WO2016147543A1 - Composé électrochromique, composition électrochromique, élément électrochromique et élément d'obscurcissement électrochromique - Google Patents

Composé électrochromique, composition électrochromique, élément électrochromique et élément d'obscurcissement électrochromique Download PDF

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WO2016147543A1
WO2016147543A1 PCT/JP2016/000680 JP2016000680W WO2016147543A1 WO 2016147543 A1 WO2016147543 A1 WO 2016147543A1 JP 2016000680 W JP2016000680 W JP 2016000680W WO 2016147543 A1 WO2016147543 A1 WO 2016147543A1
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group
electrochromic
general formula
compound
radically polymerizable
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PCT/JP2016/000680
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English (en)
Inventor
Toshiya Sagisaka
Satoshi Yamamoto
Takashi Okada
Masato Shinoda
Shigenobu Hirano
Fuminari Kaneko
Mamiko Inoue
Daisuke Goto
Tohru Yashiro
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Ricoh Company, Ltd.
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Priority claimed from JP2015208313A external-priority patent/JP6728628B2/ja
Application filed by Ricoh Company, Ltd. filed Critical Ricoh Company, Ltd.
Priority to EP16764377.4A priority Critical patent/EP3268448B1/fr
Priority to KR1020177029118A priority patent/KR102027049B1/ko
Priority to CN201680014554.4A priority patent/CN107429158B/zh
Priority to US15/554,289 priority patent/US10988684B2/en
Publication of WO2016147543A1 publication Critical patent/WO2016147543A1/fr

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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom
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Definitions

  • the present invention relates to electrochromic compounds, electrochromic compositions, electrochromic elements, and electrochromic dimming elements.
  • Electrochromism is a phenomenon where an oxidation-reduction reaction is reversibly caused to reversibly change a color, as voltage is applied.
  • the electrochromism is typically established between two facing electrodes, and causes oxidation-reduction reactions with a structure where the space between the electrode is filled with an electrolyte layer capable of conducting ions.
  • an oxidation reaction which is a reverse reaction of the reduction reaction, is caused adjacent to the other electrode.
  • the electrochromic element is formed with materials, which are colorless and transparent.
  • viologen compound that is transparent in the neutralized state, and exhibits an electrochromic phenomenon where the compound colors in the reduced state.
  • titanium oxide is suitably used.
  • titanium oxide particles it has been reported that use of titanium oxide particles as particles bearing the electrochromic compound in the laminate structure can maintain a high optical density and high contrast ratio.
  • a polymer obtained by polymerizing an electrochromic composition including a radically polymerizable compound containing tryarylamine, which is transparent in the neutralized state, and exhibits an electrochromic phenomenon where the polymer colors in the reduced state is effective. It has been reported that use of the compound as an electrochromic material can secure high operation stability, and high lightfastness (for example, see NPL 1).
  • an element be driven with the lower voltage than the voltage as reported in the aforementioned literature. Moreover, it is desired to maintain the higher driving stability to achieve practical use of the electrochromic element.
  • the present invention aims to provide an electrochromic compound, which has excellent durability to repetitive use, and is colorless in a discharged state, without having an absorption band in a visible wavelength range, as discharged.
  • the electrochromic compound of the present invention is represented by the following general formula (1).
  • General Formula (1) In the general formula (1), X 1 and X 2 are each independently a carbon atom or a nitrogen atom, R 1 , R 2 and R 3 are each independently a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group, x is an integer selected from 0 through 3, y and z are each independently an integer selected from 0 through 4, and at least one of L 1 and L 2 is a monovalent functional group bonded to a nitrogen atom of a pyridinium ring directly, or via a divalent substituent.
  • the present invention can provide an electrochromic compound, which has excellent durability to repetitive use, and is colorless in a discharged state, without having an absorption band in a visible wavelength range, as discharged.
  • FIG. 1 is a schematic view illustrating one example of the electrochromic element of the present invention.
  • FIG. 2 is a schematic view illustrating another example of the electrochromic element of the present invention.
  • FIG. 3 is a schematic view illustrating one example of an electrochromic dimming element using the electrochromic compound of the present invention.
  • FIG. 4 is a graph depicting an evaluation result of the repeating test performed on the electrochromic element of Example 10.
  • FIG. 5 is a diagram depicting changes in the transmittance spectrums of discharging and charging in Example 10.
  • FIG. 6 is a diagram depicting a change in the absorption spectrum of Comparative Example 1.
  • FIG. 7 is a diagram depicting a change in the absorption spectrum of Comparative Example 2.
  • An electrochromic compound of the present invention is represented by the following general formula (1).
  • General Formula (1) In the general formula (1), X 1 and X 2 are each independently a carbon atom or a nitrogen atom, R 1 , R 2 and R 3 are each independently a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group, x is an integer selected from 0 through 3, y and z are each independently an integer selected from 0 through 4, and at least one of L 1 and L 2 is a monovalent functional group bonded to a nitrogen atom of a pyridinium ring directly, or via a divalent substituent.
  • At least one of R 1 to R 3 , and L 1 and L 2 contain a functional group capable of directly or indirectly bonding to a hydroxyl group, in view of a structure and general characteristics of a resulting electrochromic element. Moreover, it is preferred in view of a management of reaction raw materials and a synthesis reaction that at least one of L 1 and L 2 contain a functional group capable of directly or indirectly bonding to a hydroxyl group. Furthermore, it is particularly preferred that the functional group capable of directly or indirectly bonding to a hydroxyl group be a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, a silyl group, or a silanol group.
  • Examples of the halogen atom as any of R 1 to R 3 in the general formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom is preferable in view of stability.
  • Examples of the substituted or unsubstituted alkyl group as any of R 1 to R 3 include a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a t-butyl group, a s-butyl group, a n-butyl group, an i-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a 9-heptadecyl group, a 3,7-dimethyloctyl group, a 2-ethylhexyl group, a trifluoromethyl group, a 2-cyanoethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a
  • alkyl groups may be bonded to each other to form a ring.
  • alkoxy group, and the alkylthio group include an alkoxy group or alkylthio group, prepared by inserting an oxygen atom or sulfur atom into a linking site of the alkyl group.
  • the electrochromic compound of the present invention represented by the general formula (1) contains a pyridinium structure. Since the pyridinium structure is a monovalent cation, a counter anion is present in the electrochromic compound of the present invention, which is represented by the general formula (1).
  • the counter anion is appropriately selected depending on the intended purpose without any limitation, provided that the anion stably forms a pair with the cation site of the pyridinium structure. Examples of the anion include Br ion, Cl ion, ClO 4 ion, PF 6 ion, BF 4 ion, and CF 3 SO 3 ion.
  • L 1 and L 2 in the general formula (1) include a functional group directly bonding to a nitrogen atom in a ring, or a monofunctional group indirectly bonding to a nitrogen atom in a ring via a divalent hydrocarbon residue, where the hydrocarbon residue may contain a substituent.
  • the divalent hydrocarbon residue include an alkylenyl group that may include a substituent, an alkenylenyl group that may include a substituent, and an arylenyl group that may include a substituent.
  • substituent of the divalent hydrocarbon residue include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.
  • At least one of a plurality of L may be a functional group capable of directly or indirectly bonding to a hydroxyl group.
