Organic compound, electrochromic element, optical filter, lens unit, imaging device, and window

Abstract

To provide an organic compound that absorbs light in a region about 500 nm by redox reaction and is reversibly colored or discolored.SOLUTION: The present invention discloses an organic compound represented by general formula (1). In the general formula (1), X1 and X2 each denote an alkyl group, an alkoxy group, an aryl group, a heterocyclic group or an aralkyl group, R1 to R8 each denote a hydrogen atom or a substituent, R9 and R10 each denote an alkyl group or an aryl group.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to an organic compound having electrochromic properties, an electrochromic element, an optical filter, a lens unit, an imaging device, and a window. [Background technology]

[0002] An electrochromic element is an element having a pair of electrodes and an electrochromic layer disposed between the pair of electrodes. It is an element that adjusts the amount of light passing through the electrochromic layer by applying a voltage to the pair of electrodes. In other words, an electrochromic element can control the light transmittance. In this specification, electrochromic may be abbreviated to EC.

[0003] Electrochromic materials, in which the optical absorption properties (coloration state and light transmittance) of a substance change due to an electrochemical oxidation-reduction reaction, are known to include a variety of materials, including inorganic materials, polymeric materials, and organic low-molecular-weight materials.

[0004] Using these materials, EC elements have been applied to switchable mirrors in automobiles, electronic paper, etc. These devices utilize the property that a wide variety of color tones can be displayed by selecting the materials, and many electrochromic compounds have been developed to date.

[0005] Patent Document 1 describes an organic compound of the following structural formula that becomes colored in a reduced state.

[0006] [ka] [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2019-137672 A Summary of the Invention [Problem to be solved by the invention]

[0008] In order to commercialize electrochromic elements, compounds having various characteristics depending on the type of device and application are needed, and electrochromic compounds with properties different from those of the compounds described in Patent Document 1 are needed.

[0009] The present invention has been made in view of the above problems, and has an object to provide an organic compound which absorbs light in the region around 500 nm through an oxidation-reduction reaction, thereby becoming colored or decolorized. [Means for solving the problem]

[0010] The present invention provides an organic compound represented by the following general formula (1):

[0011] [ka] In general formula (1), X1 and X2 are each independently selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and a substituted or unsubstituted aralkyl group.

[0012] R1 to R8 are each independently selected from a hydrogen atom and a substituent. The substituents represented by R1 to R8 are any one of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group.

[0013] R9 and R 10 is either a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Effect of the Invention

[0014] According to the present invention, it is possible to provide an organic compound which absorbs light in the region around 500 nm through an oxidation-reduction reaction, and becomes colored or decolorized. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 is a schematic cross-sectional view of an example of an electrochromic element according to an embodiment. [Diagram 2] FIG. 2 is a schematic diagram illustrating an example of a driving device including an electrochromic element according to an embodiment. [Diagram 3] 1A and 1B are schematic diagrams illustrating an example of an imaging device in which an optical filter is disposed in a lens unit and in which an optical filter is disposed in the imaging device, respectively. [Figure 4] 4(a) is a schematic view showing a window using an EC element according to the present embodiment, and (b) is a schematic cross-sectional view taken along the line XX' of FIG. 4(a). [Diagram 5] FIG. 2 is a diagram showing ultraviolet-visible absorption spectra of Example Compound A-31 in a colored state and a decolorized state. [Figure 6] FIG. 1 shows ultraviolet-visible absorption spectra of Example Compound A-22 in a colored state and a decolorized state. [Figure 7] FIG. 2 is a diagram showing ultraviolet-visible absorption spectra of exemplary compound A-25 in a colored state and a decolorized state. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The organic compound according to this embodiment is characterized by being represented by the following general formula (1): Since the organic compound has electrochromic properties, it can be called an electrochromic compound.

[0017] [ka] In the general formula (1), X1 and X2 are each independently selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and a substituted or unsubstituted aralkyl group. Among the above, X1 and X2 may be an alkyl group, an aryl group, or an aralkyl group.

[0018] R1 to R8 are each independently selected from a hydrogen atom and a substituent. The substituents represented by R1 to R8 are any of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. R1 to R8 may be a hydrogen atom among the above.

[0019] R9 and R 10 are each independently selected from the substituents. 10 The substituent represented by is either an alkyl group which may have a substituent or an aryl group which may have a substituent. More preferably, R and R 10 are the same substituents.

[0020] The alkyl group in this embodiment may have 1 to 20 carbon atoms. The alkyl group preferably has 1 to 8 carbon atoms, and may be linear, branched, or cyclic. A hydrogen atom in the alkyl group may be replaced with a halogen atom, preferably a fluorine atom. A carbon atom in the alkyl group may be replaced with an ester group or a cyano group. Specific examples of the alkyl group include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, an octyl group, a cyclohexyl group, and a trifluoromethyl group.

[0021] Examples of the aralkyl group according to the present embodiment include a benzyl group and a phenethyl group. The aralkyl group may have a substituent, specifically, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. The hydrogen atom of the alkyl group or alkoxy group may be replaced with a halogen atom, preferably a fluorine atom.

[0022] The alkoxy group according to the present embodiment may have 1 to 20 carbon atoms. The alkoxy group preferably has 1 to 8 carbon atoms, and may be linear, branched, or cyclic. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropyloxy group, a tertiary butyloxy group, an octyloxy group, a cyclohexyloxy group, and a trifluoromethyloxy group. The hydrogen atom of the alkoxy group may be replaced by a halogen atom. When the halogen atom is replaced by a halogen atom, a fluorine atom is preferable.

[0023] Examples of the aryl group according to the present embodiment include a phenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a naphthyl group, a fluoranthenyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a tetracenyl group, a pentacenyl group, a triphenylenyl group, and a perylenyl group. When the aryl group has a substituent, it may have at least one of a halogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms. The hydrogen atom of the alkyl group or alkoxy group may be replaced with a halogen atom, preferably a fluorine atom.

