WO2010058684A1 - 表示素子 - Google Patents
表示素子 Download PDFInfo
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- WO2010058684A1 WO2010058684A1 PCT/JP2009/068477 JP2009068477W WO2010058684A1 WO 2010058684 A1 WO2010058684 A1 WO 2010058684A1 JP 2009068477 W JP2009068477 W JP 2009068477W WO 2010058684 A1 WO2010058684 A1 WO 2010058684A1
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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
- G02F1/1514—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 characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—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 characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1525—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 characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
Definitions
- the present invention relates to a novel electrochemical display element.
- 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 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.
- an electrochromic method using an electrochromic compound hereinafter abbreviated as EC method
- an electrodeposition method hereinafter referred to as ED
- EC method an electrochromic method using an electrochromic compound
- ED electrodeposition method
- the EC method is capable of full-color display at a low voltage of about 3V or less, and has advantages such as a simple cell configuration and excellent white display quality.
- the ED method can also be driven at a low voltage of 3V or less and is simple. With such a cell structure, there are advantages such as excellent black and white contrast and black display quality, and various methods have been disclosed (see, for example, Patent Documents 1 to 5).
- the present inventor has investigated an EC display element that arranges an electrochromic compound in the ED display element and performs color display other than black and white in addition to white display and black display.
- Has many advantages such as bright white display, high-contrast monochrome display and full-color display with a simple material structure, but the rewriting speed when performing color display other than monochrome is slightly slow. It became clear that it had the problem.
- the present invention has been made in view of the above problems, and the object thereof is to realize black and white display and full color display with a simple member configuration, and to improve rewriting speed when performing color display other than black and white. It is to provide a display element.
- a display element wherein the acidity of the electrolyte is 5.0 or more and 9.0 or less, and white display, black display, and color display other than black are performed by driving the counter electrode.
- Rl 1 represents a halogen atom, an aliphatic group, an aliphatic oxy group, an acylamino group, a carbamoyl group, an acyl group, a sulfonamide group, or a sulfamoyl group
- n represents an integer of 1 to 4.
- Rl 2 represents an aromatic group or an aromatic heterocyclic group
- Rl 3 represents a hydrogen atom, an aliphatic group, an aromatic group or an aromatic heterocyclic group.
- X represents> N—Rl 4 , an oxygen atom or a sulfur atom
- Rl 4 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group.
- the groups represented by Rl 1 to Rl 4 may be further substituted with an arbitrary substituent.
- n represents an integer of 0 to 5
- Rg 21 represents 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 aryloxy group, an alkylthio group.
- R 1 , R 2 and R 3 represent a substituted or unsubstituted hydrocarbon group which may be the same or different from each other.
- 4 The display element according to any one of 1 to 3, wherein a polymer compound having an amino group is contained between the pair of counter electrodes.
- At least one selected from the compound represented by the general formula (A), a polymer compound having an amino group, and an amine compound supported on fine particles is fixed to a region other than the surface of the pair of counter electrodes. 6.
- the present invention it is possible to provide a display element that can realize black and white display and full color display with a simple member configuration, and has improved rewriting speed when performing color display other than black and white.
- the present inventor contains at least an electrolyte and a compound represented by the following general formula (L) between a pair of counter electrodes, and the electrolyte includes a metal salt compound and the following: And a mercapto compound represented by the general formula (G), wherein the electrolyte has an acidity of 5.0 or more and 9.0 or less, and a white display, a black display, and a black display by driving the counter electrode.
- the metal salt compound and the mercapto compound represented by the general formula (G) according to the present invention are contained between the pair of counter electrodes, and the acidity is 5.0 or more, 9 0.0 or less and a compound represented by the general formula (L) according to the present invention, and by applying a voltage of both positive and negative polarities between the counter electrodes, white display, black display, and other than black and white
- the color display can be switched reversibly.
- electrolyte As used in the present invention generally refers to a substance that dissolves in a solvent such as water and exhibits a ionic conductivity in a solution (hereinafter referred to as “narrowly defined electrolyte”). A mixture containing other metals, compounds, or the like, regardless of whether it is an electrolyte or a non-electrolyte, is called an electrolyte (“broadly defined electrolyte”).
- the electrolyte according to the present invention contains at least a metal salt compound and a mercapto compound represented by the general formula (G) according to the present invention, and has an acidity of 5.0 or more and 9.0 or less.
- 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 applicable 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, etc.
- state species of the phase such as the solid state, the solubilized state in liquid or the gaseous 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.
- the molar concentration of halogen ions or halogen atoms contained in the electrolyte solution is [X] (mol / kg)
- the silver or silver contained in the electrolyte solution is a compound that contains silver in the chemical structure.
- 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 metal oxidation-reduction reaction, and X 2 easily cross-oxidizes with the deposited metal to dissolve the deposited metal. Therefore, the molar concentration of halogen atoms is preferably as low as possible relative to the molar concentration of metallic silver. In the present invention, 0 ⁇ [X] / [Metal] ⁇ 0.001 is more preferable.
- the halogen species preferably have a total molar concentration of [I] ⁇ [Br] ⁇ [Cl] ⁇ [F] from the viewpoint of improving memory properties.
- the electrolyte according to the present invention contains a mercapto compound represented by the general formula (G) as a metal salt solvent for promoting the dissolution and precipitation of a metal salt (particularly, a silver salt) together with the metal compound.
- a metal salt solvent for promoting the dissolution and precipitation of a metal salt (particularly, a silver salt) together with the metal compound.
- Z represents a nitrogen-containing heterocyclic ring.
- n represents an integer of 0 to 5
- Rg 21 represents a halogen atom, alkyl group, aryl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, alkoxy group, aryloxy 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, aryloxycarbonyl group , an alkylcarbonyl group, an arylcarbonyl group, an acyloxy group, a carboxyl group, a carbon
- Examples of the nitrogen-containing heterocycle represented by Z in the general formula (G) include tetrazole ring, triazole ring, oxadiazole ring, thiadiazole ring, indole ring, oxazole ring, benzoxazole ring, benzothiazole ring, benzoselena Examples thereof include a sol ring and a naphthoxazole ring.
- Examples of the halogen atom represented by Rg 21 in the general formula (G) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Examples of the alkyl group include methyl, ethyl, propyl, i- Examples include propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl, hydroxyethyl, methoxyethyl, trifluoromethyl, benzyl, etc.
- Examples of the aryl group include phenyl, naphthyl, and the like.
- Examples of the alkylcarbonamide group include acetylamino, propionylamino, butyroylamino and the like.
- Examples of the arylcarbonamide group include benzoylamino and the like.
- Examples of the sulfonamide group include methanesulfo Nylamino group, ethanesulfonylamino group and the like.