  • the functional group capable of directly or indirectly bonding to a hydroxyl group may be a functional group, which itself has a hydroxyl group, is capable of bonding directly to or indirectly to a nitrogen atom in a ring via the divalent hydrocarbon residue, and is easily changed into a hydroxyl group (e.g., a strong Lewis acid group that can be easily hydrolyzed into a hydroxyl group with moistures).
  • a structure of the functional group capable of directly or indirectly bonding to a hydroxyl group is not particularly limited, provided that the functional group is a functional group that can be directly or indirectly bonded to a hydroxyl group with hydrogen bonding, adsorption, or a chemical reaction.
  • the functional group capable of directly or indirectly bonding to a hydroxyl group include a phosphonic acid group, a phosphoric acid group, a carboxyl group, a trichlorosilyl group, a trialkoxysilyl group, a monochlorosilyl group, and a monoalkoxysilyl group.
  • the trialkoxysilyl group is preferably a triethoxysilyl group, or a trimethoxysilyl group.
  • a trialkoxysilyl group and phosphonic acid group which have high bonding forces to the below-mentioned conductive or semiconductive nano structure.
  • These functional groups capable of directly or indirectly bonding to a hydroxyl group may be arranged at any site in the molecule of the electrochromic compound of the present invention.
  • the functional group capable of directly or indirectly bonding to a hydroxyl group is preferably arranged at the L site in the general formula (1).
  • electrochromic compound of the present invention represented by the general formula (1) are listed below, but the electrochromic compound of the present invention is not limited to the following examples.
  • a production method of the electrochromic compound of the present invention which is represented by the general formula (1), is specifically described.
  • the electrochromic compound can be obtained, for example, by allowing a nitrogen-containing heteroaromatic ring derivative represented by the following general formula (1a) and a pyridine compound represented by the following general formula (1b) to react through a cross-coupling reaction in an appropriate solvent using a palladium catalyst or a nickel catalyst.
  • a cross-coupling reaction conventional methods, such as Suzuki-Miyaura cross-coupling, and Stille coupling.
  • R 1 is the same as the aforementioned R 1 described above.
  • Hal is a halogen atom, preferably a chlorine atom, a bromine atom, or an iodine atom.
  • y and R 2 are both the same as y and R 2 described above.
  • Z is a substituent active for coupling, such as a boronic acid group, a boronic acid ester group, and a trialkylstannyl group.
  • a compound, in which two halogens represented by the general formula (1a) are substituted with pyridine units represented by the general formula (1b), can be obtained by using the compound represented by the general formula (1b) in the amount of 2 mol or greater relative to the compound represented by the general formula (1a). Moreover, different units each represented by the general formula (1b) can be introduced by performing a reaction in stages.
  • the A is a monovalent group that may contain a functional group selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, and the monovalent group may include a substituent.
  • the B is preferably a halogen atom, a tosyl group, a mesyl group, or a trifyl group. The solubility of the compound, or adsorption ability of the compound to bearing particles can be controlled by appropriately changing the substituent A.
  • the solvent used for the reaction may be appropriately selected depending on the intended purpose without any limitation, but the solvent is preferably a polarity solvent, more preferably an aprotic polar solvent.
  • the solvent include acetone, acetonitrile, dimethylformamide, dimethylacetoamide, N-methylpyrrolidone, dioxane, and tetrahydrofuran. These solvents may be used alone or in combination.
  • the purification of the crude product obtained after the reaction can be performed, specifically, by various purification methods known in the art, such as solvent washing, recrystallization, column chromatography, and reprecipitation.
  • the electrochromic composition of the present invention includes a conductive or semiconductive nanostructure, and the electrochromic compound (the electrochromic compound represented by the general formula (1)) of the present invention, which can be bonded to or adsorbed onto the conductive or semiconductive nano structure.
  • the electrochromic composition When the electrochromic composition is used in an electrochromic element, the electrochromic composition colors in black, and a resulting electrochromic element has excellent memory properties, specifically, excellent retainability of a colored image.
  • the conductive or semiconductive nano structure is a structure having nano-scale irregularities, such as nano particles, and a nano-porous structure.
  • the electrochromic compound of the present invention contains a sulfonic acid group, a phosphoric acid group, or a carboxyl group as a bonding or adsorption structure
  • the electrochromic compound easily forms a composite with the nano structure, to thereby provide an electrochromic composition having excellent coloring image retainability.
  • a plurality of the sulfonic acid groups, phosphoric acid groups, and carboxyl groups may be included in the electrochromic compound.
  • the electrochromic compound of the present invention include a silyl group or silanol group
  • the electrochromic compound is bonded to the nano structure via a siloxane bond, which is a solid bond. Accordingly, a stable electrochromic composition is attained.
  • the siloxane bond is a chemical bond via a silicon atom and an oxygen atom.
  • the bonding method and bonding embodiment of the electrochromic composition are not particularly limited, as long as the electrochromic composition has a structure where the electrochromic compound and the nano structure are bonded together with a siloxane bond.
  • a material for constituting the conductive or semiconductive nano structure is preferably metal oxide in view of transparency and conductivity.
  • the metal oxide include titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, yttrium oxide, boron oxide, magnesium oxide, indium oxide, strontium titanate, potassium titanate, barium titanate, calcium titanate, calcium oxide, ferrite, hafnium oxide, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide, vanadium oxide, aluminosilicic acid, calcium phosphate, and aluminosilicate. These metal oxides may be used alone or in combination.
  • titanium oxide preferred in view of electric properties, such as electroconductivity, or physical properties, such as optical characteristics, are titanium oxide, zinc oxide, tin oxide, zirconium oxide, iron oxide, magnesium oxide, indium oxide, and tungsten oxide. Titanium oxide is particularly preferable in view of a coloring-discharging response speed.
  • a shape of the metal oxide is appropriately selected depending on the intended purpose without any limitation, but the shape of the metal oxide is preferably metal oxide particles having the average primary particle diameter of 30 nm or smaller. As the average primary particle diameter of the metal oxide is smaller, transmittance of the metal oxide to light is improved more. Accordingly, a shape thereof having a large surface area per unit volume (referred to as “specific surface area” hereinafter) is used.
  • the electrochromic compound is more efficiently born on the nano structure, leading to an electrochromic element that realizes excellent coloring-discharging display contrast ratio, and excellent multi-color display.
  • the specific surface area of the nano structure is appropriately selected depending on the intended purpose without any limitation, but the specific surface area of the nano structure is preferably 100 m 2 /g or greater.
  • the electrochromic element of the present invention includes a first support, a first electrode formed on the first support, a first electroactive layer, a second support disposed to face the first support, a second electrode formed on the second support at a side of the first support, a second electroactive layer, and an electrolyte filling between the first electrode and the second electrode.
  • the electrochromic element of the present invention preferably further includes an insulating porous layer, and may further contain other members, if necessary.
  • the first electroactive layer contains an electrochromic compound, which colors through a reduction reaction, and is represented by the above general formula (1), and the second electroactive layer contains a charge-storing material.
  • the aforementioned other members are appropriately selected depending on the intended purpose without any limitation, and examples of the aforementioned other members include an antideterioration layer, and a protective layer.
  • FIG. 1 is a cross-sectional view illustrating an example of the electrochromic device according to a first embodiment.
  • the electrochromic device contains a first support 11, a first electrode 12 formed on the first support 11, a first electroactive layer 13 disposed to be in contact with the first electrode 12, a second support 18, a second electrode 17 formed on the second support 18, a second electroactive layer 16 disposed to be in contact with the second electrode 17, an insulating porous layer 14, which is disposed between the first electrode 12 and the second electrode 17 to prevent electrical short circuit between the both electrodes, and is formed to be in contact with the first electroactive layer 13 and the second electroactive layer 16, and an electrolyte 15 configured to perform ion conduction between the electrodes.