[0024] Examples of the heterocyclic group according to this embodiment include a thienyl group, a pyrrolyl group, a pyridyl group, an oxazolyl group, an oxadiazolyl group, a thiazolyl group, a thiadiazolyl group, a terthienyl group, a quinolyl group, an isoquinolyl group, and a carbazolyl group. When the heterocyclic group has a substituent, it may have at least one of an alkyl group having 1 to 8 carbon atoms and an alkoxy group having 1 to 8 carbon atoms. The hydrogen atom of the alkyl group or alkoxy group may be replaced with a halogen atom, preferably a fluorine atom.

[0025] Examples of halogen atoms according to this embodiment include fluorine, chlorine, bromine, and iodine.

[0026] When X1 and X2 are alkyl groups, they may have an adsorption group or an acid ester group thereof for adsorption to a porous electrode. Specific examples of the adsorption group or the acid ester group thereof include a carboxyl group and a carboxyl ester group, a sulfonic acid group and a sulfonic acid ester group, a phosphonic acid group and a phosphonic acid ester group, and a trialkoxysilyl group. Furthermore, in order to improve solubility in an organic solvent, the alkyl group may have an ionic group such as pyridinium or quinolinium at its terminal.

[0027] When the aralkyl group and aryl group represented by X1 and X2 have an alkyl group or an alkoxy group as a substituent, the end of the group may have an adsorptive group or an acid ester group thereof that is adsorbed to a porous electrode, or an ionic group to improve solubility in an organic solvent. Specific examples of the adsorptive group or an acid ester group thereof, and the ionic group are the same as those given for the alkyl group represented by X1 and X2.

[0028] The organic compound represented by the general formula (1) may exist with an anion. When it exists with an anion, it is described as follows.

[0029] [ka] A1 - and A2 - each independently represents a monovalent anion.

[0030] Anion A1 - and A2 - may be the same or different, PF6 - , ClO4 - , BF4 - , AsF6 - , SbF6 - , CF3SO3 - , (CF3SO2)2N - Anions such as Br -, Cl - , I - The halogen anions are preferably selected from PF6 - , ClO4 - , BF4 - , CF3SO3 - , (CF3SO2)2N - More preferably, A1 - and A2 - are the same anion.

[0031] The method for producing the organic compound according to the present embodiment is not particularly limited, and for example, the organic compound can be produced by the following method: When X1 and X2 are an alkyl group and an aralkyl group, the organic compound represented by the following general formula (2) is reacted with a halide in a predetermined solvent, and then the resultant is subjected to an anion exchange reaction with a salt containing a desired anion in the predetermined solvent.

[0032] On the other hand, when X1 and X2 are aryl groups, the compound can be obtained by reacting with 2,4-dinitrophenyl halide, reacting the resulting compound with a desired arylamine, and then performing an anion exchange reaction with a salt containing an anion in a specific solvent. It can also be obtained by reacting with a hypervalent iodine compound, followed by an anion exchange reaction. It is also possible to react only one imine by selecting the solvent and reaction temperature. It is also possible to introduce different substituents into the two imines by repeating the reaction.

[0033] [ka] The method for producing the organic compound represented by the above general formula (2) is not particularly limited, but it can be produced, for example, according to the production method shown below. 10 represents a hydrogen atom or a substituent as in general formula (1), X represents a halogen atom, and R represents an alkyl group.

[0034] [ka] Intermediate 1 can be synthesized by coupling a 3-carboxylate-4-halogeno-pyridine derivative with a 5-halogeno-quinoline derivative. Intermediate 2 can be synthesized by reacting intermediate 1 with the desired halogen in the presence of a base. Organic compounds represented by general formula (2) can be synthesized by subjecting intermediate 2 to an intramolecular Friedel-Crafts reaction in the presence of an acid catalyst.

[0035] Specific structural formulae of the organic compounds according to the present invention are shown below, however, the compounds according to the present invention are not limited to these.

[0036] [ka]

[0037] [ka]

[0038] [ka] Exemplary compounds A1 to A9 are those in which X1 and X2 in the general formula (1) are alkyl groups, and R9 and R 10 is an alkyl group.

[0039] Exemplary compounds A10 to A12 are those in which X1 and X2 in the general formula (1) are alkyl groups, and R9 and R 10 At least one of the groups is an aryl group. The aryl group is particularly a phenyl group.

[0040] In the exemplary compounds A13 to A23, at least one of X1 and X2 in the general formula (1) is an aryl group, particularly a phenyl group. A23 has an alkyl group in R2. That is, it is an example having a substituent in any of R1 to R8.

[0041] Exemplary compounds A24 to A29 are exemplary compounds having a substituent at any one of R1 to R8, that is, examples having a substituent at R2 or R7.

[0042] Exemplary compounds A30 and A31 are compounds having a methyl fluoride group at X1 and X2, that is, examples having an alkyl group substituted with a halogen atom at X1 and X2.

[0043] In the exemplary compounds A32 to A36, X1 and X2 each have a substituent having a hetero atom.

[0044] The organic compound according to the present embodiment has a structure represented by general formula (1), and therefore has high transparency when dissolved in a solvent. The organic compound according to the present embodiment is a compound that is colored in a reduced state. A compound that is colored in a reduced state is a compound whose visible light transmittance in a reduced state is lower than that in an oxidized state.

[0045] The organic compound according to this embodiment is an electrochromic material that exhibits stable coloring at ambient temperatures, and can be used in EC elements, optical filters using the same, lens units, imaging devices, and the like.

[0046] EC element The EC compound according to the present embodiment can be used as an electrochromic layer of an electrochromic device. The electrochromic device according to the present embodiment will be described below with reference to the drawings.

[0047] The EC element 1 in Fig. 1 has a pair of transparent substrates 10, a pair of electrodes 11, and an EC layer 12 disposed between the pair of electrodes. A spacer 13 keeps the distance between the pair of electrodes constant.

