radical
  • nitroxide radical is an oxygen-centered radical generated by radically cleaving the oxygen-hydrogen bond of hydroxylamine.
  • Nitroxide radicals are known to have two reversible redox pairs as shown in the scheme below.
  • the nitroxide radical becomes an oxoammonium cation by one-electron oxidation, which is reduced to regenerate the radical.
  • the nitroxide radical is converted into an aminoxy anion by one-electron reduction, which is oxidized to regenerate the radical. Therefore, the nitroxide radical can function as a p-type counter electrode reactant or an n-type counter electrode reactant.
  • the N-oxyl derivative is immobilized on the electrode surface by introducing a group that chemically or physically adsorbs to the electrode surface into the N-oxyl derivative, or by polymerizing the N-oxyl derivative to form a thin film on the electrode surface.
  • the method of doing is mentioned.
  • 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-hydroxyphthalimide derivatives N-hydroxyphthalimide derivatives, hydroxamic acid derivatives, etc.
  • PINO phthalimide N-oxyl
  • NHPI N-hydroxyphthalimide
  • THICA trihydroxyimino cyanuric acid
  • 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 and performing oxidation.
  • the promoter shown in the above category 1) can be represented by the following general formula (M1), and promoters represented by the following general formulas (M2) to (M5) are preferable.
  • a polycyclic N-oxyl derivative represented by the general formula (M6) is preferable.
  • Promoters obtained by polymerizing these are, for example, JP-A Nos. 2004-227946, 2004-228008, 2006-73240, 2007-35375, 2007-70384, and 2007-184227. No. 2007, No. 2007-298713, and the like can be synthesized.
  • 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 group which may have a hydrogen atom or a substituent. These aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclic groups 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.
  • 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.
  • Rm 31 and Rm 32 may be connected to each other to form a ring structure.
  • 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 which may be substituted, or an aromatic hydrocarbon, which is substituted directly or through a oxygen atom, a nitrogen atom or a sulfur atom with a carbonyl carbon atom.
  • Rm 32 represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group which may have a substituent, and these aliphatic hydrocarbon group, aromatic carbon group About a hydrogen group and a heterocyclic group, it is synonymous with each in general 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.
  • the compound represented by the general formula (M3) is preferably added in the state of N—OH to produce a display element.
  • Z 2 represents an atomic group necessary for forming a cyclic structure, and may further have a substituent.
  • the N-oxyl derivative according to the present invention is a compound represented by the general formula (M4).
  • Z 2 represents an atomic group necessary for forming a cyclic structure, and preferably forms a 5-membered ring or a 6-membered ring.
  • Z 2 may further have a substituent, and examples of the substituent include the substituents exemplified in Formula (M1).
  • Z 2 may be a condensed ring.
  • the compound represented by the general formula (M4) is preferably added in the state of N—OH to produce a display element.
  • 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.
  • the N-oxyl derivative according to the present invention is a compound represented by the general formula (M5).
  • Rm 51 to Rm 55 each independently represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group which may have a substituent, and these aliphatic hydrocarbons
  • the 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 an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is particularly preferable.
  • Rm 61 and Rm 62 each independently represent a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent, and Z 3 , Z 4 and Z 5 form a cyclic structure. And n represents 0 or 1.
  • formula (M6) represents an aliphatic hydrocarbon group which may have a hydrogen atom or a substituent each independently Rm 61 and Rm 62, as the Rm 61 and Rm 62 or a hydrogen atom, carbon atoms 4
  • the following linear alkyl groups are preferable, and at least one of Rm 61 and Rm 62 is preferably a hydrogen atom.
  • Z 3 , Z 4 and Z 5 each represent an atomic group necessary for forming a cyclic structure (for example, carbon, nitrogen, oxygen, sulfur, etc.), and each preferably forms a 5-membered ring or a 6-membered ring.
  • Z 3 , Z 4 and Z 5 may further have a substituent.
  • N 0 or 1
  • the electrolyte solvent used in the present invention is preferably an aprotic polar solvent, particularly propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, ⁇ -butyrolactone, sulfolane, dioxolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, adiponitrile, Methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethyl sulfoxide, dioxolane, sulfolane, trimethyl phosphate and triethyl phosphate are preferred.
  • the solvent may be used alone or in combination of two or more.
  • 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 CH 2
  • 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 represent a hydrogen atom, 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 compounds represented by the general formulas (S1) and (S2) according to the present invention are one type of electrolyte solvent.
  • another solvent is used as long as the object effects of the present invention are not impaired. Can be used together.