- Examples of the arylsulfonamido group include benzenesulfonylamino group and toluenesulfonylamino group.
- Examples of the aryloxy group include phenoxy and the like, and alkylthio group.
- Examples of the group include each group such as methylthio, ethylthio, and butylthio.
- Examples of the arylthio group include phenylthio group and tolylthio group.
- Examples of the alkylcarbamoyl group include methylcarbamoyl, dimethylcarbamoyl, Examples include ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, piperidylcarbamoyl, morpholylcarbamoyl and the like, and arylcarbamoyl groups include, for example, phenylcarbamoyl, methylphenyl Examples thereof include carbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl, etc.
- alkylsulfamoyl groups include methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl.
- examples of each group include moyl, piperidylsulfamoyl, morpholylsulfamoyl, and arylsulfamoyl groups include, for example, phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl.
- Examples of the alkylsulfonyl group include a methanesulfonyl group and an ethanesulfonyl group.
- Examples of the arylsulfonyl group include a phenylsulfonyl group and a 4-chlorophenylsulfur group.
- Each group such as nyl, p-toluenesulfonyl and the like
- examples of the alkoxycarbonyl group include groups such as methoxycarbonyl, ethoxycarbonyl and butoxycarbonyl
- examples of the aryloxycarbonyl group include phenoxycarbonyl and the like.
- alkylcarbonyl group examples include acetyl, propionyl, and butyroyl groups.
- arylcarbonyl group include benzoyl group and alkylbenzoyl group.
- acyloxy group examples include acetyloxy, propionyloxy, butyroyloxy and the like, and examples of the heterocyclic group include oxazole ring, thiazole ring, triazole ring, selenazole ring, tetrazole ring, oxadiazole ring, thiadiazole ring, Examples include a thiazine ring, a triazine ring, a benzoxazole ring, a benzthiazole ring, an indolenine ring, a benzselenazole ring, a naphthothiazole ring, a triazaindolizine ring, a diazaindolizine ring, and a
- Exemplified Compounds G-12, G-18, G-19, and G-20 are particularly preferable from the viewpoint that the objective effect of the present invention can be exhibited.
- the mercapto compound represented by the general formula (G) according to the present invention can be obtained by a person skilled in the art according to a conventionally known synthesis method, or can be easily obtained as a commercial product.
- the acidity of the electrolyte is set to 5.0 or more and 9.0 or less, and more preferably adjusted to 6.0 or more and 8.0 or less.
- the acidity of the electrolyte is set to 5.0 or more, the rewriting speed when performing color display other than white display and black table can be improved.
- the imidazole dye represented by the general formula (L) according to the present invention is considered to release H + ions when colored (color display), and therefore the H + ion concentration in the electrolyte is low. This is probably because when the acidity is low, that is, the acidity is high, color development is more likely to occur. On the other hand, if the H + ion concentration becomes too low, that is, the acidity number becomes too large, specifically, if the acidity exceeds 9.0, it becomes difficult to decolorize. Even if a voltage is applied, it cannot be driven.
- the imidazole dye represented by the general formula (L) according to the present invention takes in H + ions when decoloring, and as a result, the H + ion concentration in the electrolyte is too low. That is, it is presumed that this is due to the fact that if the acidity value is too high, decoloration is difficult to occur. Therefore, by adjusting the acidity of the electrolyte to 5.0 or more and 9.0 or less, preferably 6.0 or more and 8.0 or less, the rewriting speed when performing color display can be improved. is there.
- any means may be used as a means for adjusting the acidity of the electrolyte.
- the electrolyte is an organic solvent system
- R 1 , R 2 and R 3 represent a substituted or unsubstituted hydrocarbon group which may be the same as or different from each other.
- Examples of the hydrocarbon group represented by R 1 , R 2 , or R 3 independently include an alkyl group, a halogenated alkyl group, a cycloalkyl group, or an aromatic hydrocarbon group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group.
- the aromatic hydrocarbon group examples include an aryl group and an aralkyl group, specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group.
- the substituent of the hydrocarbon group includes an alkyl group (eg, methyl group, ethyl group), an acylamino group (eg, acetylamino group, propanoylamino group, i-butanoylamino group, n-butanoylamino group) , Benzoylamino group, m-sulfobenzoylamino group), alkoxycarbonylamino group (for example, methoxycarbonylamino group, ethoxycarbonylamino group), aryloxycarbonylamino group (for example, phenoxycarbonylamino group), alkoxycarbonyl group ( For example, ethoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), ureido group (for example, methylureido group, phenylureido group), sulfonylamino group (for example, methanesulf
- the hydrocarbon group represented by R 1 , R 2 , or R 3 may have a substituent, and examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom), an alkyl group (for example, Methyl, ethyl, i-propyl, hydroxyethyl, methoxymethyl, trifluoromethyl, t-butyl etc.), cycloalkyl group (eg cyclopentyl, cyclohexyl etc.), aralkyl group (eg benzyl, 2-phenethyl etc.), aryl Groups (eg, phenyl, naphthyl, p-tolyl, p-chlorophenyl, etc.), alkoxy groups (eg, methoxy, ethoxy, i-propoxy, butoxy, etc.), aryloxy groups (eg, phenoxy, etc.), cyano groups, heterocyclic radical
- Examples of the compound represented by the general formula (A) include trimethylamine, triethylamine, tripropylamine, tributylamine, triisopropanolamine, triethanolamine, tris (hydroxymethyl) aminomethane, N, N-dimethylaniline and the like. Can be mentioned.
- Examples of the monomer having an amino group include N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N , N-dimethylacrylamide, acryloylmorpholine, N-isopropylacrylamide, N, N-diethylacrylamide and the like.
- polymer which has an amino group it can obtain as a commercial item, for example, 1) It is an aminoethylation acrylic polymer containing the primary amine group which grafted the polyethyleneimine by Nippon Shokubai Co., Ltd. to the side chain.
- Polyment series for example, NK-350 (average molecular weight about 100,000, amine number 0.6 to 1.0 mmol / g.solid), NK-380 (average molecular weight about 100,000, amine number 0.7 to 1.3 mmol) / G ⁇ solid), 2) PAA series of polyallylamine having only a primary amino group in the side chain manufactured by Nittobo, for example, PAA-01 (average molecular weight: about 1000, pH about 11), PAA-03 (Average molecular weight: about 3000, pH about 11), PAA-05 (average molecular weight: about 5000, pH about 11), PAA-08 (average molecular weight: 8000, pH about 11), PAA-15 (average molecular weight: mention may be made of about 15000, pH about 11), and the like.
