JP2021011441A - Organic compound, and electrochromic element, optical film, lens unit, imaging device and window material containing the same - Google Patents

Abstract

To provide a phenazine derivative that has a light absorption peak in a wavelength range longer than before in the oxidation state.SOLUTION: Provided is an organic compound represented by the following general formula (1). In the formula, A1 and A2 are H, or substituent. However, at least one of A1 and A2 is an alkyl group or an alkoxy group. R3 is H or a substituent. A3 is each independently selected from a halogen atom, an alkyl group, an alkoxy group, an aryl group and an aryloxy group. R1 and R2 are each independently selected from an alkyl group and an aralkyl group.SELECTED DRAWING: Figure 1

Description

The present invention relates to an electrochromic organic compound, an electrochromic element having the same, an optical film, a lens unit, an image pickup device, and a window material.

Various materials as materials having electrochromic properties (hereinafter sometimes abbreviated as "EC") in which the properties of optical absorption (coloration state and light transmittance) of a substance are changed by an electrochemical redox reaction. It has been known.

Examples of the organic low molecular weight compound having EC property (organic low molecular weight EC compound) include a viologen derivative which is a cathodic EC compound which is colored by reduction, a phenazine derivative which is an anodic EC compound which is colored by oxidation, and the like.

Since these low-molecular-weight EC compounds have a shorter π-conjugated length than the conductive polymer, they have light absorption only in the ultraviolet region and no absorption in the visible light region. On the other hand, in the case of an anodic EC compound, visible light is absorbed in an oxidized state, and in the case of a cathodic EC compound, visible light is absorbed in a reduced state. This is because the conjugation length in the oxidized state or the reduced state is longer than the conjugation length in the neutral state, so that the wavelength region that absorbs light is the visible light region. That is, the organic low molecular weight EC compound is decolorized in the neutral state and colored in the oxidized or reduced state.

Conventionally, EC elements have been applied to dimming mirrors, electronic papers, dimming glasses, etc. of automobiles. These EC elements utilize the fact that various color tones can be displayed by selecting a material. In order to expand the applications of EC elements by creating materials with various color tones when using EC elements, material development has been actively carried out. For example, when considering application to a full-color display or the like, it is preferable to use a material that colors cyan, magenta, or yellow. Considering the application to a wider range of applications, an EC material having various absorption wavelengths at the time of coloring is required.

In Patent Document 1, since the phenyl group having an alkoxy group at the 2-position is substituted, phenazine has a wavelength of about 580 nm in the oxidized state and does not have visible light absorption in the neutral state. Derivatives are disclosed.

JP-A-2017-200905

The phenazine derivative described in Patent Document 1 is substituted with a phenyl group having an alkoxy group at the 2-position, absorbs light having a wavelength of about 580 nm in the oxidized state, and has light absorption in the visible light region in the neutral state. Do not. However, there is room for further improvement in order for the EC element to express various color tones.

The present invention has been made in view of the above problems, and an object of the present invention is to have a light absorption peak in a wavelength region at a longer wavelength than before in an oxidized state, and to reduce light absorption in a visible light region in a neutral state. It is an object of the present invention to provide the organic compound.

One embodiment of the present invention provides an organic compound represented by the following general formula (1).

In the general formula (1), A ₁ and A ₂ are independently selected from a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, and a heterocyclic group, respectively. However, at least one of A ₁ and A ₂ is the alkyl group or the alkoxy group. R ₃ is independently selected from a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an aryloxy group. A ₃ is independently selected from a halogen atom, an alkyl group, an alcohol group, an aryl group, and an aryloxy group. R ₁ and R ₂ are independently selected from the alkyl group or the aralkyl group, respectively.

According to the organic compound as one aspect of the present invention, it is possible to provide a phenazine derivative having a light absorption peak in a wavelength region longer than the conventional one in an oxidized state.