[0048] The EC layer has the organic compound according to the present invention. The EC layer may have a layer made of an EC compound and a layer made of an electrolyte. The EC layer may also be provided as a solution containing an EC compound and an electrolyte. In this form, the EC layer can be said to be a solution layer. In the EC element according to this embodiment, the EC layer is preferably a solution layer. When the EC layer is a solution layer, the EC organic compound, the solution, and other dissolved substances may be collectively referred to as an EC medium.

[0049] Next, the members constituting the EC element according to this embodiment will be described.

[0050] The electrolyte is not limited as long as it is an ion-dissociating salt and has good solubility in a solvent and high compatibility with a solid electrolyte. Among them, an electrolyte having electron donating properties is preferable. These electrolytes can also be called supporting electrolytes. Examples of the electrolyte include inorganic ion salts such as various alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, and cyclic quaternary ammonium salts. Specific examples include alkali metal salts of Li, Na, and K, such as LiClO4, LiSCN, LiBF4, LiAsF6, LiCF3SO3, LiPF6, LiI, NaI, NaSCN, NaClO4, NaBF4, NaAsF6, KSCN, and KCl, as well as quaternary ammonium salts and cyclic quaternary ammonium salts, such as (CH3)4NBF4, (C2H5)4NBF4, (n-C4H9)4NBF4, (n-C4H9)4NPF6, (C2H5)4NBr, (C2H5)4NClO4, and (n-C4H9)4NClO4.

[0051] The solvent for dissolving the EC compound and the electrolyte is not particularly limited as long as it can dissolve the EC compound and the electrolyte, but it is particularly preferable to use a solvent having polarity.Specific examples of the solvent include water and organic polar solvents such as methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, γ-butyrolactone, γ-valerolactone, sulfolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, acetonitrile, propiononitrile, benzonitrile, dimethylacetamide, methylpyrrolidinone, and dioxolane.

[0052] Furthermore, the EC medium may contain a polymer or a gelling agent to make it highly viscous or gel-like. These polymers and gelling agents may also be called thickeners. By containing a thickener and increasing the viscosity of the EC solution, the organic compounds are less likely to form associations, and the temperature dependence of the absorption spectrum can be reduced. Therefore, it is preferable that the EC solution contains a thickener.

[0053] The viscosity of the EC solution may be 10 cP or more and 5000 cP or less, or 50 cP or more and 1000 cP or less. The viscosity of the EC solution may be 150 cP or less, preferably 100 cP or less, and more preferably 65 cP or less. The viscosity of the EC solution may be 20 cP or more, and preferably 50 cP or more.

[0054] The thickener may be present in an amount of 20 wt% or less, preferably 1 wt% to 15 wt%, and more preferably 5 wt% to 10 wt%, assuming that the total weight of the EC solution is 100 wt%.

[0055] The polymer is not particularly limited, and examples thereof include polyacrylonitrile, carboxymethyl cellulose, polyvinyl chloride, polyalkylene oxide, polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, polyester, Nafion (registered trademark), etc. Polymethyl methacrylate, polyethylene oxide, and polypropylene oxide are preferred.

[0056] When the viscosity of the EC solution is high, the movement of molecules in the EC solution can be suppressed, which may suppress association. On the other hand, it is not preferable for the viscosity to be too high, as it suppresses the movement of electrons in the EC solution, which reduces the response speed of the EC element.

[0057] Next, the transparent substrate and the transparent electrode will be described. As the transparent substrate, for example, colorless or colored glass, reinforced glass, etc., or colorless or colored transparent resin is used. In this embodiment, "transparent" means that the transmittance of visible light is 90% or more. Specific examples include polyethylene terephthalate, polyethylene naphthalate, polynorbornene, polyamide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, etc.

[0058] Examples of materials for the transparent electrode include metals and metal oxides such as indium tin oxide (ITO), fluorine-doped tin oxide (FTO), tin oxide (NESA), indium zinc oxide (IZO), silver oxide, vanadium oxide, molybdenum oxide, gold, silver, platinum, copper, indium, and chromium, silicon-based materials such as polycrystalline silicon and amorphous silicon, and carbon materials such as carbon black, graphite, and glassy carbon. In addition, conductive polymers whose conductivity has been improved by doping treatment or the like, such as polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, and complexes of polyethylenedioxythiophene (PEDOT) and polystyrenesulfonic acid, are also preferably used.

[0059] Furthermore, a porous electrode may be provided on the electrode. The porous electrode is preferably a material having a large surface area, such as a porous shape having fine pores on the surface and inside, a rod shape, or a wire shape. Examples of materials that can be used for the porous electrode include metals, metal oxides, and carbon. More preferred are metal oxides such as titanium oxide, tin oxide, iron oxide, strontium oxide, tungsten oxide, zinc oxide, tantalum oxide, vanadium oxide, indium oxide, nickel oxide, manganese oxide, and cobalt oxide.

[0060] The spacer is disposed between a pair of transparent electrodes and provides a space for accommodating the EC layer having the EC compound of the present invention. Specifically, polyimide, polytetrafluoroethylene, fluororubber, epoxy resin, etc. can be used. This spacer makes it possible to maintain the distance between the electrodes of the EC element.

[0061] The EC element according to this embodiment may have a liquid inlet formed by a pair of electrodes and a spacer. After a composition containing an EC compound is injected through the liquid inlet, the inlet is covered with a sealing member and further sealed with an adhesive or the like to form an element. The sealing member also plays a role in isolating the adhesive and the EC compound so that they do not come into contact with each other. The shape of the sealing member is not particularly limited, but a tapered shape such as a wedge shape is preferable.

[0062] The method for forming the EC element according to this embodiment is not particularly limited, and a method can be used in which a liquid containing an EC compound that has been prepared in advance is injected into a gap between a pair of electrode substrates by a vacuum injection method, an air injection method, a meniscus method, or the like.