  • the insulating porous layer 14 configured to prevent electrical short circuit between the both electrodes may be formed on a surface of the second electroactive layer 16, as illustrated in FIG. 2.
  • the constitutional elements are specifically described hereinafter.
  • the first support 11 has a function of supporting the first electrode 12, the first electroactive layer 13, and the insulating porous layer 14.
  • the second support 18 has a function of supporting the second electrode 17, the second electroactive layer 16, and the insulating porous layer.
  • an organic material or inorganic material known in the art can be used as it is, provided that the material is a transparent material capable of supporting the aforementioned layers.
  • a glass substrate such as non-alkali glass, borosilicate glass, float glass, and soda-lime glass, can be used.
  • a resin substrate such as of a polycarbonate resin, an acrylic resin, polyethylene, polyvinyl chloride, polyester, an epoxy resin, a melamine resin, a phenol resin, a polyurethane resin, and a polyimide resin
  • a surface of the support may be coated with a transparent insulating layer, or an antireflection layer, in order to enhance water-vapor barrier properties, gas barrier properties, and visibility.
  • a shape of the support is appropriately selected depending on the intended purpose without any limitation, and the shape thereof may be a rectangle or a circle, and may have a flat surface, or a spherical surface structure, such as a lens.
  • the first electrode 12 and the second electrode 17 are not particularly limited, as long as either or both of the first electrode 12 and the second electrode 17 is or are transparent.
  • materials of the first electrode 12 and the second electrode 17 are not particularly limited, as long as the materials are conductive materials. Use of the aforementioned electrodes can enhance coloring contrast.
  • the transparent conductive material for example, an inorganic material, such as tin-doped indium oxide (abbrev. ITO), fluorine-doped tin oxide (abbrev. FTO), and antimony-doped tin oxide (abbrev. ATO), can be used.
  • the transparent conductive material is preferably an inorganic material containing at least one selected from the group consisting of indium oxide (referred to as In oxide hereinafter), tin oxide (referred to as Sn oxide hereinafter), and zinc oxide (referred to as Zn oxide hereinafter).
  • In oxide, Sn oxide and Zn oxide are materials, which can be easily formed into a film by sputtering, and give excellent transparency and electroconductivity. Among them particularly preferred are InSnO, GaZnO, SnO, In 2 O 3 , and ZnO.
  • an electrode which is prepared by forming transparent carbon nanotube, or a highly-conductive non-transparent material, such as Au, Ag, Pt, and Cu, into a fine network, to improve conductivity with maintaining transparency, may be used.
  • a thickness of each of the first electrode 12 and the second electrode 17 is adjusted to attain sufficient electric resistance value required for oxidation-reduction reactions of the electrochromic layer.
  • a thickness of each of the first electrode 12 and the second electrode 17 is preferably 50 nm or greater but 500 nm or less.
  • Examples of a production method of each of the first electrode 12 and the second electrode 17 include vacuum vapor deposition, sputtering, and ion plating.
  • the production method is appropriately selected depending on the intended purpose without any limitation, provided that a material of each of the first electrode 12 and the second electrode 17 can be applied through coating, to thereby form a layer.
  • various coating or printing methods such as spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire-bar coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, and inkjet printing, can be used.
  • a metal plate such as titanium, and zinc, can be also used as the electrode.
  • the electrochromic compound represented by the general formula (1) can be used for the first electroactive layer 13.
  • Use of the certain heterocyclic compound in the first electroactive layer can be realize low voltage driving, and achieve operation stability.
  • titanium oxide is suitably used.
  • titanium oxide particles are preferably used as bearing particles of the electrochromic compound, in order to secure a high optical density and high contrast ratio.
  • the electrochromic compound colors and discharges through oxidation and reduction reactions only at a surface of the electrode.
  • the electrochromic compound can change an absorption spectrum thereof through the presence of substituents at L 1 and L 2 in the general formula (1).
  • an absorption band such as color tone
  • an absorption band can be adjusted by blending a dye having substituents at both L 1 and L 2 and a dye having a substituent at either L 1 or L 2 in the first electroactive layer, and adjusting the abundance ratio of each dye.
  • Examples of a formation method of the first electroactive layer include vacuum vapor deposition, sputtering, and ion plating.
  • various coating or printing methods such as spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire-bar coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, and inkjet printing, can be used.
  • the second electroactive layer contains a charge-storing material.
  • the charge-storing material is a material, which itself can store electric charge, and is used in the second electrochromic layer as a material that can store electric charge.
  • the second electroactive layer also functions as the second electrode 17.
  • Examples of the charge-storing material include conductive or semiconductive bearing particles, a compound including a radical, and a compound including triarylamine.
  • a material of the conductive or semiconductive bearing particles is not particularly limited, as long as the material is a material which is configured to, as the conductive or semiconductive bearing particles, prevent corrosion of the counter electrode due to irreversible an oxidation or reduction reaction.
  • the material include various materials, such as an insulating material (e.g., Al 2 O 3 , SiO 2 , and an insulating material containing any of the foregoing materials), a semiconductive material (e.g., zinc oxide, titanium oxide, a semiconductive material containing any of the foregoing materials), and an organic material (e.g., polyimide).
  • conductive or semiconductive metal oxide particles e.g., antimony-doped in oxide, nickel oxide
  • a binder such as an acrylic binder, an alkyd binder, an isocyanate binder, an urethane binder, an epoxy binder, and a phenol binder.
  • a material exhibiting an oxidation reaction which is a reverse reaction of a reaction of the electrochromic compound contained in the first electroactive layer 13 is more preferably used than the conductive or semiconductive bearing particles.
  • the first electrochromic layer and the second electrochromic layer carry out opposite reactions to each other at the same time.
  • a material colors through a reduction reaction is used as the first electrochromic layer.
  • a material that is oxidation reactive which is a reverse reaction to the reaction of the first electrochromic layer, is used for the second electrochromic layer.
  • the oxidation reactive material examples include a compound including a functional group containing radical.
  • the compound including a functional group containing radical may be a compound that is turned into a precursor of a radical compound, i.e., a compound turned into a radical state through oxidation or reduction, such as an electrode reaction. In this case, a radical side is generated through an oxidation or reduction reaction, such as an electrode reaction, after producing a gel.
  • oxidation reactive compound examples include an azobenzene compound, a tetrathiafulvalene compound, a triphenylmethane compound, a triphenylamine compound, and a leuco dye.
  • a radically polymerizable compound including a triarylamine structure site is particularly preferable in view of high driving durability and lightfastness.
  • the second electroactive layer contain an oxidation-reactive material including a triarylamine structure site, where the oxidation-reactive material including a triarylamine structure site contains a cross-linked product obtained by crosslinking a radically polymerizable compound including a triarylamine structure site, and a polymerizable composition including another radically polymerizable compound different from the radically polymerizable compound including a triarylamine structure site. It is preferred that the radically polymerizable compound including a triarylamine structure site, or the another radically polymerizable compound different from the radically polymerizable compound including a triarylamine structure site contain two or more radically polymerizable functional groups.
  • Examples of the radically polymerizable compound including a triarylamine structure site include a compound represented by the following general formula (2).