  • examples of the solvent that can be used in the present invention include J.M. 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, “Nonequeous Electrolytes Handbook”, Vol. 1, Academic Press (1972).
  • Porous white scattering layer In the present invention, it is possible to have a porous white scattering layer containing a white scattering material from the viewpoint of further increasing display contrast and white display reflectance.
  • 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.
  • 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 other natural compounds such as polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrolidone, and acrylamide. Synthetic polymer compounds such as coalescence and derivatives thereof may be mentioned.
  • 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.
  • polyvinyl alcohol polyethylene glycol
  • polyvinylpyrrolidone compounds can be preferably used.
  • Polymers dispersed in an aqueous solvent include latexes such as natural rubber latex, styrene butadiene rubber, butadiene rubber, nitrile rubber, chloroprene rubber, isoprene rubber, polyisocyanate, epoxy, acrylic, silicon, polyurethane, Examples thereof include a thermosetting resin in which urea, phenol, formaldehyde, epoxy-polyamide, melamine, alkyd resin, vinyl resin and the like are dispersed in an aqueous solvent. Of these polymers, the water-based polyurethane resin described in JP-A-10-76621 is preferably used.
  • the average molecular weight of the water-based polymer is preferably in the range of 10,000 to 2,000,000, more preferably in the range of 30,000 to 500,000 in terms of weight average.
  • 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 is preferably used among the above white pigments.
  • titanium dioxide surface-treated with an inorganic oxide Al 2 O 3 , AlO (OH), SiO 2, etc.
  • titanium dioxide that has been treated with an organic substance such as trimethylolethane, triethanolamine acetate, or trimethylcyclosilane is more preferably used.
  • titanium oxide or zinc oxide from the viewpoint of preventing coloring at high temperatures and the reflectance of the element due to the refractive index.
  • the water admixture 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 by volume, more preferably 0.3 to 0.05.
  • the film thickness of the porous white scattering layer is preferably in the range of 5 to 50 ⁇ m, more preferably in the range of 10 to 30 ⁇ m.
  • the coating method can be appropriately selected from known coating methods.
  • air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnation coater, reverse roller coater, transfer roller coater, curtain coater, double roller coater, slide hopper coater, gravure coater, kiss roll coater, bead coater examples include cast coaters, spray coaters, calendar coaters, and extrusion coaters.
  • 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.
  • 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.
  • Various chemical sensitizers noble metal sensitizers, photosensitive dyes, supersensitizers, couplers, high boiling solvents, antifoggants, stabilizers, development inhibitors, bleach accelerators, fixing accelerators, color mixing inhibitors, Formalin Scavenger, Toning Agent, Hardener, Surfactant, Thickener, Plasticizer, Slipper, Ultraviolet Absorber, Irradiation Dye, Filter Light Absorbing Dye, Antibacterial Agent, Polymer Latex, Heavy Metal, Antistatic Agent Further, a matting agent or the like can be contained as necessary.
  • auxiliary layers such as a protective layer, a filter layer, an antihalation layer, a crossover light cut layer, and a backing layer, and may be contained in these auxiliary layers.
  • the substrate constituting the display element of the present invention is preferably a transparent substrate.
  • a transparent substrate include polyester (for example, polyethylene terephthalate), polyimide, polymethyl methacrylate, polystyrene, polypropylene, polyethylene, Polyamide, nylon, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyether sulfone, silicon resin, polyacetal resin, fluororesin, cellulose derivative, polyolefin film, plate-like substrate, glass substrate and the like are preferably used.
  • the transparent substrate used in the present invention refers to a substrate having a transmittance for visible light of at least 50%.
  • an opaque substrate such as an inorganic substrate such as a metal substrate or a ceramic substrate can be used.
  • the surface resistance value indicating the conductivity of the display-side electrode is preferably 100 ⁇ / ⁇ or less, and more preferably 10 ⁇ / ⁇ or less.
  • the thickness of the electrode is not particularly limited, but is generally 0.1 to 20 ⁇ m.
  • a nanoporous electrode having a nanoporous structure can be provided on the surface of the display side electrode.
  • This nanoporous electrode is substantially transparent when a display element is formed, and can carry an electroactive substance such as an electrochromic dye.
  • the nanoporous structure referred to in the present invention refers to a state in which an infinite number of nanometer-sized pores exist in a layer and ionic species contained in the electrolyte can move within the nanoporous structure.
  • a dispersion containing fine particles constituting the nanoporous electrode is formed in layers by an ink jet method, a screen printing method, a blade coating method, etc., and then heated at a predetermined temperature.
  • a method of making porous by drying, baking, a method of making nanoporous by anodizing or photoelectrochemical etching after forming an electrode layer by sputtering, CVD, atmospheric pressure plasma, etc. Is mentioned.