[0063] The EC element according to the present embodiment may have the organic compound according to the present embodiment and a different organic compound (second organic compound) from this organic compound. The second organic compound may be one or more types, and may be a compound that is colored in an oxidized state, a compound that is colored in a reduced state, or a compound that has both properties. Since the organic compound represented by the general formula (1) is a compound that is colored in a reduced state, the second organic compound is preferably a compound that is colored in an oxidized state. A compound that is colored in an oxidized state is a compound whose visible light transmittance in an oxidized state is lower than that in a reduced state. It is sufficient that the transmittance changes in any part of the visible light range, and it is not necessary that the transmittance changes in the entire visible light range. Specifically, the organic compound according to the present embodiment can absorb a desired color as an EC element by combining it with a coloring material of another color. The different organic compound when colored preferably has an absorption wavelength in the range of 400 nm to 800 nm, more preferably has an absorption wavelength in the range of 420 nm to 700 nm. Having an absorption wavelength in a specific range means that the peak of the absorption spectrum is in a specific range. By combining the organic compound of the present invention with a plurality of other materials, it is also possible to prepare an EC element that absorbs the entire visible range and is colored black.

[0064] The EC element according to this embodiment preferably contains five or more kinds of EC compounds in addition to the organic compound according to the present invention, because a filter having the EC element can easily absorb light of each wavelength uniformly.

[0065] Other EC compounds according to this embodiment include, for example, compounds of the following structural formula:

[0066] Other EC compounds that become colored in the oxidized state include oligothiophene-based compounds, phenazine-based compounds such as 5,10-dihydro-5,10-dimethylphenazine and 5,10-dihydro-5,10-diisopropylphenazine, metallocene-based compounds such as ferrocene, tetra-t-butylferrocene and titanocene, phenylenediamine-based compounds such as N,N',N,N'-tetramethyl-p-phenylenediamine, and pyrarizone-based compounds such as 1-phenyl-2-pyrazoline.

[0067] Compounds that become colored in a reduced state include N,N'-diheptylbipyridinium diperchlorate, N,N'-diheptylbipyridinium ditetrafluoroborate, N,N'-diheptylbipyridinium dihexafluorophosphate, N,N'-diethylbipyridinium diperchlorate, N,N'-diethylbipyridinium ditetrafluoroborate, N,N'-diethylbipyridinium dihexafluorophosphate, N,N'-dibenzylbipyridinium diperchlorate, N,N'-dibenzylbipyridinium ditetrafluoroborate, and N,N'-di Examples of the compound include viologen compounds such as benzyl bipyridinium dihexafluorophosphate, N,N'-diphenyl bipyridinium diperchlorate, N,N'-diphenyl bipyridinium ditetrafluoroborate, and N,N'-diphenyl bipyridinium dihexafluorophosphate; anthraquinone compounds such as 2-ethyl anthraquinone, 2-t-butyl anthraquinone, and octamethyl anthraquinone; ferrocenium salt compounds such as ferrocenium tetrafluoroborate and ferrocenium hexafluorophosphate; and styrylated compounds.

[0068] In this embodiment, the phenazine compound is a compound containing a 5,10-dihydrophenazine skeleton in its chemical structure. The phenazine compound includes a compound having a substituent in 5,10-dihydrophenazine. For example, the hydrogen atoms at the 5th and 10th positions of 5,10-dihydrophenazine may be substituted with an alkyl group such as a methyl group, an ethyl group, or a propyl group, or an aryl group such as a phenyl group. The phenazine compound may be a compound having an alkyl group having 1 to 20 carbon atoms in 5,10-dihydrophenazine. The phenazine compound may be a compound having an alkoxy group having 1 to 20 carbon atoms in 5,10-dihydrophenazine. The phenazine compound may be a compound having an aryl group having 4 to 60 carbon atoms in 5,10-dihydrophenazine. The same applies to other compounds, such as viologen compounds.

[0069] Of the above, the second organic compound is preferably any one of a phenazine-based compound, a metallocene-based compound, a phenylenediamine-based compound, and a pyrazoline-based compound.

[0070] The compounds contained in the EC layer of the EC element according to the present embodiment can be extracted and analyzed by a known method to confirm that they are present in the EC element. For example, they can be extracted by chromatography and analyzed by NMR. In addition, when the electrochromic layer is solid, they can be analyzed by TOF-SIMS or the like.

[0071] <Applications of EC elements> The EC element according to this embodiment can be used in optical filters, lens units, imaging devices, window materials, and the like.

[0072] <Optical filters> The optical filter according to this embodiment includes an EC element and an active element connected to the EC element. The active element drives the EC element and adjusts the amount of light passing through the EC element. Examples of the active element include a transistor. The transistor may have an oxide semiconductor such as InGaZnO in an active region.

[0073] The optical filter includes an EC element according to this embodiment and a driving device connected to the EC element. Fig. 2 is a schematic diagram showing an example of a driving device 20 for the EC element and an EC element driven by the driving device 20. The driving device 20 for the EC element 1 of this embodiment includes a driving power supply 8, a resistance switch 9, and a controller 7.

[0074] The driving power supply 8 applies to the EC element a voltage necessary for the EC material contained in the EC layer to cause an electrochemical reaction. It is more preferable that the driving voltage is a constant voltage. This is because, when the EC material is composed of multiple types of materials, the absorption spectrum may change due to the difference in redox potential or molar absorption coefficient of the materials, so a constant voltage is preferable. The driving power supply 8 starts applying voltage or maintains the applied state according to a signal from the controller 7, and the constant voltage application state is maintained during the period in which the light transmittance of the EC element is controlled.

[0075] The method of controlling the transmittance of the EC element by the controller 7 is adapted to a method suitable for the element being used. Specifically, there is a method of inputting predefined conditions to the EC element 1 for a desired set value of transmittance, or a method of comparing the set value of transmittance with the transmittance of the EC element 1 and selecting and inputting conditions that match the set value. Examples of parameters that can be changed include voltage, current, and duty ratio. The controller 7 can change the coloring density of the EC element by changing the voltage, current, or duty ratio.