- PAA-01 average molecular weight: about 1000, pH about 11
- PAA-03 Average molecular weight: about 3000, pH about 11
- PAA-05 average molecular weight: about 5000,
- organic or inorganic fine particles supporting an amine compound on the particle surface can be used as means for adjusting the acidity of the electrolyte.
- Examples of the amine compound supported on the fine particles include porous polystyrene particles on which piperidine, pyridine, imidazole, piperazine and the like are supported, and porous silica particles on which piperidine, pyridine, imidazole, piperazine and the like are supported. .
- the amine compound such as the compound represented by the above general formula (A) according to the present invention, the polymer having an amino group, and the amine compound supported on the fine particles may be used after being dissolved or dispersed in the electrolyte. Furthermore, it is more preferable that these amine compounds be used in a region other than the surface of the pair of counter electrodes because these amine compounds are less likely to be oxidized and reduced electrochemically.
- 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.
- the supporting electrolyte of the present invention is preferably a quaternary ammonium salt, particularly preferably a quaternary spiro ammonium salt.
- a quaternary ammonium salt particularly preferably a quaternary spiro ammonium salt.
- 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 in general, 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.
- 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 chalcogenides, 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 7 Cl 13, Rb 3 Cu 7 Cl 10, LiN, compounds such as Li 5 NI 2, Li 6 NBr 3 , and the like.
- Li salts such as Li 2 SO 4 , Li 4 SiO 4 , Li 3 PO 4 , ZrO 2
- an imidazole dye represented by the general formula (L) is used as an electrochromic compound (hereinafter referred to as EC compound or EC dye) for the purpose of color display.
- Rl 1 represents a halogen atom, an aliphatic group, an aliphatic oxy group, an acylamino group, a carbamoyl group, an acyl group, a sulfonamide group, or a sulfamoyl group, and n is an integer of 1 to 4.
- Rl 2 represents an aromatic group or an aromatic heterocyclic group
- Rl 3 represents a hydrogen atom, an aliphatic group, an aromatic group, or an aromatic heterocyclic group.
- X represents> N—Rl 4 , an oxygen atom or a sulfur atom, and Rl 4 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group.
- the groups represented by Rl 1 to Rl 4 may be further substituted with an arbitrary substituent.
- examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom
- examples of the aliphatic group include an alkyl group (eg, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group).
- acylamino group for example, acetylamino group, benzoylamino group, methylureido group Etc .
- carbamoyl group for example An aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, a propylaminocarbonyl group, a pentylaminocarbonyl
- Rl 2 represents an aromatic group or an aromatic heterocyclic group
- Rl 3 represents a hydrogen atom, an aliphatic group, an aromatic group, or an aromatic heterocyclic group.
- the aromatic group represented by Rl 2 and Rl 3 include a phenyl group, a naphthyl group, and an anthracenyl group.
- the aromatic heterocyclic group include a furyl group, a thienyl group, a pyridyl group, and a pyridazinyl group.
- pyrimidyl group pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, pyrrolyl group, 2-quinolyl group, 1-isoquinyl group, etc. It is done.
- Examples of the aliphatic group represented by Rl 3 include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group), a cycloalkyl group (for example, Cyclohexyl group, cyclopentyl group, etc.), alkenyl group, cycloalkenyl group, alkynyl group (for example, propargyl group, etc.) and the like.
- an alkyl group for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group
- a cycloalkyl group for example, Cyclohexyl group, cyclopentyl group, etc.
- the group represented by Rl 2 is preferably a substituted or unsubstituted phenyl group, a 5-membered or 6-membered heterocyclic group (for example, a thienyl group, a furyl group, a pyrrolyl group, a pyridyl group, etc.
- Rl 3 As the group represented, a substituted or unsubstituted phenyl group, a 5-membered or 6-membered heterocyclic group, and an alkyl group are preferable.
- Rl 2 and Rl 3 may be linked to each other to form a ring structure.
- Rl 2 and Rl 3 both of them may have a substituent,
- it is a heterocyclic group, or any one is a combination of a phenyl group and a heterocyclic group which may have a substituent, and the other is a combination of an alkyl group which may have a substituent.
- X represents> N—Rl 4 , an oxygen atom or a sulfur atom, preferably> N—Rl 4 .
- Rl 4 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group, preferably a hydrogen atom, an alkyl group, an aromatic group, a heterocyclic group, an acyl group, more preferably hydrogen An atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms, and an acyl group, particularly preferably a hydrogen atom or an aryl group having 5 to 10 carbon atoms.
- the groups represented by Rl 1 to Rl 4 may be further substituted with an arbitrary substituent, and the substituent is not particularly limited.
- an alkyl group for example, Methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, etc.
- cycloalkyl group for example, cyclohexyl group, cyclopentyl group, etc.
- alkenyl group, cycloalkenyl group, alkynyl group for example, , Propargyl group, etc.
- glycidyl group acrylate group, methacrylate group, aromatic group (eg, phenyl group, naphthyl group, anthracenyl group, etc.), heterocyclic group (eg, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl 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 a weakly adsorbed state, and it is preferable that the adsorptive group is a chemisorbable group.
- At least one of the groups represented by Rl 1 to Rl 4 has a partial structure of —COOH, —P ⁇ O (OH) 2 , —OP ⁇ O (OH) 2 and —Si ( OR) 3 (R represents an alkyl group) and preferably has at least one chemisorbable group.
- an auxiliary compound that can be oxidized and reduced may be added in order to promote the electrochemical reaction of the compound that reversibly changes color 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.
- it may be immobilized on the electrode, or may be added to the electrolyte solution.
- These promoters can be used, for example, as counter electrode reactants or as redox mediators.
- 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 discolors 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.
- the durability of the display element is increased.
- 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.
- 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 oxoammonium cation has a high oxidizing ability and can function as a mediator because it can oxidize leuco dyes and the like.
- the N-oxyl derivative may be contained in the electrolyte solution or may be immobilized on the electrode surface.
- Examples of the method of immobilizing on the electrode surface include a method of introducing a group that chemically or physically adsorbs with the electrode surface into the N-oxyl derivative, 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.
- Azaadamantane N-oxyl derivatives or azabicyclo N-oxyl derivatives are preferable in that they do not cause a decrease in activity.
- 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 and performing oxidation.
- 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 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
- Organic solvent in the electrolyte according to the present invention, as a solvent, a metal salt compound that is generally used in an electrochemical cell or a battery and is reversibly dissolved and precipitated by an electrochemical redox reaction, including an electrochromic compound used in the present invention.
- a solvent capable of dissolving various additives such as a promoter can be used.
- room temperature molten salt can also be used as a solvent.
- the room temperature molten salt is a salt composed of ion pairs that are melted at room temperature (that is, in a liquid state) consisting only of ion pairs that do not contain a solvent component, and usually has a melting point of 20 ° C. or lower, A salt consisting of an ion pair that is liquid at a temperature above.