  • A is a structure represented by the following general formula (3), and is bonded to B at a site selected from R 1 through R 15 .
  • B is a structure represented by the following general formula (4), and is bonded to A at a site selected from R 16 through R 21 .
  • General Formula (3) General Formula (4)
  • R 1 to R 21 are monovalent organic groups, which may be identical or different, and at least one of the monovalent organic groups is a radically polymerizable functional group.
  • each of the monovalent organic group examples include a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, an alkoxycarbonyl group that may include a substituent, an aryloxycarbonyl group that may include a substituent, an alkylcarbonyl group that may include a substituent, an aryl carbonyl group that may include a substituent, an amide group, a monoalkylaminocarbonyl group that may include a substituent, an alkylaminocarbonyl group that may include a substituent, a monoaryl aminocarbonyl group that may include a substituent, a diarylaminocarbonyl group that may include a substituent, a sulfonic acid group, an alkoxysulfonyl group that may include a substituent, an aryloxy sulfonyl group that may include a substituent, an
  • an alkyl group particularly preferred in view of stable operation and lightfastness are an alkyl group, an alkoxyl group, a hydrogen atom, an aryl group, an aryloxy group, a halogen group, an alkenyl group, and an alkynyl group.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • Examples of the aryl group include a phenyl group, and a naphthyl group.
  • Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.
  • Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methoxyphenoxy group, and a 4-methylphenoxy group.
  • Examples of the heterocyclic group include carbazole, dibenzofuran, dibenzothiophene, oxadiazole, and thiadiazole.
  • Examples of a substituent further substituted with the substituent include a halogen atom, a nitro group, a cyano group, an alkyl group (e.g., a methyl group, and an ethyl group), an alkoxy group (e.g., a methoxy group, and an ethoxy group), an aryloxy group (e.g., a phenoxy group), an aryl group (e.g., a phenyl group, and a naphthyl group), a benzyl group, and an aralkyl group (e.g., a phenethyl group).
  • a halogen atom e.g., a methyl group, and an ethyl group
  • an alkoxy group e.g., a methoxy group, and an ethoxy group
  • an aryloxy group e.g., a phenoxy group
  • an aryl group e.g
  • Examples of the radically polymerizable functional group include a 1-substituted ethylene functional group, and 1,1-substituted ethylene functional group, which are described below.
  • X 1 is an arylene group that may include a substituent, an alkenylene group that may include a substituent, a group represented by -CO-, a group represented by -COO-, a group represented by -CON(R 100 )- [R 100 is a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group], or a group represented by -S-.
  • Examples of the arylene group in the general formula (i) include a phenylene group that may include a substituent, and a naphthylene group.
  • Examples of the alkenylene group include an ethenylene group, a propenylene group, and a butenylene group.
  • Examples of the alkyl group include a methyl group, and an ethyl group.
  • Examples of the aralkyl group include a benzyl group, a naphthylmethyl group, and a phenethyl group.
  • Examples of the aryl group include a phenyl group, and a naphthyl group.
  • radically polymerizable functional group represented by the general formula (i) include a vinyl group, a styryl group, a 2-methyl-1,3-butadienyl group, a vinylcarbonyl group, an acryloyloxy group, an acryloylamide group, and a vinyl thio ether group.
  • Y is an alkyl group that may include a substituent, an aralkyl group that may include a substituent, an aryl group that may include a substituent, a halogen atom, a cyano group, a nitro group, an alkoxy group, a group represented by -COOR 101
  • R 101 is a hydrogen atom, an alkyl group that may include a substituent, an aralkyl group that may include a substituent, an aryl group that may include a substituent, or a group represented by CONR 102 R 103 (R 102 and R 103 are each a hydrogen atom, an alkyl group that may include a substituent, an aralkyl group that may include a substituent, or an aryl group that
  • X 2 is a substituent or single bond identical to X 1 in the general formula (i), or an alkylene group, provided that at least one of Y and X 2 is an oxy carbonyl group, a cyano group, an alkenylene group, or an aromatic ring.
  • Examples of the aryl group in the general formula (ii) include a phenyl group, and a naphthyl group.
  • Examples of the alkyl group include a methyl group, and an ethyl group.
  • Examples of the alkoxy group include a methoxy group, and an ethoxy group.
  • Examples of the aralkyl group include a benzyl group, a naphthylmethyl group, and a phenethyl group.
  • radically polymerizable functional group represented by the general formula (ii) include an ⁇ -chlorinated acryloyloxy group, a methacryloyloxy group, an ⁇ -cyanoethylene group, an ⁇ -cyanoacryloyloxy group, an ⁇ -cyanophenylene group, and a methacryloylamino group.
  • examples of a substituent further substituting the substituents in X 1 , X 2 , and Y include a halogen atom, a nitro group, a cyano group, an alkyl group (e.g., a methyl group, and an ethyl group), an alkoxy group (e.g., a methoxy group, and an ethoxy group), an aryloxy group (e.g., a phenoxy group), an aryl group (e.g., a phenyl group, and a naphthyl group), and an aralkyl group (e.g., a benzyl group, and a phenethyl group).
  • an alkyl group e.g., a methyl group, and an ethyl group
  • an alkoxy group e.g., a methoxy group, and an ethoxy group
  • an aryloxy group e.g., a phen
  • radically polymerizable functional groups particularly preferred are an acryloyloxy group, and a methacryloyloxy group.
  • Examples of the radically polymerizable compound including a triarylamine structure site include compounds containing skeletons represented by the following general formulae (2-1) to (2-3).
  • R 27 through R 89 are monovalent organic groups, which may be identical or different.
  • the aforementioned another radically polymerizable compound is a compound including at least one radically polymerizable functional group, which is different from the radically polymerizable compound including triarylamine.
  • Examples of the aforementioned another radically polymerizable compound include a monofunctional radically polymerizable compound, a bifunctional radically polymerizable compound, a trifunctional or higher radically polymerizable compound, a functional monomer, and a radically polymerizable oligomer. Among them, a bifunctional or higher radically polymerizable compound is particularly preferable.
  • the radically polymerizable functional group in the aforementioned another radically polymerizable compound is identical to the radically polymerizable functional group contained in the radically polymerizable compound including triarylamine.
  • the radically polymerizable functional group an acryloyloxy group, and a methacryloyloxy group are particularly preferable.
  • the electrochromic compound including an oxidation-coloring compound is present on the first electrode, but such the electrochromic compound is preferably used in any state, as long as the electrochromic compound is compatible with the electrolyte.
  • the electrochromic compound can be present on the first electrode, as it is as a low molecular weight compound.
  • the electrochromic compound is present in a state where the electrochromic compound is cured with a photocross-linking group, such as acrylate, and methacrylate. Note that, the electrochromic compound may be present in the state where the electrochromic compound is adsorbed on bearing particles, or conductive particles.
  • Examples of a formation method of the second electroactive layer include vacuum vapor deposition, sputtering, and ion plating.
  • various coating or printing methods such as spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire-bar coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, and inkjet printing, can be used.
  • the insulating porous layer 14 has a function of retaining the electrolyte 15, as well as separating the first electrode 12 and the second electrode 17 from each other to electrically insulate between the first electrode 12 and the second electrode 17.
  • a material of the insulating porous layer 14 is not particularly limited, as long as the material is porous.
  • the material of the insulating porous layer 14 is preferably an organic or inorganic material, which has high insulating properties and durability, and excellent film formability, or a composite of the organic material and the inorganic material.