[0076] In this embodiment, known means can be used to change the voltage, change the current, and modulate the pulse width. The pulse width can also be modulated as follows.

[0077] The resistance switch 9 switches between a resistor R1 (not shown) and a resistor R2 larger than the resistor R1 and connects them in series in a closed circuit including the drive power supply 8 and the EC element. The resistance value of the resistor R1 is preferably smaller than the largest impedance of the element closed circuit, and is preferably 10Ω or less. The resistance value of the resistor R2 is preferably larger than the largest impedance of the element closed circuit, and is preferably 1MΩ or more. The resistor R2 may be air. In this case, strictly speaking the closed circuit becomes an open circuit, but it can be considered as a closed circuit by regarding the air as resistor R2.

[0078] The controller 7 sends a switching signal to the resistor switch 9 to control the switching of the resistors R1 and R2.

[0079] The controller 7 may generate the PWM signal using a comparator or the like, without using a resistor switch.

[0080] <Lens unit> The lens unit according to this embodiment includes an imaging optical system having a plurality of lenses and an optical filter having an EC element 1. The optical filter may be provided either between the plurality of lenses or outside the lens. The optical filter is preferably provided on the optical axis of the lens.

[0081] <Imaging device> The imaging device of this embodiment has an optical filter and a light receiving element that receives light that has passed through the optical filter. Specific examples of imaging devices include cameras, video cameras, and mobile phones with cameras. The imaging device may be in a form in which a main body having a light receiving element and a lens unit having a lens can be separated. In this case, when the imaging device can be separated into a main body and a lens unit, the present invention also includes a form in which an optical filter separate from the imaging device is used during imaging. In this case, the optical filter may be disposed outside the lens unit, between the lens unit and the light receiving element, between multiple lenses (when the lens unit has multiple lenses), and the like.

[0082] FIG. 3(a) is a schematic diagram of an example of an imaging device in which an optical filter is disposed in a lens unit, and FIG. 3(b) is a schematic diagram of an example of an imaging device in which an optical filter is disposed in the imaging device.

[0083] The imaging device 100 includes a lens unit 102 and an imaging unit 103. The lens unit 102 includes an imaging optical system including an optical filter 101 and a plurality of lenses or a lens group. The optical filter 101 is the optical filter of the present embodiment described above.

[0084] 3(a), the lens unit 102 represents, for example, a rear-focus type zoom lens that performs focusing behind the aperture. It has four lens groups, in order from the object side, a first lens group 104 with positive refractive power, a second lens group 105 with negative refractive power, a third lens group 106 with positive refractive power, and a fourth lens group 107 with positive refractive power. Magnification is changed by changing the distance between the second lens group 105 and the third lens group 106, and focusing is performed by moving a part of the lens groups in the fourth lens group 107.

[0085] Lens unit 102 has, for example, aperture diaphragm 108 between second lens group 105 and third lens group 106, and optical filter 101 between third lens group 106 and fourth lens group 107. The lens unit is arranged so that light passing through each of lens groups 104 to 107, aperture 108, and optical filter 101 passes through, and the amount of light can be adjusted using aperture diaphragm 108 and optical filter 101.

[0086] The lens unit 102 is detachably connected to the imaging unit 103 via a mount member (not shown).

[0087] In this embodiment, the optical filter 101 is disposed between the third lens group 106 and the fourth lens group 107 in the lens unit 102, but the imaging device 100 is not limited to this configuration. For example, the optical filter 101 may be disposed either in front of (on the subject side) or behind (on the imaging unit 103 side) the aperture stop 108, or may be disposed in front of, behind, or between any of the first to fourth lens groups 104 to 107. If the optical filter 101 is disposed at a position where light converges, there is an advantage in that the area of ​​the optical filter 101 can be reduced.

[0088] The configuration of the lens unit 102 is not limited to the above configuration, and can be selected as appropriate. For example, in addition to the rear focus type, it may be an inner focus type in which focusing is performed in front of the aperture, or other types. In addition to the zoom lens, special lenses such as a fisheye lens or a macro lens can also be selected as appropriate.

[0089] The imaging unit 103 has a glass block 109 and a light receiving element 110. The glass block 109 is a glass block such as a low-pass filter, a face plate, or a color filter. The light receiving element 110 is a sensor unit that receives light that has passed through a lens unit, and an imaging element such as a CCD or CMOS can be used. Alternatively, it may be an optical sensor such as a photodiode, and it is possible to appropriately use one that obtains and outputs information on the intensity or wavelength of light.

[0090] 3(a), when the optical filter 101 is incorporated in the lens unit 102, the driving device may be disposed inside or outside the lens unit 102. When disposed outside the lens unit 102, the EC element 1 in the lens unit 102 and the driving device are connected through wiring to control driving.

[0091] In the configuration of the imaging device 100 described above, the optical filter 101 is disposed inside the lens unit 102. However, the present invention is not limited to this configuration, and it is sufficient that the optical filter 101 is disposed at an appropriate location inside the imaging device 100, and the light receiving element 110 is disposed so as to receive light that has passed through the optical filter 101.

[0092] For example, as shown in Fig. 3(b), the imaging unit 103 may have the optical filter 101. Fig. 3(b) is a diagram for explaining the configuration of another example of the imaging device of this embodiment, and is a schematic diagram of the configuration of an imaging device having an optical filter in the imaging unit 103. In Fig. 3(b), for example, the optical filter 101 is disposed immediately before the light receiving element 110. When the imaging device itself has the optical filter 101 built in, the connected lens unit 102 itself does not need to have the optical filter 101, so it is possible to configure a dimmable imaging device using an existing lens unit 102.

[0093] The imaging device 100 of this embodiment can be applied to products that have a combination of light amount adjustment and a light receiving element. For example, it can be used in cameras, digital cameras, video cameras, and digital video cameras, and can also be applied to products that have an imaging device built in, such as mobile phones, smartphones, PCs, and tablets.