- the room temperature molten salt can be used alone or in combination of two or more.
- 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.
- a particularly preferably used solvent is 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 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.
- these solvents it is 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.
- a porous white scattering layer containing a white scattering material can be provided from the viewpoint of further increasing display contrast and white display reflectance.
- 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.
- 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 examples 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 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.
- 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 according to the present invention is preferably in the range of 10,000 to 2,000,000, more preferably in the range of 30,000 to 500,000 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 white particles.
- 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 coloring prevention at high temperature and the reflectance of the element due to the refractive index.
- 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 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 alcohol solvent a compound having high solubility in water such as methanol, ethanol, isopropanol is preferably used, and the mixing ratio with the water / alcohol solvent is preferably in the range of 0.5 to 20 in terms of mass ratio. More preferably, it is in the range of 2-10.
- 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 component between the counter electrodes of the display element, but at least one electrode surface of the counter electrode It is preferable to apply on top.
- 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
- 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.
- 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.
- 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.
- the porous as used in the present invention means that a water mixture of the water-based polymer and the white pigment is applied on an electrode and dried to form a porous white scattering material, and then silver or silver is formed on the scattering material. After applying an electrolyte solution containing the compound contained in the chemical structure, it can be sandwiched between the counter electrodes, giving a potential difference between the counter electrodes, causing a silver dissolution precipitation reaction, and ionic species can move between the electrodes Says the penetration state.
- 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.
- hardeners used in the present invention include, for example, US Pat. No. 4,678,739, column 41, 4,791,042, JP-A-59-116655, and 62-245261. No. 61-18942, 61-249054, 61-245153, JP-A-4-218044, and the like.
- 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.
- a thickener can be used for the electrolyte.
- gelatin gum arabic, poly (vinyl alcohol), hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate, cellulose acetate butyrate, poly ( Vinylpyrrolidone), poly (alkylene glycol), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly ( Styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (PVC Redene), poly (epoxide) s, poly (PVC Redene), poly (epoxide) s, poly (PVC Reden
- thickeners may be used in combination of two or more.
- compounds described on pages 71 to 75 of JP-A No. 64-13546 can be exemplified.
- the compounds preferably used are polyvinyl alcohols, polyvinyl pyrrolidones, hydroxypropyl celluloses, and polyalkylene glycols from the viewpoint of compatibility with various additives and improvement in dispersion stability of white particles.
- 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 (fusing method) (using fine pores formed between particles by partially fusing polymer fine particles or inorganic particles by adding a binder, etc.), 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.
- the substrate that can be used in the present invention is preferably a transparent substrate.
- a transparent substrate include polyester (for example, polyethylene terephthalate), polyimide, polymethyl methacrylate, polystyrene, polypropylene, polyethylene, and polyamide.
- Nylon, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyether sulfone, silicon resin, polyacetal resin, fluororesin, cellulose derivative, polyolefin and other polymer films, plate substrates, glass substrates, 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 following various electrodes can be used as the counter substrate.
- the electrode positioned on the display side is preferably a transparent electrode.
- the transparent electrode is not particularly limited as long as it is transparent and can conduct 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
- chromium carbon, aluminum, silicon, amorphous silicon, and BSO (Bismuth Silicon Oxide).
- polythiophene, polypyrrole, polyaniline, polyacetylene, polyparaphenylene, polyselenophenylene, etc., and their modifying compounds can be used alone or in combination.
- 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 nanoporous electrode having a nanoporous structure can be provided on the transparent 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 as used in the present invention refers to a state in which an infinite number of nanometer-sized pores exist in a layer and ionic species contained in the electrolyte can move within the nanoporous structure.
- 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.
- the main components of the fine particles constituting the nanoporous electrode are metals such as Cu, Al, Pt, Ag, Pd and Au, metal oxides such as ITO, SnO 2 , TiO 2 and ZnO, carbon nanotubes, glassy carbon, and diamond. It can be selected from carbon electrodes such as like carbon and nitrogen-containing carbon, and is preferably selected from metal oxides such as ITO, SnO 2 , TiO 2 , and ZnO.
- 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.
- the film thickness of the nanoporous electrode is preferably in the range of 0.1 to 10 ⁇ m, more preferably in the range of 0.25 to 5 ⁇ m.
- auxiliary electrode can be attached to at least one of the counter electrodes according to the present invention.
- the auxiliary electrode is preferably made of a material having a lower electrical resistance than the main electrode 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.
- patterning may be performed by photolithography, printing, ink jet, electrolytic plating, electroless plating, or exposure and development using a silver salt photosensitive material to form a pattern.
- the line width and line spacing of the auxiliary electrode pattern may be arbitrary values, but 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 transparent electrode and the metal auxiliary electrode. For example, a method of depositing a mask on a substrate by a sputtering method or the like, a method of patterning by a photolithography method after forming the entire surface, and the like can be given.
- 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 a coating method
- a known method such as a dipping method, a spinner method, a spray method, a roll coater method, a flexographic printing method, a screen printing method, or the like can be used.
- the following electrostatic ink jet method is capable of continuously printing a highly viscous liquid 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 has a liquid discharge head having a nozzle with an internal diameter of 30 ⁇ m or less for discharging a charged liquid, and supplies a solution into the nozzle.
- the liquid discharge device is provided with a supply unit that performs the discharge 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 from the nozzle tip.
- it comprises operation control means for controlling application of drive voltage for driving the convex meniscus forming means and application of discharge voltage by the discharge voltage application means, and this operation control means applies application of the discharge voltage by the discharge voltage application means. 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.
- an operation control unit that controls driving of the convex meniscus forming unit and voltage application by the discharge voltage applying unit, and the operation control unit includes an operation for raising the solution by the convex meniscus forming unit, and application of the discharge voltage.
- a liquid discharge device having a second discharge control unit that synchronizes the liquid, and the operation control means includes a liquid level at the tip of the nozzle after the swell operation of the solution and the application of the discharge voltage. It is also a preferred form to use a liquid ejection apparatus having a liquid level stabilization control unit that performs operation control for drawing in the inside.
- a sealant In the display element of the present invention, a sealant, a columnar structure, and spacer particles can be used as necessary.
- Sealing agent is for sealing so that it does not leak 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 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, the circuit described in FIG.
- 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.
- An electrolyte 2 was prepared in the same manner as in the preparation of the electrolyte 1 except that 0.08 parts by mass of potassium hydroxide was changed to 0.07 parts by mass of triethylamine.
- An electrolyte 3 was prepared in the same manner as in the preparation of the electrolyte 1 except that 0.08 parts by mass of potassium hydroxide was changed to 0.10 parts by mass of triethylamine.