  • a sintering method (a method where polymer particles or inorganic particles are added to a binder to partially fuse the particles to utilize pores generated between the particles), or an extraction method (a method where, after forming a constituting layer with an organic or inorganic material soluble to a solvent, and a binder insoluble to the solvent, the organic or inorganic material is dissolved with the solvent to obtain pores) can be used.
  • usable methods are a foaming method where a high-molecular-weight polymer is foamed by heating or degassing, a phase transformation method where a mixture of high-molecular-weight compounds are phase-separated by operating a good solvent and a poor solvent, and a radiation method where pores are formed by applying various radial rays.
  • the insulating porous layer include a polymer-particle mixture film containing metal oxide particles (e.g., SiO 2 particles, and Al 2 O 3 particles) and a polymer binder, a porous organic film (e.g., a polyurethane resin, and a polyethylene resin), and an inorganic insulating material film formed into a porous film.
  • a thickness of the insulating porous layer 14 is appropriately selected depending on the intended purpose without any limitation, but the thickness of the insulating porous layer 14 is preferably in a range of from 0.5 ⁇ m through 3 ⁇ m.
  • a formation method of the insulating porous layer 14 vacuum vapor deposition, sputtering, or ion plating can be used.
  • various coating or printing methods such as spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire-bar coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, and inkjet printing, can be used.
  • the electrolyte layer 15 is disposed to fill between the first electrode 12 and the second electrode 17, and is disposed to be in contact with the first electroactive layer 13 and the second electroactive layer 16.
  • an electrolyte used in the electrolyte layer 15 for example, an inorganic ionic salt (e.g., alkali metal salt, and alkaline earth metal salt), a quaternary ammonium salt, an acid supporting electrolyte, or a base supporting electrolyte can be used.
  • the supporting electrolyte include LiClO 4 , LiBF 4 , LiAsF 6 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 COO, KCl, NaClO 3 , NaCl, NaBF 4 , NaSCN, KBF 4 , Mg(ClO 4 ) 2 , and Mg(BF 4 ) 2 .
  • the ionic liquid is not particularly limited, as long as the ionic liquid is a material typically researched or reported. Particularly, an organic ionic liquid has a molecular structure which is present as a liquid in a wide temperature range including room temperature.
  • examples of the cationic component include: a imidazole derivative salt, such as N,N-dimethylimidazole salt, N,N-methylethylimidazole salt, and N,N-methylpropylimidazole salt; an aromatic (e.g., a pyridinium derivative) salt, such as N,N-dimethylpyridinium salt, and N,N-methylpropylpyridinium salt; and an aliphatic quaternary ammonium (e.g., tetraalkyl ammonium) compound, such as trimethylpropyl ammonium salt, trimethylhexyl ammonium salt, and triethylhexyl ammonium salt.
  • a imidazole derivative salt such as N,N-dimethylimidazole salt, N,N-methylethylimidazole salt, and N,N-methylpropylimidazole salt
  • the anionic component in the molecular structure is preferably a fluorine-containing compound in view of stability in the atmosphere.
  • examples of the anionic component include BF 4 - , CF 3 SO 3 - , PF 4 - , and (CF 3 SO 2 ) 2 N - .
  • the ionic liquid prepared with a combination of any of the aforementioned cationic components and any of the aforementioned anionic components can be used.
  • the solvent examples include propylene carbonate, acetonitrile, ⁇ -butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, polyethylene glycol, and alcohol. These solvents may be used alone, or in combination.
  • the electrolyte layer 15 is not necessarily a low-viscous liquid, and can be in a various state, such as a gel, a cross-linked polymer, or a liquid dispersion.
  • a strength and reliability of an electrochromic element can be improved by forming the electrolyte layer 15 in the gel or solid state.
  • a method for solidifying it is preferred that an electrolyte and a solvent be retained in a polymer resin. As a result, high ion conductivity and solid strength can be attained.
  • a photocurable resin be used as the polymer resin. Use of the photocurable resin can achieve production of an element at a lower temperature and shorter period compared to a method where a thin film is formed by heat polymerization, or evaporating the solvent.
  • a thickness of the electrolyte layer 15 is appropriately selected depending on the intended purpose without any limitation, but the thickness of the electrolyte layer 15 is preferably in a range of from 100 nm through 10 ⁇ m.
  • the electrochromic device 10 can be produced by providing a first support 11, on which a first electrode 12, a first electroactive layer 13, and an insulating porous layer 14 are sequentially formed, and a second support 18, on which a second electrode 17, and a second electroactive layer 16 are sequentially formed, and bonding the first electrode 12 and the second electrode 17 together via an electrolyte layer 15.
  • the electrolyte layer 15 can be cured by light or heat, the electrolyte layer 15 can be cured after bonding.
  • the insulating porous layer may be formed on the first electroactive layer 13, or formed on the second electroactive layer 16, or produced by blending with the electrolyte 15.
  • Examples of a material constituting the display substrate, to which the first electrode (the display element in the example of FIG. 1) is disposed include glass, and plastic. In the case where a plastic film is used as the display substrate, a light and flexible display element can be produced.
  • the second electrode As for the second electrode (the counter electrode in the example of FIG. 1), a transparent conductive film (e.g., ITO, FTO, and zinc oxide), a conductive metal film (e.g., zinc, and platinum), or carbon is used.
  • the counter electrode is typically formed on the counter substrate.
  • the counter substrate is preferably a glass plate, or a plastic film. In the case where a metal plate, such as titanium, and zinc, is used as the counter electrode, moreover, the counter electrode also functions as the substrate.
  • the electrochromic dimming element of the present invention includes a first support, a first electrode formed on the support, a first electroactive layer, a second support disposed to face the first support, a second electrode formed on the second support at a side of the first support, a second electroactive layer, and an electrolyte filling between the first electrode and the second electrode.
  • the electrochromic dimming element of the present invention may further contain other members.
  • the first electroactive layer contains an electrochromic compound, which colors through a reduction reaction, and is represented by the following general formula (1), and the second electroactive layer contains a charge-storing material.
  • members constituting the electrochromic dimming element are transparent to light.
  • the phrase “transparent to light” means that the average value of light transmittance in visible light range (from 400 nm through 700 nm) is 80% or greater.
  • the average value of the light transmittance is a value determined by attaining values of transmittance in the visible light range (from 400 nm through 700 nm) per 1nm, and calculating the arithmetical means of the values.
  • the light transmittance can be measured by means of a spectrophotometer (U-33000 spectrophotometer, manufactured by Hitachi, Ltd.).
  • Examples of the members constituting the electrochromic dimming element include electrodes, an electrochromic layer, an electrolyte layer, supports, an insulating porous layer, an antideterioration layer, and a protective layer.
  • the aforementioned other members are appropriately selected depending on the intended purpose without any limitation, and examples of the aforementioned other members include an insulating porous layer, an antideterioration layer, and a protective layer.
  • FIG. 3 is a schematic view illustrating one example of an electrochromic dimming element using the electrochromic compound of the present invention.
  • the electrochromic dimming element 30 includes a display electrode 1, a counter electrode 2 disposed to face the display electrode 1 with a gap, an electrolyte 3 disposed between the both electrodes (the display electrode 1 and the counter electrode 2), and a display layer 5, which is disposed at a surface of the display electrode 1, and contains at least the electrochromic composition 4a of the present invention.