[0094] According to the imaging device 100 of this embodiment, by using the optical filter 101 as a light adjusting component, it is possible to appropriately change the amount of light adjustment with one filter, which has the advantages of reducing the number of components and saving space.

[0095] <Window> The window according to the present embodiment includes an EC element and an active element connected to the EC element. The active element drives the EC element and adjusts the amount of light passing through the EC element. The active element may be, for example, a transistor. The transistor may have an oxide semiconductor such as InGaZnO in an active region. The window according to the present embodiment may also be called a variable transmittance window.

[0096] Fig. 4(a) is an overview diagram showing a light control window as a window material using the EC element according to this embodiment, and Fig. 4(b) is a schematic diagram showing the X-X' cross section of Fig. 4(a). The light control window 111 of this embodiment is composed of an EC element 1 (optical filter), transparent plates 113 that sandwich it, and a frame 112 that surrounds and integrates the whole. The EC element 1 has a drive device (not shown), which may be integrated within the frame 112, or may be arranged outside the frame 112 and connected to the EC element 1 through wiring.

[0097] There are no particular limitations on the material of transparent plate 113 as long as it has a high light transmittance, and a glass material is preferable in consideration of use as a window. The material of frame 112 is not important, but anything that covers at least a part of EC element 1 and has an integrated form may be regarded as a frame. In FIG. 4, EC element 1 is a component independent of transparent plate 113, but for example, transparent substrate 10 of EC element 1 may be regarded as transparent plate 113.

[0098] Such a light-control window can be used to adjust the amount of sunlight entering a room during the day, for example. Since it can be used to adjust the amount of heat as well as the amount of sunlight, it can be used to control the brightness and temperature inside a room. It can also be used as a shutter to block the view from outside to inside the room. Such a light-control window can be used not only as glass windows for buildings, but also as windows for vehicles such as cars, trains, airplanes, and ships.

[0099] In this way, the EC element 1 containing the organic compound represented by general formula (1) in the EC layer 12 can be used for optical filters, lens units, imaging devices, window materials, etc. Each of the optical filters, lens units, imaging devices, and window materials of this embodiment can provide various absorption colors by using the organic compound represented by general formula (1) alone or in combination with an EC compound having coloring absorption in another wavelength band. Furthermore, each of the optical filters, lens units, imaging devices, and window materials of this embodiment contains the organic compound represented by general formula (1), so that the transparency in the decolorized state can be improved.

[0100] Moreover, an electrochromic mirror can be formed by providing a reflective member on one of the light paths of the electrochromic element. The electrochromic mirror may be provided in an automobile as an anti-glare mirror. The electrochromic mirror can be configured by having an electrochromic element and a reflective member inside or outside the electrochromic element. Having a reflective member inside means that the electrode of the electrochromic element is reflective. Having a reflective member outside means that a reflective member is provided in contact with the transparent electrode of the electrochromic element or via another transparent member. EXAMPLES

[0101] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0102] [Example 1 <Synthesis of Exemplary Compound A-22>]

[0103] [ka]

[0104] (1) Synthesis of intermediate 11 A reaction vessel was charged with 692 mg (4.0 mmol) of quinoline-4-boronic acid, 755 mg (4.4 mmol) of methyl 4-chloropyridine-3-carboxylate, 24 ml of 1,4-dioxane, and 0.6 ml of water, and dissolved oxygen was removed with nitrogen. Next, 54 mg (0.24 mmol) of palladium acetate, 197 mg (0.48 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (S-Phos), and 1.66 g (12 mmol) of potassium carbonate were added under a nitrogen atmosphere, and the reaction was carried out at 100°C for 8 hours. After adding water to the reaction solution to stop the reaction, the aqueous layer was extracted with ethyl acetate, and the mixture was separated and purified by silica gel chromatography (mobile phase: hexane / ethyl acetate) to obtain intermediate 11 (759 mg, 77% yield).

[0105] (2) Synthesis of intermediate 12 In a reaction vessel, 529 mg (2.0 mmol) of intermediate 11 and anhydrous tetrahydrofuran (20 ml) were charged and cooled to -5°C. Next, 5.3 ml of methylmagnesium bromide solution (approximately 3.0 M tetrahydrofuran solution, 16.0 mmol) was slowly added dropwise and stirred for 1 hour, and then the temperature was raised to room temperature. An aqueous solution of ammonium chloride was added to this solution to stop the reaction, and the solution was extracted with ethyl acetate and separated and purified by silica gel chromatography (mobile phase: chloroform / methanol) to obtain intermediate 12 (486 mg, yield 92%).

[0106] (3) Synthesis of intermediate 13 In a reaction vessel, 486 mg (1.8 mmol) of intermediate 12 and trifluoromethanesulfonic acid (5 mL) were charged and stirred for 8 hours at 80° C. After neutralizing this solution with an aqueous sodium hydroxide solution, the aqueous layer was extracted with ethyl acetate and separated and purified by silica gel chromatography (mobile phase: hexane / ethyl acetate) to obtain intermediate 13 (412 mg, yield 91%).