- An electrolyte 5 was prepared in the same manner as in the preparation of the electrolyte 1 except that 0.08 parts by mass of potassium hydroxide was changed to 0.21 parts by mass of triethylamine.
- An electrolyte 6 was prepared in the same manner as in the preparation of the electrolyte 1 except that 0.08 parts by mass of potassium hydroxide was changed to 0.28 parts by mass of triethylamine.
- An electrolyte 7 was prepared in the same manner as in the preparation of the electrolyte 1 except that 0.08 parts by mass of potassium hydroxide was changed to 0.2 parts by mass of triethanolamine.
- electrolyte 8 was prepared in the same manner as in the preparation of the electrolyte 1 except that 0.08 parts by mass of potassium hydroxide was changed to 0.1 parts by mass of polyallylamine PAA-01 (manufactured by Nittobo).
- the electrolyte 9 was prepared in the same manner as in the preparation of the electrolyte 1 except that 0.08 parts by mass of potassium hydroxide was changed to 1 part by mass of 3- (1-piperidino) propyl-modified silica gel (introduced amount 1.1 mmol / g). Prepared.
- An electrolyte 10 was prepared in the same manner as in the preparation of the electrolyte 1 except that 0.08 parts by mass of potassium hydroxide was removed.
- An electrolyte 11 was prepared in the same manner as in the preparation of the electrolyte 1 except that 0.08 parts by mass of potassium hydroxide was changed to 0.2 parts by mass of potassium hydroxide.
- An electrolyte 12 was prepared in the same manner as in the preparation of the electrolyte 4 except that the exemplified compound G-18 was used instead of the exemplified compound G-19.
- An electrolyte 13 was prepared in the same manner as in the preparation of the electrolyte 4 except that the exemplified compound G-19 (2-mercaptobenzimidazole) was omitted.
- An electrolyte 14 was prepared in the same manner as in the preparation of the electrolyte 9 except that the exemplified compound G-18 was used instead of the exemplified compound G-19.
- An electrolyte 15 was prepared in the same manner as in the preparation of the electrolyte 9 except that the exemplified compound G-19 (2-mercaptobenzimidazole) was omitted.
- a transparent electrode is formed according to a known method on an ITO (Indium Tin Oxide) film having a pitch of 145 ⁇ m and a width of 130 ⁇ m as a conductive layer on a 2 cm ⁇ 4 cm glass substrate having a thickness of 1.5 mm. Was made.
- ITO Indium Tin Oxide
- Electrode 2 On the transparent electrode of electrode 1, a titanium dioxide layer having a thickness of 5 ⁇ m (about 4 to 10 particles having an average particle diameter of 17 nm was necked) was formed, and electrode 2 was produced.
- Electrode 3 (Preparation of electrode 3) The electrode 2 was immersed in the following treatment solution 1 and allowed to stand at room temperature for about 1 hour, washed with ethanol and water, subsequently heated at 100 ° C. for about 1 hour, and then allowed to cool. Next, the following treatment liquid 2 was applied on the titanium dioxide layer under the condition of about 100 mg / cm 2 , left at room temperature for about 3 hours, and then washed with ethanol and water to produce an electrode 3.
- Treatment liquid 1 While stirring 20 g of pure water, 0.1 g of 3-aminopropyltrimethoxysilane was added dropwise, and the mixture was stirred at room temperature for about 1 hour to prepare Treatment Solution 1.
- the electrode 2 produced above is immersed in the treatment liquid 3 and left at room temperature for about 1 hour, washed with ethanol and water, then heated at 100 ° C. for about 1 hour, and then allowed to cool to produce the electrode 4. did.
- the treatment liquid 4 is applied on the titanium dioxide layer of the electrode 2 so as to be about 100 mg / cm 2 , left at room temperature for about 1 hour, washed with ethanol and water, and subsequently at 100 ° C. for about 1
- the electrode 5 was produced by heating for a time.
- display elements 2 to 8 were produced in the same manner except that electrolytes 2 to 8 were used instead of the electrolyte 1, respectively.
- display elements 11 and 12 In the production of the display element 1, display elements 11 and 12 were produced in the same manner except that the electrolytes 10 and 11 were used in place of the electrolyte 1, respectively.
- display elements 13 and 14 In the production of the display element 1, display elements 13 and 14 were produced in the same manner except that the electrolytes 12 and 13 were used in place of the electrolyte 1, respectively.
- Display elements 15 and 16 were manufactured in the same manner except that electrolytes 14 and 15 were used in place of electrolyte 1 in the manufacture of display element 9.
- Display elements 17 and 18 were produced in the same manner except that electrodes 4 and 5 were used in place of electrode 3 in the production of display element 4.
- Table 2 shows the main configuration of each display element and the evaluation results obtained.
- the display element having the configuration defined in the present invention has a faster rewriting speed from white display to color display than the comparative example.