  • the sol-gel method, Adv. Mater It can also be formed by the method described in 2006, 18, 2980-2983.
  • fine particles having an average particle diameter of about 5 nm to 10 ⁇ m.
  • shape of the fine particles those having an arbitrary shape such as an indefinite shape, a needle shape, and a spherical shape can be used.
  • metals such as platinum, gold, silver, copper, aluminum, zinc, nickel, titanium, bismuth and their alloys, carbon, etc. are also preferably used. be able to.
  • auxiliary electrode An auxiliary electrode can be attached to at least one of the pair of opposing electrodes according to the present invention.
  • the auxiliary electrode is preferably made of a material having a lower electrical resistance than the main electrode part.
  • metals such as platinum, gold, silver, copper, aluminum, zinc, nickel, titanium, and bismuth and alloys thereof can be preferably used.
  • the auxiliary electrode can be installed either between the main electrode portion and the substrate, or on the surface of the main electrode portion opposite to the substrate. In any case, it is only necessary that the auxiliary electrode is electrically connected to the main electrode portion.
  • the arrangement pattern of the auxiliary electrodes There is no particular limitation on the arrangement pattern of the auxiliary electrodes. It can be appropriately formed according to the required performance, such as linear, mesh, or circular.
  • the divided electrode parts may be connected to each other.
  • the auxiliary electrode is required to be provided with a shape and frequency that do not impair the visibility of the display element.
  • a known method can be used. For example, a patterning method by photolithography, a printing method, an ink jet method, electrolytic plating or electroless plating, or a method of forming a pattern by exposing and developing using a silver salt photosensitive material may be used.
  • the line width and line interval of the auxiliary electrode pattern of the present invention may be arbitrary values, it is necessary to increase the line width in order to increase the conductivity.
  • the area coverage of the auxiliary electrode viewed from the display element observation side is preferably 30% or less, and more preferably 10% or less.
  • the line width of the auxiliary electrode is preferably 1 ⁇ m or more and 100 ⁇ m or less, and the line interval is preferably 50 ⁇ m to 1000 ⁇ m.
  • a known method can be used to form the display-side electrode and the counter electrode (and auxiliary electrode). For example, mask deposition may be performed on the substrate by sputtering or the like, or patterning may be performed by photolithography after the entire surface is formed.
  • electrodes can be formed by electrolytic plating, electroless plating, printing methods, and ink jet methods.
  • an electrode pattern including a catalyst layer having a monomer polymerization ability on a substrate using an inkjet method a monomer component that is polymerized by the catalyst and becomes a conductive polymer layer after polymerization is added, It is also possible to form a metal electrode pattern by polymerizing and further performing metal plating such as silver on the conductive polymer layer, and the process is greatly reduced because no photoresist or mask pattern is used. It can be simplified.
  • the electrode material is formed by coating
  • known methods such as a dipping method, a spinner method, a spray method, a roll coater method, a flexographic printing method, and a screen printing method can be used.
  • the following electrostatic inkjet can print a highly viscous liquid continuously with high accuracy, and is preferably used for forming the transparent electrode and the metal auxiliary electrode of the present invention.
  • the viscosity of the ink is preferably 30 mPa ⁇ s or more, and more preferably 100 mPa ⁇ s or more.
  • At least one of the transparent electrode of the composite electrode and the metal auxiliary electrode supplies a liquid discharge head having a nozzle with an internal diameter of 30 ⁇ m or less for discharging charged liquid, and a solution into the nozzle. It is preferably formed using a liquid discharge apparatus including a supply unit and a discharge voltage application unit that applies a discharge voltage to the solution in the nozzle.
  • the solution in the nozzle is formed by using a discharge device provided with a convex meniscus forming means for forming a state where the solution rises in a convex shape from the nozzle tip.
  • an operation control unit that controls application of a drive voltage for driving the convex meniscus forming unit and application of a discharge voltage by the discharge voltage application unit is provided, and the operation control unit applies the discharge voltage by the discharge voltage application unit. It is also preferable to use a liquid ejection apparatus having a first ejection control unit that applies a driving voltage to the convex meniscus forming means when ejecting liquid droplets while performing the above.
  • an operation control unit that controls driving of the convex meniscus forming unit and voltage application by the discharge voltage applying unit is provided, and the operation control unit is configured to swell the solution by the convex meniscus forming unit and apply the discharge voltage.