[0107] (4) Synthesis of Example Compound A-22 In a reaction vessel, 138 mg (0.56 mmol) of intermediate 13, 1.51 g (2.80 mmol) of bis(4-tert-butylphenyl)iodonium hexafluorophosphate, 18 mg (0.10 mmol) of copper(II) acetate monohydrate, and 2.5 mL of N,N-dimethylformamide were added, and the mixture was reacted at 100° C. for 20 hours. After the reaction was completed, the mixture was concentrated under reduced pressure, and an acetonitrile solution (10 ml) of tetrabutylammonium bromide (2 g) was added. The precipitated solid was collected by filtration and dissolved in water. An aqueous solution of 200 mg of ammonium hexafluorophosphate was added dropwise to the mixture, and the mixture was stirred at room temperature for 3 hours. The precipitated crystals were filtered, washed with water, isopropyl alcohol, and diethyl ether in that order, and 250 mg (yield: 56%) of exemplary compound 22 was obtained. The structure of this compound was confirmed by NMR measurement. 1H NMR(DMSO-d6,500MHz) σ(ppm):9.98(s,1H),9.94(d,1H),9.58(d,1H),9.54(d,1H),9.41(d,1H),8.53(d,1H),8. 33(t,1H),7.95(m,2H),7.84(m,6H),7.66(d,1H),1.99(s,6H)),1.42(s,9H),1.39(s,9H)

[0108] [Example 2 <Synthesis of Exemplary Compound A-30>] In a reaction vessel, 99 mg (0.4 mmol) of intermediate 13, 202 mg (0.9 mmol) of 1,1,1-trifluoro-3-iodopropane, and 5 ml of acetonitrile were charged, and the mixture was stirred at 80° C. for 48 hours. After the reaction was completed, ethyl acetate was added, and the precipitated crystals were filtered and washed with ethyl acetate to obtain 240 mg (yield: 80%) of exemplary compound A-30. The structure of this compound was confirmed by NMR measurement. 1 H NMR(DMSO-d6,500MHz) σ(ppm):9.81(m,2H),9.30(m,2H),9.17(d,1H),8.69(d,1H),8.48(m,2H),5.19(t,2H),4.80(t,2H),2.58(m,2H),2.30(m,2H),1.91(s,6H)

[0109] [Example 3 <Synthesis of Exemplary Compound A-31>] 75mg (0.1mmol) of the exemplary compound A-30 was dissolved in water and a small amount of acetone, and an aqueous solution of 300mg of potassium hexafluorophosphate was added dropwise, followed by stirring at room temperature for 3 hours. The precipitated crystals were filtered and recrystallized with acetonitrile / isopropyl alcohol to obtain 71mg (yield: 90%) of the exemplary compound A-31. The structure of this compound was confirmed by NMR measurement. 1 H NMR(DMSO-d6,500MHz) σ(ppm):9.81(m,2H),9.30(m,2H),9.17(d,1H),8.69(d,1H),8.48(m,2H),5.19(t,2H),4.80(t,2H),2.58(m,2H),2.30(m,2H),1.91(s,6H)

[0110] [Example 4 <Synthesis of Exemplary Compound A-24>]

[0111] [ka]

[0112] (1) Synthesis of intermediate 21 A reaction vessel was charged with 692 mg (4.0 mmol) of quinoline-4-boronic acid, 817 mg (4.4 mmol) of methyl 4-chloro-6-methylpyridine-3-carboxylate, 24 ml of 1,4-dioxane, and 0.6 ml of water, and dissolved oxygen was removed with nitrogen. Next, 54 mg (0.24 mmol) of palladium acetate, 197 mg (0.48 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (S-Phos), and 1.66 g (12 mmol) of potassium carbonate were added under a nitrogen atmosphere, and the reaction was carried out at 100°C for 8 hours. After adding water to the reaction solution to stop the reaction, the aqueous layer was extracted with ethyl acetate, and the mixture was separated and purified by silica gel chromatography (mobile phase: hexane / ethyl acetate) to obtain intermediate 21 (781 mg, 75% yield).

[0113] (2) Synthesis of intermediate 22 In a reaction vessel, 56 mg (2.0 mmol) of intermediate 21 and 20 ml of anhydrous tetrahydrofuran were charged and cooled to -5°C. Next, 5.3 ml of methylmagnesium bromide solution (approximately 3.0 M tetrahydrofuran solution, 16.0 mmol) was slowly added dropwise and stirred for 1 hour, and then the temperature was raised to room temperature. An aqueous solution of ammonium chloride was added to this solution to stop the reaction, and the solution was extracted with ethyl acetate and separated and purified by silica gel chromatography (mobile phase: chloroform / methanol) to obtain intermediate 22 (490 mg, yield 88%).

[0114] (3) Synthesis of intermediate 23 In a reaction vessel, 490 mg (1.8 mmol) of intermediate 12 and trifluoromethanesulfonic acid (5 mL) were charged and stirred for 8 hours at 80° C. After neutralizing this solution with an aqueous sodium hydroxide solution, the aqueous layer was extracted with ethyl acetate and separated and purified by silica gel chromatography (mobile phase: hexane / ethyl acetate) to obtain intermediate 23 (421 mg, yield 92%).

[0115] (4) Synthesis of Example Compound A-24 In a reaction vessel, 104 mg (0.4 mmol) of intermediate 23, 166 mg (0.9 mmol) of 1-iodobutane, and 5 ml of DMF were charged, and the mixture was stirred at 80° C. for 16 hours. After the reaction was completed, ethyl acetate was added, and the precipitated crystals were filtered and washed with ethyl acetate to obtain 214 mg (yield: 80%) of exemplary compound A-24. The structure of this compound was confirmed by NMR measurement. 1 H NMR(DMSO-d6,500MHz) σ(ppm):9.83(d,1H),9.66(s,1H),9.23(s,1H),9.02(d,1H),8.64(d,1H),8.45(m,2H),5.15(t, 2H),4.68(t,2H),2.98(s,3H),2.05(m,4H),1.95(m,4H),1.85(s,6H),1.47(m,4H),0.95(m,6H)

[0116] [Example 5 <Synthesis of Exemplary Compound A-25>] Example compound A-24: 126 mg (0.2 mmol) was dissolved in water. An aqueous solution of 300 mg of potassium hexafluorophosphate was added dropwise, and the mixture was stirred at room temperature for 3 hours. The precipitated crystals were filtered, washed with isopropyl alcohol and diethyl ether in that order, and then recrystallized from acetonitrile / isopropyl alcohol to obtain example compound A-25 (120 mg, yield: 90%). The structure of this compound was confirmed by NMR measurement. 11H NMR (DMSO-d6, 500 MHz) σ (ppm): 9.83 (d, 1H), 9.66 (s, 1H), 9.23 (s, 1H), 9.02 (d, 1H), 8.64 (d, 1H), 8.45 (m, 2H), 5.15 (t, 2H), 4.68 (t, 2H), 2.98 (s, 3H), 2.05 (m, 4H), 1.95 (m, 4H), 1.85 (s, 6H), 1.47 (m, 4H), 0.95 (m, 6H)

[0117] [Example 6] <Fabrication of EC Element> Tetrabutylammonium perchlorate as an electrolyte was dissolved in propylene carbonate at a concentration of 0.1 M, and then the exemplified compound A-31 of Example 3 was dissolved at a concentration of 40.0 mM to obtain an EC medium.