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Abstract
Description
2.前記電解質の酸性度が、6.0以上、8.0以下であることを特徴とする前記1に記載の表示素子。
4.前記一対の対向電極間に、アミノ基を有する高分子化合物を含有することを特徴とする前記1から3のいずれか1項に記載の表示素子。
本発明の表示素子においては、一対の対向電極間に、金属塩化合物と、本発明に係る一般式(G)で表されるメルカプト化合物を含有し、かつ酸性度が、5.0以上、9.0以下である電解質と、本発明に係る一般式(L)で表される化合物とを有し、対向電極間に正負両極性の電圧を印加することにより、白表示と黒表示と白黒以外のカラー表示とを可逆的に切り替えることができる。
本発明でいう「電解質」とは、一般に、水などの溶媒に溶けて溶液がイオン伝導性を示す物質(以下、「狭義の電解質」という。)をいうが、本発明の説明においては、狭義の電解質に電解質、非電解質を問わず他の金属、化合物等を含有させた混合物を電解質(「広義の電解質」)という。
本発明に係る金属塩化合物とは、対向電極上の少なくとも1方の電極上で、該対向電極の駆動操作で、溶解・析出を行うことができる金属種を含む塩であれば、如何なる化合物であってもよい。好ましい金属種は、銀、ビスマス、銅、ニッケル、鉄、クロム、亜鉛等であり、特に好ましいのは銀、ビスマスである。
本発明に適用可能な銀塩化合物とは、銀または、銀を化学構造中に含む化合物、例えば、酸化銀、硫化銀、金属銀、銀コロイド粒子、ハロゲン化銀、銀錯体化合物、銀イオン等の化合物の総称であり、固体状態や液体への可溶化状態や気体状態等の相の状態種、中性、アニオン性、カチオン性等の荷電状態種は、特に問わない。
本発明の表示素子においては、電解質液に含まれるハロゲンイオンまたはハロゲン原子のモル濃度を[X](モル/kg)とし、前記電解質液に含まれる銀または銀を化学構造中に含む化合物の銀の総モル濃度を[Metal](モル/kg)としたとき、下式(1)で規定する条件を満たすことが好ましい。
本発明でいうハロゲン原子とは、ヨウ素原子、塩素原子、臭素原子、フッ素原子のことをいう。[X]/[Metal]が0.1よりも大きい場合は、金属の酸化還元反応時に、X-→X2が生じ、X2は析出した金属と容易にクロス酸化して析出した金属を溶解させ、メモリー性を低下させる要因の1つになるので、ハロゲン原子のモル濃度は金属銀のモル濃度に対してできるだけ低い方が好ましい。本発明においては、0≦[X]/[Metal]≦0.001がより好ましい。ハロゲンイオンを添加する場合、ハロゲン種については、メモリー性向上の観点から、各ハロゲン種モル濃度総和が[I]<[Br]<[Cl]<[F]であることが好ましい。
本発明に係る電解質においては、上記金属化合物と共に、金属塩(特に、銀塩)の溶解析出を促進するための金属塩溶剤として、一般式(G)で表されるメルカプト化合物を含有することを特徴の一つとする。
本発明において、電解質の酸性度を、5.0以上、9.0以下とすることを特徴とし、更には、6.0以上、8.0以下に調整することが好ましい。電解質の酸性度を5.0以上とすることにより、白表示、黒表以外のカラー表示を行なう際の書換え速度を向上させることができる。
本発明において、電解質の酸性度を調整する手段として、アミノ基を含有するモノマー単位を有するポリマーを挙げることができる。
本発明において、電解質の酸性度を調整する手段として、粒子表面にアミン化合物を担持した有機あるいは無機微粒子を用いることができる。
本発明の表示素子において用いることができる支持電解質としては、電気化学の分野又は電池の分野で通常使用される塩類、酸類、アルカリ類が使用できる。
更には、
本発明においては、カラー表示を目的としたエレクトロクロミック化合物(以下EC化合物若しくはEC色素と記す)として、前記一般式(L)で表されるイミダゾール系色素を用いることを特徴の一つとする。
本発明の表示素子においては、電気化学的な酸化還元反応により可逆的に変色する化合物の電気化学反応を促進するために、酸化還元されうる補助化合物(以下、プロモーターと記す)を添加することが好ましい。プロモーターは酸化還元反応の結果として、可視領域(400~700nm)の光学濃度が変化しないものでもよいし、変化するもの、即ち前記電気化学的な酸化還元反応により可逆的に変色する化合物であってもよく、電極上に固定化されていてもよく、電解質液中に添加されていてもよい。これらプロモーターは例えば、対極反応物質としての利用あるいは、酸化還元メディエーターとしての利用が考えられる。
2)ガルビノキシル等、0-位に嵩高い置換基を導入したアリロキシ遊離基を有する化合物、
3)フェロセン等のメタロセン誘導体、
4)ベンジル(ジフェニルエタンジオン)誘導体、
5)テトラゾリウム塩/ホルマザン誘導体、
6)フェナジン、フェノチアジン、フェノキサジン、アクリジン等のアジン系化合物、
7)ビオロゲン等ピリジニウム化合物、
その他、ベンゾキノン誘導体、ベルダジル等ヒドラジル遊離基化合物、チアジル遊離基化合物、ヒドラゾン誘導体、フェニレンジアミン誘導体、トリアリルアミン誘導体、テトラチアフルバレン誘導体、テトラシアノキノジメタン誘導体、チアントレン誘導体等もプロモーターとして用いることができる。
本発明に係る電解質には、溶媒としては、一般に電気化学セルや電池に用いられ、本発明で用いられるエレクトロクロミック化合物を初め、電気化学的な酸化還元反応により可逆的に溶解析出する金属塩化合物、プロモーター等各種添加剤を溶解できる溶媒を使用することができる。
本発明においては、表示コントラスト及び白表示反射率をより高める観点から、白色散乱物を含有する多孔質白色散乱層を有することができる。
本発明の表示素子においては、電解質に増粘剤を使用することができ、例えば、ゼラチン、アラビアゴム、ポリ(ビニルアルコール)、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、セルロースアセテート、セルロースアセテートブチレート、ポリ(ビニルピロリドン)、ポリ(アルキレングリコール)、カゼイン、デンプン、ポリ(アクリル酸)、ポリ(メチルメタクリル酸)、ポリ(塩化ビニル)、ポリ(メタクリル酸)、コポリ(スチレン-無水マレイン酸)、コポリ(スチレン-アクリロニトリル)、コポリ(スチレン-ブタジエン)、ポリ(ビニルアセタール)類(例えば、ポリ(ビニルホルマール)及びポリ(ビニルブチラール))、ポリ(エステル)類、ポリ(ウレタン)類、フェノキシ樹脂、ポリ(塩化ビニリデン)、ポリ(エポキシド)類、ポリ(カーボネート)類、ポリ(ビニルアセテート)、セルロースエステル類、ポリ(アミド)類、疎水性透明バインダとして、ポリビニルブチラール、セルロースアセテート、セルロースアセテートブチレート、ポリエステル、ポリカーボネート、ポリアクリル酸、ポリウレタン等が挙げられる。
〔電子絶縁層〕
本発明の表示素子においては、電気絶縁層を設けることができる。