  • a second discharge control unit that performs synchronization with the liquid discharge device, wherein the operation control means is configured to supply the liquid at the tip of the nozzle after the swell operation of the solution and the application of the discharge voltage. It is also a preferred form to use a liquid discharge apparatus having a liquid level stabilization control unit that performs operation control for drawing the surface inward.
  • 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 spacer diameter corresponds to the cell gap thickness.
  • 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 merits such as gradation and memory function. For example, a circuit described in FIG. 5 of JP-A-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.
  • Electrolyte 4 was prepared by dissolving 2 parts by mass.
  • Electrolyte 5 was prepared by dissolving 2 parts by mass.
  • Electrode 1 An ITO (Indium Tin Oxide) film having a thickness of 1 cm is formed as a conductive layer on a glass substrate having a thickness of 1.5 mm and a width of 2 cm ⁇ 4 cm according to a known method, thereby producing an electrode 1. did.
  • ITO Indium Tin Oxide
  • Electrode 2 On the ITO film-forming surface of the electrode 1, the following titanium dioxide dispersion was screen-printed so that the average film thickness after drying was 20 ⁇ m, and then dried at 50 ° C. for 30 minutes to evaporate the solvent.
  • the electrode 2 having a porous white scattering layer was produced by drying in an atmosphere of 1 ° C. for 1 hour.
  • Electrode 3 (Preparation of electrode 3) The electrode 1 and the platinum electrode are arranged at positions facing each other, and this electrode pair is immersed in a glass container containing the electrolyte 6 until the amount of electricity supplied between the electrode 1 and the platinum electrode is 12 mC / cm 2. A voltage of 3 V was applied, and a polypyrrole film formed by electrolytic polymerization of pyrrole was formed on the electrode 1. The electrode 1 on which the polypyrrole film was formed was taken out of the glass container, washed with ethanol, and dried to obtain an electrode 3.
  • Electrode 4 On the surface of the electrode 1 on which the ITO film was formed, a titanium dioxide layer having a thickness of 0.085 ⁇ m (about 4 to 10 particles having an average particle diameter of 10 nm had been necked) was formed, whereby an electrode 4 was produced.
  • ⁇ Preparation of treatment liquid 1> In 20 parts by mass of pure water, 0.05 part by mass of the following compound (A-1), 0.06 part by mass of the following compound (A-2), and 0.07 part of the following compound (A-3) A treatment liquid 1 was prepared by dissolving a part by mass.
  • Electrode 7 On the ITO film forming surface of electrode 1, a 0.075 ⁇ m thick titanium dioxide layer (about 4 to 10 particles having an average particle diameter of 10 nm had been necked) was formed, and electrode 7 was produced.
  • Electrode 9 (Preparation of electrode 9) The electrode 1 and the platinum electrode are arranged at opposite positions, and this electrode pair is immersed in a glass container containing the electrolyte 6 until the amount of electricity supplied between the electrode 1 and the platinum electrode is 40 mC / cm 2. A voltage of 3 V was applied, and a polypyrrole film formed by electrolytic polymerization of pyrrole was formed on the electrode 1. The electrode 1 on which the polypyrrole film was formed was taken out from the glass container, washed with ethanol, and dried to obtain an electrode 9.
  • Electrode 12 was produced in the same manner as in the production of the electrode 6 except that the electrode 10 was used instead of the electrode 4.
  • Electrode 13 On the surface of the electrode 1 on which the ITO film was formed, a titanium dioxide layer having a thickness of 0.06 ⁇ m (about 4 to 10 particles having an average particle diameter of 10 nm had been necked) was formed, whereby an electrode 13 was produced.
  • Electrode 14 was produced in the same manner as in the production of the electrode 3 except that the electrode 13 was used instead of the electrode 1.
  • Electrode 4 was immersed in the following treatment liquid 3 and allowed to stand at room temperature for about 24 hours, then washed with ethanol and dried to produce an electrode 16.
  • a display element 2 was produced in the same manner as in the production of the display element 1 except that the electrode 5 was used instead of the electrode 3.
  • a display element 4 was produced in the same manner as in the production of the display element 1 except that the electrode 8 was used instead of the electrode 3.
  • a display element 6 was produced in the same manner as in the production of the display element 5 except that the electrolyte 3 was used instead of the electrolyte 2.
  • a display element 9 was produced in the same manner as in the production of the display element 1 except that the electrode 9 was used instead of the electrode 3.
  • a display element 10 was produced in the same manner as in the production of the display element 2 except that the electrode 11 was used instead of the electrode 5.
  • a display element 12 was produced in the same manner as in the production of the display element 5 except that the electrode 1 was used instead of the electrode 13.
  • a display element 13 was produced in the same manner as in the production of the display element 6 except that the electrode 1 was used instead of the electrode 13.
  • a display element 14 was produced in the same manner as in the production of the display element 1 except that the electrode 14 was used instead of the electrode 3.
  • a display element 16 was produced in the same manner as in the production of the display element 7 except that the electrode 15 was used instead of the electrode 13.