  • an electrochromic compound in the electrochromic composition of the present invention an electrochromic compound including, in a molecular structure thereof, a functional group (adsorption group) capable of directly or indirectly bonding to a hydroxyl group, so-called a linking group, is used.
  • the linking group is bonded to the conductive or semiconductive nano structure, to thereby form an electrochromic composition.
  • the electrochromic composition is disposed on the display electrode 1 in the form of a layer, to thereby form the display layer 5.
  • a transparent conductive substrate is preferably used as a material constituting the display electrode 1.
  • the transparent conductive substrate is preferably a glass plate or a plastic film, which is coated with a transparent conductive film.
  • the transparent conductive film material is not particularly limited, as long as the transparent conductive material is a material having electroconductivity, but a transparent conductive material that is transparent and has excellent conductivity is used as the transparent conductive material, as it is necessary to secure light transmittance. Use of the aforementioned material can enhance visibility of color to be colored.
  • the transparent conductive material include tin-doped indium oxide (abbrev.
  • the transparent conductive material is preferably an inorganic material containing one selected from the group consisting of indium oxide (referred to as In oxide hereinafter), tin oxide (referred to as Sn oxide hereinafter), and zinc oxide (referred to as Zn oxide hereinafter).
  • In oxide indium oxide
  • Sn oxide tin oxide
  • Zn oxide zinc oxide
  • the In oxide, Sn oxide and Zn oxide are materials, which can be easily formed into a film by sputtering, and give excellent transparency and electroconductivity.
  • Examples of a material constituting a display substrate (with no numeral reference indicated) to which the display electrode 1 is disposed include glass, and plastic. In the case where a plastic film is used as the display substrate, a light and flexible display element can be produced. Similar to the display electrode 1, a transparent conductive substrate is used as the counter electrode 2.
  • the transparent conductive substrate is preferably a glass plate or a plastic film, which is coated with a transparent conductive film.
  • the transparent conductive film material is not particularly limited, as long as the transparent conductive material is a material having electroconductivity, but a transparent conductive material that is transparent and has excellent conductivity is used as the transparent conductive material, as it is necessary to secure light transmittance. Use of the aforementioned material can enhance visibility of color to be colored.
  • the transparent conductive material examples include tin-doped indium oxide (abbrev. ITO), fluorine-doped tin oxide (abbrev. FTO), and antimony-doped tin oxide (abbrev. ATO).
  • the transparent conductive material is preferably an inorganic material containing at least one selected from the group consisting of indium oxide (referred to as In oxide hereinafter), tin oxide (referred to as Sn oxide hereinafter), and zinc oxide (referred to as Zn oxide hereinafter).
  • In oxide, Sn oxide and Zn oxide are materials, which can be easily formed into a film by sputtering, and give excellent transparency and electroconductivity.
  • the electrochromic composition when a material that induces a reduction reaction is used in the counter electrode 2, in the case where the electrochromic composition colors as a result of oxidization, or a material that induces an oxidization reaction is used as the counter electrode 2, in the case where the electrochromic composition colors as a result of reduction, coloring and discharging reactions in the display layer 5 containing the electrochromic composition are performed more stably.
  • a material constituting the electrolyte 3 a material prepared by dissolving a supporting electrolyte in a solvent is typically used. In case of a dimming element, particularly, the electrolyte 3 needs to be colorless, and transparent.
  • an inorganic ionic salt e.g., alkali metal salt, and alkaline earth metal salt
  • a quaternary ammonium salt an acid supporting electrolyte, or a base supporting electrolyte
  • the supporting electrolyte include LiClO 4 , LiBF 4 , LiAsF 6 , LiPF 6 , CF 3 SO 3 Li, CF 3 COOLi, KCl, NaClO 3 , NaCl, NaBF 4 , NaSCN, KBF 4 , Mg(ClO 4 ) 2 , and Mg(BF 4 ) 2 .
  • These supporting electrolytes may be used alone or in combination.
  • the solvent examples include propylene carbonate, acetonitrile, ⁇ -butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, polyethylene glycol, and alcohol.
  • the aforementioned solvents may be used alone or in combination.
  • the electrolyte is not limited to a liquid electrolyte, in which a supporting electrolyte is dissolved in a solvent.
  • An electrolyte in the form of a gel, or a solid electrolyte, such as a polymer electrolyte, can be used as the electrolyte.
  • a solid electrolyte for example, there is a perfluorosulfonic acid polymer film.
  • the solution-based electrolyte has an advantage that high ion conductivity can be attained.
  • the solid electrolyte is suitable for producing an electrode having high durability without causing deterioration.
  • any method can be used without any limitation, as long as the predetermined voltage and current can be applied.
  • Use of a passive driving method can produce an inexpensive dimming element.
  • use of a transparent active driving element can perform dimming with high precision at high speed. Examples of the transparent active driving element include an IGZO.
  • the electrochromic dimming element of the present invention can be stably operated, and has excellent transparency to light. Accordingly, the electrochromic dimming element of the present invention can be suitably used, for example, for an anti-glare mirror, a dimming glass, and dimming spectacles.
  • Electrochromic Compound (Ex.-1) (identical to Electrochromic Compound (1-1) in Table 1) was synthesized according to the following synthesis scheme (1).
  • Electrochromic Compound (Ex.-2) (Identical to Electrochromic Compound (1-2) in Table 1))> Electrochromic Compound (Ex.-2) (yield with two stages: 33%) was obtained as pale yellow solids in the same manner as in Example 1, provided that the synthesis was performed according to the following synthesis scheme (2), and (8-bromooctyl)phosphonate was replaced with (4-(bromomethyl)phenyl)methylphosphonate.
  • Electrochromic Compound (Ex.-3) (Identical to Electrochromic Compound (1-3) in Table 1))> Electrochromic Compound (Ex.-3) (yield with two stages: 25%) was obtained as colorless solids in the same manner as in Example 1, provided that the synthesis was performed according to the following synthesis scheme (3), and 2,5-diibromopyridine was replaced with 2,5-diibromopyrazine.
  • Electrochromic Compound (Ex.-4) (Identical to Electrochromic Compound (1-4) in Table 1))> Electrochromic Compound (Ex.-4) (yield with two stages: 30%) was obtained as colorless solids in the same manner as in Example 1, provided that the synthesis was performed according to the following synthesis scheme (4), and 2,5-diibromopyridine was replaced with 2,5-diibromopyrimidine.
  • Electrochromic Compound (Ex.-5) (Identical to Electrochromic Compound (1-5) in Table 1))> Electrochromic Compound (Ex.-5) (yield with two stages: 24%) was obtained as colorless solids in the same manner as in Example 1, provided that the synthesis was performed according to the following synthesis scheme (5), and 2,5-diibromopyridine was replaced with 2,5-diibromo-3-methylpyridine.
  • Electrochromic Compound (Ex.-6) (Identical to Electrochromic Compound (1-6) in Table 1))> Electrochromic Compound (Ex.-6) (yield with two stages: 27%) was obtained as colorless solids in the same manner as in Example 1, provided that the synthesis was performed according to the following synthesis scheme (6), and 2,5-diibromopyridine was replaced with 3,6-diibromo-2-methylpyridine.
  • Electrochromic Compound (Ex.-7) (Identical to Electrochromic Compound (1-7) in Table 1))> Electrochromic Compound (Ex.-7) (yield with two stages: 10%) was obtained as colorless solids in the same manner as in Example 1, provided that the synthesis was performed according to the following synthesis scheme (7), and (8-bromooctyl)phosphonate was replaced with (3-bromopropyl)phosphonate.