本発明の表示素子の構成層には、保護層、フィルター層、ハレーション防止層、クロスオーバー光カット層、バッキング層等の補助層を挙げることができ、これらの補助層中には、各種の化学増感剤、貴金属増感剤、感光色素、強色増感剤、カプラー、高沸点溶剤、カブリ防止剤、安定剤、現像抑制剤、漂白促進剤、定着促進剤、混色防止剤、ホルマリンスカベンジャー、色調剤、硬膜剤、界面活性剤、増粘剤、可塑剤、スベリ剤、紫外線吸収剤、イラジエーション防止染料、フィルター光吸収染料、防ばい剤、ポリマーラテックス、重金属、帯電防止剤、マット剤等を、必要に応じて含有させることができる。
〈表示側透明基板〉
本発明で用いることのできる基板としては、透明基板であることが好ましく、このような透明基板としては、ポリエステル(例えば、ポリエチレンテレフタレート等)、ポリイミド、ポリメタクリル酸メチル、ポリスチレン、ポリプロピレン、ポリエチレン、ポリアミド、ナイロン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリカーボネート、ポリエーテルスルフォン、シリコン樹脂、ポリアセタール樹脂、フッ素樹脂、セルロース誘導体、ポリオレフィンなどの高分子のフィルムや板状基板、ガラス基板などが好ましく用いられる。本発明に用いられる透明な基板とは、可視光に対する透過率が少なくとも50%以上の基板をいう。
本発明の表示素子においては、対向基板として下記の各種電極を用いることができる。
対向電極のうち、表示側には位置する電極としては、透明電極であることが好ましい。
透明電極の一つの態様として、上記透明電極上にナノ多孔質化構造を有するナノ多孔質電極を設けることができる。このナノ多孔質電極は、表示素子を形成した際に実質的に透明で、エレクトロクロミック色素等の電気活性物質を担持することができる。
本発明に係る対向電極のうち少なくとも一方の電極に、補助電極を付帯させることができる。
透明電極、金属補助電極を形成するには、公知の方法を用いることができる。例えば、基板上にスパッタリング法等でマスク蒸着する方法や、全面形成した後に、フォトリソグラフィ法でパターニングする方法等が挙げられる。
本発明の表示素子においては、複合電極の透明電極及び金属補助電極の少なくとも1方が、帯電した液体を吐出する内部直径が30μm以下のノズルを有する液体吐出ヘッドと、前記ノズル内に溶液を供給する供給手段と、前記ノズル内の溶液に吐出電圧を印加する吐出電圧印加手段とを備えた液体吐出装置を用いて形成されることが好ましい態様の1つである。さらにノズル内の溶液がノズル先端部から凸状に盛り上がった状態を形成する凸状メニスカス形成手段を設けた吐出装置を用いて形成されることが好ましい。
本発明の表示素子には、必要に応じて、シール剤、柱状構造物、スペーサー粒子を用いることができる。
本発明の表示素子の駆動操作は、単純マトリックス駆動であっても、アクティブマトリック駆動であってもよい。本発明でいう単純マトリックス駆動とは、複数の正極を含む正極ラインと複数の負極を含む負極ラインとが対向する形で互いのラインが垂直方向に交差した回路に、順次電流を印加する駆動方法のことを言う。単純マトリックス駆動を用いることにより、回路構成や駆動ICを簡略化でき安価に製造できるメリットがある。アクティブマトリックス駆動は、走査線、データライン、電流供給ラインが碁盤目状に形成され、各碁盤目に設けられたTFT回路により駆動させる方式である。画素毎にスイッチングが行えるので、階調やメモリー機能などのメリットがあり、例えば、特開2004-29327号の図5に記載されている回路を用いることができる。
本発明の表示素子は、電子書籍分野、IDカード関連分野、公共関連分野、交通関連分野、放送関連分野、決済関連分野、流通物流関連分野等の用いることができる。具体的には、ドア用のキー、学生証、社員証、各種会員カード、コンビニストアー用カード、デパート用カード、自動販売機用カード、ガソリンステーション用カード、地下鉄や鉄道用のカード、バスカード、キャッシュカード、クレジットカード、ハイウェーカード、運転免許証、病院の診察カード、電子カルテ、健康保険証、住民基本台帳、パスポート、電子ブック等が挙げられる。
(電解質1の調製)
ジメチルスルホキシド2.5質量部中に、テトラフルオロホウ酸スピロ-(1,1′)-ビピロリジニウム0.025質量部と、カルボキシTEMPO(4-カルボキシ-2,2,6,6-テトラメチルピペリジン-1-オキシル フリーラジカル)0.05質量部と、p-トルエンスルホン酸銀0.1質量部と、例示化合物G-19(2-メルカプトベンズイミダゾール)0.2質量部と、水酸化カリウム0.08質量部とを、それぞれ添加、攪拌、溶解して、電解質1を調製した。
上記電解質1の調製において、水酸化カリウム0.08質量部をトリエチルアミン0.07質量部に変更した以外は同様にして、電解質2を調製した。
上記電解質1の調製において、水酸化カリウム0.08質量部をトリエチルアミン0.10質量部に変更した以外は同様にして、電解質3を調製した。
上記電解質1の調製において、水酸化カリウム0.08質量部をトリエチルアミン0.14質量部に変更した以外は同様にして、電解質4を調製した。
上記電解質1の調製において、水酸化カリウム0.08質量部をトリエチルアミン0.21質量部に変更した以外は同様にして、電解質5を調製した。
上記電解質1の調製において、水酸化カリウム0.08質量部をトリエチルアミン0.28質量部に変更した以外は同様にして、電解質6を調製した。
上記電解質1の調製において、水酸化カリウム0.08質量部をトリエタノールアミン0.2質量部に変更した以外は同様にして、電解質7を調製した。
上記電解質1の調製において、水酸化カリウム0.08質量部をポリアリルアミンPAA-01(日東紡社製)0.1質量部に変更した以外は同様にして、電解質8を調製した。
上記電解質1の調製において、水酸化カリウム0.08質量部を3-(1-ピペリジノ)プロピル修飾シリカゲル(導入量1.1mmol/g)1質量部に変更した以外は同様にして、電解質9を調製した。
上記電解質1の調製において、水酸化カリウム0.08質量部を除いた以外は同様にして、電解質10を調製した。
上記電解質1の調製において、水酸化カリウム0.08質量部を水酸化カリウム0.2質量部に変更した以外は同様にして、電解質11を調製した。
上記電解質4の調製において、例示化合物G-19に代えて、例示化合物G-18を用いた以外は同様にして、電解質12を調製した。
上記電解質4の調製において、例示化合物G-19(2-メルカプトベンズイミダゾール)を除いた以外は同様にして、電解質13を調製した。
上記電解質9の調製において、例示化合物G-19に代えて、例示化合物G-18を用いた以外は同様にして、電解質14を調製した。
上記電解質9の調製において、例示化合物G-19(2-メルカプトベンズイミダゾール)を除いた以外は同様にして、電解質15を調製した。
上記調製した電解質1~15に対して等量の純水を加えて撹拌し、水層の25℃におけるpHを、東亜電波工業(株)のデジタルpHメーター HM-30Sを用い測定し、これを酸性度とした。なお、表示素子10については、電解質10を空セルに注入したあと室温で1時間放置し、その後、セルを分解して取り出して、封止剤に添加したポリアリルアミンPAA-01(日東紡社製)を電解液に拡散、含有させた電解液10′について上記と同様にして測定した。得られた結果を、後述の表2に示す。