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

L'invention concerne un élément d'affichage capable d'obtenir un bon rapport de contraste avec une quantité réduite d'un colorant de développement de couleur, c'est-à-dire un élément d'affichage capable d'obtenir un bon rapport de contraste avec une faible consommation énergétique. Plus précisément, l'invention concerne un élément d'affichage comportant un espace de développement de couleur situé entre au moins une paire d'électrodes qui se font face. L'élément d'affichage est caractérisé en ce que l'espace de développement de couleur satisfait les formules (1) et (2) suivantes. Formule (1): n2·d2 ≤ 90 ou n2·d2 ≥ 185 Formule (2): 100 ≤ n1·d1 ≤ 175 (Dans les formules, n1 et d1 représentent respectivement l'indice de réfraction n1 et l'épaisseur d1 (nm) de l'espace de développement de couleur lorsque l'élément d'affichage présente un affichage coloré (ou noir) ; tandis que n2 et d2 représentent respectivement l'indice de réfraction n2 et l'épaisseur d2 (nm) de l'espace de développement de couleur lorsque l'élément d'affichage présente un affichage blanc.)
PCT/JP2011/051288 2010-02-08 2011-01-25 Élément d'affichage WO2011096298A1 (fr)

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JP2011552732A JPWO2011096298A1 (ja) 2010-02-08 2011-01-25 表示素子

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JP2010-025302 2010-02-08

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
JP2015052733A (ja) * 2013-09-09 2015-03-19 株式会社リコー エレクトロクロミック材料、エレクトロクロミック組成物及びエレクトロクロミック表示素子
CN108172900A (zh) * 2017-12-18 2018-06-15 中节能万润股份有限公司 一种新型锂盐及其制备方法和应用
EP3731011A4 (fr) * 2019-02-27 2021-06-30 Suzhou Institute of Nano-Tech and Nano-Bionics (Sinano), Chinese Academy of Scie Structure électrochromique polychrome, son procédé de préparation et son application
JP7698913B2 (ja) 2023-02-08 2025-06-26 中国科学院蘇州納米技術与納米▲ファン▼生研究所 全色可逆切替可能な電気制御変色デバイス、その製造方法、及びその使用

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JPS561014A (en) * 1979-06-18 1981-01-08 Furukawa Electric Co Ltd:The Optical filter of controllable transmission characteristic
JPH01277826A (ja) * 1988-04-30 1989-11-08 Toyoda Gosei Co Ltd エレクトロクロミック調光板
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JP2007241178A (ja) * 2006-03-13 2007-09-20 Konica Minolta Holdings Inc 表示素子
WO2009037971A1 (fr) * 2007-09-18 2009-03-26 Konica Minolta Holdings, Inc. Élément d'affichage

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JPS54101345A (en) * 1978-01-26 1979-08-09 Minolta Camera Co Ltd Electrochromic element of less reflection loss
JPS561014A (en) * 1979-06-18 1981-01-08 Furukawa Electric Co Ltd:The Optical filter of controllable transmission characteristic
JPH01277826A (ja) * 1988-04-30 1989-11-08 Toyoda Gosei Co Ltd エレクトロクロミック調光板
JP2003195364A (ja) * 2001-12-26 2003-07-09 Shibuya Kogyo Co Ltd 光学部品とそれを用いた光スイッチ
JP2007241178A (ja) * 2006-03-13 2007-09-20 Konica Minolta Holdings Inc 表示素子
WO2009037971A1 (fr) * 2007-09-18 2009-03-26 Konica Minolta Holdings, Inc. Élément d'affichage

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015052733A (ja) * 2013-09-09 2015-03-19 株式会社リコー エレクトロクロミック材料、エレクトロクロミック組成物及びエレクトロクロミック表示素子
CN108172900A (zh) * 2017-12-18 2018-06-15 中节能万润股份有限公司 一种新型锂盐及其制备方法和应用
CN108172900B (zh) * 2017-12-18 2019-08-16 中节能万润股份有限公司 一种新型锂盐及其制备方法和应用
EP3731011A4 (fr) * 2019-02-27 2021-06-30 Suzhou Institute of Nano-Tech and Nano-Bionics (Sinano), Chinese Academy of Scie Structure électrochromique polychrome, son procédé de préparation et son application
JP7698913B2 (ja) 2023-02-08 2025-06-26 中国科学院蘇州納米技術与納米▲ファン▼生研究所 全色可逆切替可能な電気制御変色デバイス、その製造方法、及びその使用

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