  • Electrochromic Compound (Ex.-8) (yield with two stages: 98%) was obtained as colorless solids in the same manner as in Example 1, provided that the synthesis was performed according to the following synthesis scheme (8), and (8-bromooctyl)phosphonate was replaced with (p-(bromomethyl)phenyl)boronic acid.
  • Electrochromic Compound (Ex.-9) (yield with two stages: 91%) was obtained as colorless solids in the same manner as in Example 1, provided that the synthesis was performed according to the following synthesis scheme (9), and (8-bromooctyl)phosphonate was replaced with 4-(2-bromoethyl)benzoic acid.
  • Example 10 ⁇ Production of Electrochromic Element> (a) Formations of Display Electrode and Electrochromic Display Layer First, a glass substrate (first support 11) in the size of 30 mm ⁇ 30 mm was provided. An ITO film in the thickness of about 100 nm was formed in the 16 mm ⁇ 23 mm region on the top surface of the glass substrate through sputtering, to thereby form a display electrode (first electrode 12). The sheet resistance between the edges of the display electrode 12 was measured, and the sheet resistance was about 200 ⁇ .
  • a titanium oxide nanoparticle dispersion liquid (SP210, manufactured by Showa Co., Ltd.) was applied onto the glass substrate, on which the display electrode had been formed, through spin coating, and the coated film was subjected to annealing for 15 minutes at 120°C, to thereby form a titanium oxide particle film.
  • Electrochromic Compound (1-1) synthesized in Example 1 was applied onto the titanium oxide particle film through spin coating, following by annealing for 10 minutes at 120°C, to thereby form a first electroactive layer 13 (display layer), in which the electrochromic compound had been adsorbed on surfaces of the titanium oxide particles each having the diameter of about 1.0 ⁇ m.
  • a coating liquid was prepared by blending the following materials with the following blending ratio.
  • triarylamine compound (1) including monofunctional acrylate represented by the following structural formula: 50 parts by mass -IRGACURE184 (manufactured by BASF Japan K.K.): 5 parts by mass -PEG400DA including bifunctional acrylate (Nippon Kayaku Co., Ltd.): 50 parts by mass -Methyl ethyl ketone: 900 parts by mass
  • the obtained coating liquid was applied by spin coating, and the obtained film was cured for 60 seconds by means of a UV irradiation device, followed by annealing for 10 minutes at 60°C, to thereby form a cured crosslinked layer.
  • a second electroactive layer 16 composed of the polymerized layer (the crosslinked layer) was formed.
  • ⁇ Filling with Electrolyte Layer 15 As an electrolyte layer 15, a liquid having the following composition was provided.
  • -IRGACURE184 (manufactured by BASF Japan K.K.): 5 parts by mass -PEG400DA (manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass -Ionic liquid (manufactured by MERCK KGaA): 50 parts by mass
  • the obtained liquid was measured and collected with a micropipette by 30 mg, and the collected liquid was dripped onto the ITO glass substrate having the first electrode 17 and the electrochromic layer, which had been obtained above.
  • the ITO glass substrate having the crosslinked layer was bonded via a spacer of 75 ⁇ m in the manner that drawing parts of the electrodes were provided.
  • the bonded element, as obtained, was cured by applying UV rays to the element for 60 seconds by means of a UV irradiation device, to thereby obtain an electrochromic element.
  • ⁇ Test 1 Coloring Voltage Evaluation> An optical change of the produced electrochromic element during coloring was monitored (LCD5200, manufactured by Otsuka Electronics Co., Ltd.) under the following conditions. As the first condition, the voltage of minus 1.5 V was applied to the electrochromic element to color. As the second condition, the voltage of minus 2.2 V was applied to the electrochromic element to color. Thereafter, the minimum transmittance with respect to the visible wavelength range was determined, and the result was evaluated based on the following criteria. The minimum transmittance of the transmission spectrum for the coloring was 22%, when the voltage of minus 1.5 V was applied. When the voltage of minus 2.2 V was applied, the minimum transmittance was reduced to 18%. The result is presented in Table 3-2. -Evaluation Criteria- Good: The minimum transmittance of the visible wavelength range was 30% or less. Not good: The minimum transmittance of the visible wavelength range was greater than 30%.
  • ⁇ Test 2 Repeating Test> ⁇ Electrical Degradation>> -Evaluation 1-
  • the predetermined voltages were applied to the electrochromic element to repeatedly color and discharge the produced electrochromic element 500 times. Specifically, the voltage of +2.2 V was applied between the first electrode 12 and the second electrode 17 for 0.4 seconds to inject the charge amount of 3.7 mC. As a result of this process, coloring in black was confirmed in the area where the first electrode 12 and the second electrode 17 were overlapped to each other, due to coloring of each electrochromic compound contained in the first electroactive layer and the second electroactive layer. As a result, the transmittance of the minimum transmittance (650 nm) was reduced to 25%.
  • a coloring-discharging cycle was repeated 500 times in the aforementioned manner. Electrical and optical changes of the electrochromic element was confirmed before and after the repeated coloring-discharging cycles. The electrical degradation was confirmed by the following method (Evaluation 2).
  • the predetermined voltage was supplied to the electrochromic element in the same manner as the method for coloring in the repeating test. The voltage of + 2.2V was applied between the first electrode 12 and the second electrode 17 for 10 seconds. The charged amount 10 seconds after the coloring, and the variation in the transmission spectrums of discharging and coloring were observed. The coloring was determined as when the charge of 3.7 mC was injected.
  • the electrochromic element exhibited color, which had a broad absorption spectrum having the maximum absorption at 570 nm, as a result of the electrochromic reaction. However, the electrochromic element hardly colored after repeating the reaction about 3 times, and the durability of the element was poor.
  • the change in the absorption spectrum of Comparative Example 1 is depicted in FIG. 6. The results are presented in Table 3-2.
  • the electrochromic element exhibited color, which had the maximum absorption at 620 nm, and had a broad absorption spectrum from 700 nm to 400 nm. After repeating the electrochromic reaction about 3 times, the electrochromic element hardly colored, and the durability of the element was poor.
  • the change in the absorption spectrum of Comparative Example 2 is depicted in FIG. 7.
  • the electrochromic element exhibited color, which had the maximum absorption at 450 nm, and had a broad absorption spectrum from 600 nm to 400 nm. However, the coloring density was poor, and it was difficult to discharge the color.
  • the electrochromic element exhibited a color, which had the maximum absorptions at 850 nm and 450 nm, as a result of the electrochromic reaction.
  • the electrochromic element had poor durability to repetitive use, and the electrochromic element stopped discharging after repeating the cycle of coloring and discharging about 3 times.
  • Example 11 An electrochromic element was produced in the same manner as in Example 10, provided that Electrochromic Compound (1-1) of the first electroactive layer was replaced with Electrochromic Compound (1-2) represented by the following structural formula. The coloring voltage evaluation and the repeating test were performed on the produced electrochromic element in the same manner as in Example 10. The results are presented in Table 3-2.
  • Electrochromic elements were each produced in the same manner as in Example 10, provided that the triarylamine compound (1) of the second electroactive layer was replaced with triarylamine compounds (2) to (5) represented by the following structural formulae, respectively.
  • the coloring voltage evaluation and the repeating test were performed on each of the produced electrochromic elements in the same manner as in Example 10. The results are presented in Table 3-2.