(電極1の作製)
厚さ1.5mmで2cm×4cmのガラス基板上に、導電層としてピッチ145μm、幅130μmのITO(Indium Tin Oxide、インジウム錫酸化物)膜を公知の方法に従って透明電極を形成して、電極1を作製した。
電極1の透明電極上に、厚み5μmの二酸化チタン層(平均粒子径17nmの粒子が4~10個程度ネッキング済み)を形成し、電極2を作製した。
上記電極2を、下記処理液1に浸漬し、室温で約1時間放置した後、エタノール及び水で洗浄し、続いて100℃で約1時間加熱し、その後放冷した。次いで、下記処理液2を二酸化チタン層上に約100mg/cm2となる条件で付与し、室温で約3時間放置した後、エタノール及び水で洗浄して、電極3を作製した。
純水20gを撹拌しながら、3-アミノプロピルトリメトキシシラン0.1gを滴下し、室温で約1時間攪拌して、処理液1を調製した。
EC化合物として例示化合物(L1)0.025gと、1-エチル-3-(3-ジメチルアミノプロピル)カルボジミド塩酸塩0.032gとを、ジメチルホルムアミド1.0gに溶解して、処理液2を調製した。
例示化合物(L18)を3mmol/Lとなるようにアセトニトリル/エタノールに溶解させて、処理液3を調製した。
酢酸0.02質量部、純水1.0質量部、メタノール1.0質量部を攪拌しているところへ、例示化合物(L26)の0.01質量部をメタノール0.15質量部に溶解させた溶液を滴下し、室温で約1時間攪拌して処理液4を調製した。
電極1上に、下記二酸化チタン分散物を乾燥後の平均膜厚が20μmになるようにスクリーン印刷し、その後50℃で30分間乾燥して溶媒を蒸発させた後、85℃の雰囲気中で1時間乾燥させて、電極1上に多孔質白色散乱層を有する電極6を作製した。
水及びエタノールの1:1の混合溶液に、クラレポバールPVA235(クラレ社製、ポリビニルアルコール樹脂)を固形分濃度で2質量%になるように添加し、加熱溶解させた後、二酸化チタンCR-90(石原産業社製)を、固形分濃度で20質量%となるように添加し、超音波分散機で分散させて、二酸化チタン分散物を得た。
(表示素子1の作製)
電極6の周辺部を、平均粒径40μmのガラス製球形ビーズを体積分率として10%含むオレフィン系封止剤で縁取りした後に、電極3と電極6とを、それぞれストライプ状の電極が直交するように貼り合わせ、さらに加熱押圧して空セルを作製した。該空セルに電解質1を真空注入し、注入口をエポキシ系の紫外線硬化樹脂にて封止し、表示素子1を作製した。
上記表示素子1の作製において、電解質1に代えて、それぞれ電解液2~8を用いた以外は同様にして、表示素子2~8を作製した。
電極6の周辺部を、平均粒径150μmのプラスチック製球形ビーズを体積分率として10%含むオレフィン系封止剤で縁取りした後に、電極3と電極6とを、それぞれストライプ状の電極が直交するように貼り合わせ、さらに加熱押圧して空セルを作製した。該空セルに電解質9を真空注入し、注入口をエポキシ系の紫外線硬化樹脂にて封止し、表示素子9を作製した。
電極6の周辺部を、平均粒径150μmのプラスチック製球形ビーズを体積分率として10%とポリアリルアミンPAA-01(日東紡社製)10%とを含むオレフィン系封止剤で縁取りした後に、電極3と電極6とを、それぞれストライプ状の電極が直交するように貼り合わせ、さらに加熱押圧して空セルを作製した。該空セルに電解質10を真空注入し、注入口をエポキシ系の紫外線硬化樹脂にて封止し、表示素子8を作製した。
上記表示素子1の作製において、電解質1に代えて、それぞれ電解質10、11を用いた以外は同様にして、表示素子11、12を作製した。
上記表示素子1の作製において、電解質1に代えて、それぞれ電解質12、13を用いた以外は同様にして、表示素子13、14を作製した。
上記表示素子9の作製において、電解質1に代えて、それぞれ電解質14、15を用いた以外は同様にして、表示素子15、16を作製した。
上記表示素子4の作製において、電極3に代えて、それぞれ電極4、5を用いた以外は同様にして、表示素子17、18を作製した。
〔表示速度〕
定電圧電源の両端子に作製した表示素子の両電極を接続し、表示側の電極に+1.5Vの電圧を0.5秒間印加し、カラー表示した時の可視光領域の極大吸収波長での反射率(Rc)と、白状態の上記同波長での反射率(Rw)をコニカミノルタセンシング社製の分光測色計CM-3700dで測定し、Rc/Rwの値を表示速度の指標とした。この数値が小さいほど表示速度が速いことを意味する。
Claims (6)
- 一対の対向電極間に少なくとも電解質と下記一般式(L)で表される化合物とを含有し、該電解質が、金属塩化合物と下記一般式(G)で表されるメルカプト化合物とを含有し、該電解質の酸性度が、5.0以上、9.0以下であり、かつ対向電極の駆動操作により、白表示、黒表示及び黒以外のカラー表示を行なうことを特徴とする表示素子。
〔式中、Rl1は、ハロゲン原子、脂肪族基、脂肪族オキシ基、アシルアミノ基、カルバモイル基、アシル基、スルホンアミド基またはスルファモイル基を表し、nは1から4の整数を表す。Rl2は芳香族基または芳香族複素環基を表し、Rl3は水素原子、脂肪族基、芳香族基または芳香族複素環基を表す。Xは>N-Rl4、酸素原子または硫黄原子を表し、Rl4は水素原子、脂肪族基、芳香族基、複素環基またはアシル基を表す。Rl1からRl4で表される基は、更に任意の置換基で置換されていても良い。〕
〔式中、Zは含窒素複素環を表す。nは0から5の整数を表し、Rg21はハロゲン原子、アルキル基、アリール基、アルキルカルボンアミド基、アリールカルボンアミド基、アルキルスルホンアミド基、アリールスルホンアミド基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アルキルカルバモイル基、アリールカルバモイル基、カルバモイル基、アルキルスルファモイル基、アリールスルファモイル基、スルファモイル基、シアノ基、アルキルスルホニル基、アリールスルホニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アシルオキシ基、カルボキシル基、カルボニル基、スルホニル基、アミノ基、ヒドロキシ基または複素環基を表し、nが2以上の場合、それぞれのRg21は同じであってもよく、異なってもよく、お互いに連結して縮合環を形成してもよい。〕 - 前記電解質の酸性度が、6.0以上、8.0以下であることを特徴とする請求項1に記載の表示素子。
- 前記一対の対向電極間に、アミノ基を有する高分子化合物を含有することを特徴とする請求項1から3のいずれか1項に記載の表示素子。
- 前記一対の対向電極間に、微粒子に担持されたアミン化合物を含有することを特徴とする請求項1から4のいずれか1項に記載の表示素子。
- 前記一般式(A)で表される化合物、アミノ基を有する高分子化合物及び微粒子に担持されたアミン化合物から選ばれる少なくとも1種が、前記一対の対向電極の表面以外の領域に固定されていることを特徴とする請求項3から5のいずれか1項に記載の表示素子。
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