[0118] Next, an insulating layer (SiO2) was formed at the four ends of a pair of glass substrates with transparent conductive films (ITO). A PET film (Melinex S (registered trademark) manufactured by Teijin DuPont Films, 125 μm thick) that defines the substrate interval was placed between the pair of glass substrates with transparent electrode films. Then, leaving an injection port for injecting the EC medium, the substrate and the PET film were adhered and sealed with an epoxy adhesive to fabricate an empty cell with an injection port. Next, the EC medium was injected through the injection port by a vacuum injection method, and then the injection port was sealed with an epoxy adhesive to obtain an EC element.

[0119] The EC element immediately after fabrication showed a transmittance of around 80% over the entire visible light region and had high transparency.

[0120] <Characteristic Evaluation of EC Element> Figure 5 shows the ultraviolet-visible absorption spectra of the colored state and the bleached state of this element. As the light source, a deuterium, halogen light source DH-2000S from Ocean Optics was used. As shown in Figure 5, when a voltage of 2.0 V was applied to this element, absorption derived from the reduced species of the exemplified compound A-31 was shown, and the element was colored. Furthermore, when a voltage of -0.5 V was applied to this element, it was bleached. This element can reversibly change between the colored state and the bleached state.

[0121] [Example 7] A device was prepared and evaluated in the same manner as in Example 6, except that exemplary compound A-22 was used instead of exemplary compound A-31. FIG. 6 shows the ultraviolet-visible absorption spectrum of the device in the colored state and the decolored state. As shown in FIG. 6, when a voltage of 2.0 V was applied to the device, the device exhibited absorption due to the reduced species of exemplary compound A-22, and was colored. Furthermore, when a voltage of −0.5 V was applied to the device, the device was decolored, and reversible coloring and decoloring were performed. This device can reversibly change between a colored state and a decolored state.

[0122] [Example 8] A device was prepared and evaluated in the same manner as in Example 6, except that exemplary compound A-25 was used instead of exemplary compound A-31. FIG. 7 shows the ultraviolet-visible absorption spectrum of the device in the colored state and the decolored state. As shown in FIG. 7, when a voltage of 2.0 V was applied to the device, the device exhibited absorption due to the reduced species of exemplary compound A-25, and was colored. Furthermore, when a voltage of −0.5 V was applied to the device, the device was decolored, and reversible coloring and decoloring were performed. This device can reversibly change between a colored state and a decolored state. [Explanation of symbols]

[0123] 1 EC element 10 Transparent substrate 11 Transparent electrode 12 EC layer 13 Spacer

Claims

1. An organic compound represented by the following general formula (1): 【Chemistry 1】 In the general formula (1), X １ and X ２ are each independently selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and a substituted or unsubstituted aralkyl group. R １ ~R ８ are each independently selected from a hydrogen atom and a substituent. １ ~R ８ The substituent represented by the formula (I) is any one of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. R ９ and R １０ is either a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

2. A is an anion １ － and A which is an anion ２ － 2. The organic compound according to claim 1, further comprising:

3. The above A １ － and the above A ２ － and are the same anion.

4. The X １ and the above X ２ The organic compound according to any one of claims 1 to 3, characterized in that:

5. The X １ and the above X ２ and are the same substituent.

6. The R ９ and R １０ The organic compound according to any one of claims 1 to 5, characterized in that:

7. The R １ ~R ８ The organic compound according to any one of claims 1 to 6, characterized in that all of the following are hydrogen atoms.

8. An electrochromic element having a pair of electrodes and an electrochromic layer disposed between the pair of electrodes, An electrochromic device, wherein the electrochromic layer contains the organic compound according to claim 1 .

9. 9. The electrochromic device according to claim 8, wherein the electrochromic layer comprises an electrochromic compound different from the organic compound.

10. 10. The electrochromic device according to claim 9, wherein the different electrochromic compound is any one of a phenazine-based compound, a metallocene-based compound, a phenylenediamine-based compound, and a pyrazoline-based compound.

11. 11. The electrochromic device according to claim 8, wherein the electrochromic layer comprises five or more kinds of electrochromic compounds.

12. 12. The electrochromic device according to claim 8, wherein the electrochromic layer is a solution layer.

13. 13. The electrochromic device according to claim 12, wherein the solution layer comprises a thickener.

14. 14. The electrochromic device according to claim 13, wherein the weight ratio of the thickener is 20 wt % or less when the weight of the electrochromic layer is 100 wt %.

15. 15. The electrochromic device according to claim 12, wherein the viscosity of the solution layer is 150 cP or less.

16. 16. An optical filter comprising: an electrochromic element according to claim 8; and a transistor connected to the electrochromic element.

17. 17. A lens unit comprising: the optical filter according to claim 16; and an imaging optical system having a plurality of lenses.

18. 17. An imaging device comprising: the optical filter according to claim 16; and a light receiving element that receives light that has passed through the optical filter.

19. 16. A window material comprising: the electrochromic element according to claim 8; and a transistor connected to the electrochromic element.

20. 16. An electrochromic mirror comprising: the electrochromic element according to claim 8; and a reflective member provided inside or outside the electrochromic element.

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