  • Example 16 An electrochromic element was produced in the same manner as in Example 10, provided that the triarylamine compound (1) of the second electroactive layer was replaced with antimony-doped tin oxide (abbreviation: ATO) that was a transparent conductive material.
  • ATO antimony-doped tin oxide
  • the coloring voltage evaluation and the repeating test were performed on the produced electrochromic element in the same manner as in Example 10. The results are presented in Table 3-2.
  • Electrochromic elements were each produced in the same manner as in Example 10, provided that Electrochromic Compound (1-1) of the first electroactive layer was replaced with Electrochromic Compounds (1-3), (1-5), and (1-6) represented by the following structural formulae, respectively.
  • the coloring voltage evaluation and the repeating test were performed on each of the produced electrochromic elements in the same manner as in Example 10. The results are presented in Table 3-2.
  • Electrochromic elements were each produced in the same manner as in Example 10, provided that Electrochromic Compound (1-1) of the first electroactive layer was replaced with Electrochromic Compounds (Comp. 11) to (Comp. 26), which were represented by the structural formulae of the following Tables 2-1 and 2-2, respectively.
  • the coloring voltage evaluation and the repeating test were performed on each of the produced electrochromic elements in the same manner as in Example 10. The results are presented in Table 3-2.
  • the charge-storing materials (B) used in Examples are classified into materials that cause a capacitive reaction, such as ATO, and materials that cause an oxidation reaction, such as the triarylamine compound (1) through the triarylamine compound (5). It is presumed from the results that the better properties of the electrochromic element can be secured by using the material that causes an oxidation reaction as the charge-storing material (B), rather than that ATO that causes a capacitive reaction. Among the aforementioned materials, use of the triarylamine compound (1) lead the better properties.
  • An electrochromic compound represented by the following general formula (1) General Formula (1) where X 1 and X 2 are each independently a carbon atom or a nitrogen atom, R 1 , R 2 and R 3 are each independently a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group, x is an integer selected from 0 through 3, y and z are each independently an integer selected from 0 through 4, and at least one of L 1 and L 2 is a monovalent functional group bonded to a nitrogen atom of a pyridinium ring directly, or via a divalent substituent.
  • General Formula (1) where X 1 and X 2 are each independently a carbon atom or a nitrogen atom, R 1 , R 2 and R 3 are each independently a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group, x is an integer selected from 0
  • ⁇ 2> The electrochromic compound according to ⁇ 1>, wherein at least one selected from the group consisting of R 1 to R 3 and L 1 and L 2 contains a functional group capable of directly or indirectly bonding to a hydroxyl group.
  • ⁇ 3> The electrochromic compound according to ⁇ 2>, wherein at least of L 1 and L 2 contains a functional group capable of directly or indirectly bonding to a hydroxyl group.
  • ⁇ 4> The electrochromic compound according to ⁇ 2> or ⁇ 3>, wherein the functional group capable of directly or indirectly bonding to a hydroxyl group is a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, a silyl group, or a silanol group.
  • An electrochromic composition comprising: a conductive or semiconductive nano structure; and the electrochromic compound according to any one of ⁇ 1> to ⁇ 4>, where the electrochromic compound can be bonded to or adsorbed on the conductive or semiconductive nano structure.
  • An electrochromic element comprising: a first support; a first electrode formed on the first support; a first electroactive layer; a second support disposed to face the first support; a second electrode formed on the second support at a side of the first support; a second electroactive layer; and an electrolyte filling between the first electrode and the second electrode, wherein the first electroactive layer contains an electrochromic compound, which colors through a reduction reaction, and is represented by the following general formula (1), and the second electroactive layer contains a charge-storing material, General Formula (1) where X 1 and X 2 are each independently a carbon atom or a nitrogen atom, R 1 , R 2 and R 3 are each independently a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group, x is an integer selected from 0 through 3, y and z are each independently an integer selected from 0 through 4, and at least one of L 1 and L 2 is a monovalent
  • the second electroactive layer contains an oxidation-reactive material including a triarylamine structure site, where the oxidation-reactive material including a triarylamine structure site contains a cross-linked product obtained by crosslinking a radically polymerizable compound including a triarylamine structure site, and a polymerizable composition including another radically polymerizable compound different from the radically polymerizable compound including a triarylamine structure site.
  • ⁇ 11> The electrochromic element according to any one of ⁇ 8> to ⁇ 10>, wherein one or more radically polymerizable functional groups contained in the radically polymerizable compound including a triarylamine structure site are at least one of an acryloyloxy group and a methacryloyloxy group.
  • An electrochromic dimming element including: a first support; a first electrode formed on the first support; a first electroactive layer; a second support disposed to face the first support; a second electrode formed on the second support at a side of the first support; a second electroactive layer; and an electrolyte filling between the first electrode and the second electrode, wherein the first electroactive layer contains an electrochromic compound, which colors through a reduction reaction, and is represented by the following general formula (1), and the second electroactive layer contains a charge-storing material, and wherein members constituting the electrochromic dimming element are transparent to light,
  • General Formula (1) where X 1 and X 2 are each independently a carbon atom or a nitrogen atom, R 1 , R 2 and R 3 are each independently a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group, x is an integer selected from 0 through 3, y and z are each independently an integer
  • the electrochromic compound according to any one of ⁇ 1> to ⁇ 4>, the electrochromic composition according to ⁇ 5>, the electrochromic element according to any one of ⁇ 6> to ⁇ 11>, and the electrochromic dimming element according to ⁇ 12> can solve the various problems in the art, and can achieve the object of the present invention.
  • display electrode 2 counter electrode 3: electrolyte 4a: electrochromic composition 5: display layer 10: electrochromic device 11: first support 12: first electrode 13: first electroactive layer 14: insulating porous layer 15: electrolyte layer 16: second electroactive layer 17: second electrode 18: second support 30: dimming element

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Abstract

L'invention concerne un composé électrochromique représenté par la formule générale (1) suivante dans laquelle X1 et X2 sont chacun indépendamment un atome de carbone ou un atome d'azote, R1, R2 et R3 sont chacun indépendamment un atome d'halogène, un groupe alkyle substitué ou non substitué ou un groupe alcoxy substitué ou non substitué, x est un entier choisi de 0 à 3, y et z sont chacun indépendamment un entier choisi de 0 à 4 et L1 et/ou L2 sont un groupe fonctionnel monovalent lié à un atome d'azote d'un noyau pyridinium directement ou par le biais d'un substituant divalent.
PCT/JP2016/000680 2015-03-13 2016-02-09 Composé électrochromique, composition électrochromique, élément électrochromique et élément d'obscurcissement électrochromique WO2016147543A1 (fr)

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EP16764377.4A EP3268448B1 (fr) 2015-03-13 2016-02-09 Composé électrochromique, composition électrochromique, élément électrochromique et élément d'obscurcissement électrochromique
KR1020177029118A KR102027049B1 (ko) 2015-03-13 2016-02-09 일렉트로크로믹 화합물, 일렉트로크로믹 조성물, 일렉트로크로믹 소자, 및 일렉트로크로믹 조광 소자
CN201680014554.4A CN107429158B (zh) 2015-03-13 2016-02-09 电致变色化合物、电致变色组合物、电致变色元件和电致变色调光元件
US15/554,289 US10988684B2 (en) 2015-03-13 2016-02-09 Electrochromic compound, electrochromic composition, electrochromic element, and electrochromic dimming element

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