It is sectional drawing of an example of the electrochromic element which concerns on embodiment. It is a schematic diagram which shows an example of the drive device which includes the electrochromic element which concerns on embodiment. (A) It is a schematic diagram of an example of an image pickup apparatus in which an optical filter is arranged in a lens unit. (B) It is a schematic diagram of an example of an image pickup apparatus in which an optical filter is arranged in the image pickup apparatus. (A) It is an overview view which shows the window using the EC element which concerns on one Embodiment of this invention. (B) is a schematic cross-sectional view taken along the line XX'of FIG. 4 (a). (A) It is a figure which shows the ultraviolet-visible absorption spectrum in the radical state of each of Example Compound A-16 and Comparative Compound 1 in Example 2 and Comparative Example 1. (B) It is a figure which shows the ultraviolet-visible absorption spectrum in the neutral state of each of Example Compound A-16 and Comparative Compound 1 in Example 2 and Comparative Example 1.

The organic compound according to the embodiment of the present invention is an organic compound having an electrochromic property (EC property) and is an organic compound represented by the general formula (1). In this specification, electrochromic may be abbreviated as EC. Further, in the present specification, changing to a state where the transmittance is low is sometimes referred to as coloring. On the contrary, changing to a state where the transmittance is high is sometimes called decolorization.

In the general formula (1), A ₁ and A ₂ are derived from a hydrogen 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. Each is chosen independently. However, at least one of A ₁ and A ₂ is any of the above substituents, preferably the alkyl group or the alkoxy group. That is, neither A ₁ nor A ₂ is a hydrogen atom. Further, it is preferable that at least one of A ₁ and A ₂ is a substituent having an oxygen atom.

R ₃ is independently selected from a hydrogen atom, 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 aryloxy group, respectively. R ₃ can be provided at any position other than A ₁ and A ₂ . Further may be provided a plurality of R _3, when there are a plurality of R ₃ may be each the same substituent, it may be different substituents.

A ₃ is a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, each independently selected from substituted or unsubstituted aryloxy group. R ₁ and R ₂ are independently selected from a substituted or unsubstituted alkyl group or a substituted or unsubstituted aralkyl group, respectively.

Specific examples of the substituent in the general formula (1) are shown below. However, these are merely examples of representative examples of organic compounds, and the present invention is not limited thereto.

The alkyl group in the general formula (1) may be linear, branched or cyclic. Further, the hydrogen atom of the alkyl group may be replaced with a fluorine atom or an ester group. The alkyl group may have 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, an isobutyl group, a cyclohexyl group, and a trifluoromethyl group. Preferred examples include a methyl group, an isopropyl group and an isobutyl group.

The alkoxy group in the general formula (1) may have 1 or more carbon atoms and 20 or less carbon atoms. Examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an ethylhexyloxy group, a 2-methoxyethoxy group, a benzyloxy group and the like.

Examples of the aryl group in the general formula (1) include a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, a fluoranthenyl group, an anthryl group, a pyrenyl group and the like. It is preferably a phenyl group. The aryl group may have a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or an acyl group as a substituent. The alkyl group and the alkoxy group preferably have 1 or more and 4 or less carbon atoms.

Examples of the aryloxy group in the general formula (1) include a phenoxy group and a naphthyloxy group. The aryloxy group may have a halogen atom, an alkyl group, an alkoxy group, an aryl group, or an acyl group as a substituent. The alkyl group and the alkoxy group preferably have 1 or more and 4 or less carbon atoms.

Examples of the halogen atom in the general formula (1) include fluorine, chlorine, bromine, iodine and the like.

Examples of the aralkyl group in the general formula (1) include a benzyl group and a phenylethyl group. The aralkyl group may have a halogen atom, an alkyl group, an alkoxy group, an aryl group or an acyl group as a substituent. The alkyl group and the alkoxy group preferably have 1 or more and 4 or less carbon atoms.

Since the 2-position and the 7-position in which the phenazine derivative according to the embodiment of the present invention has a substituent are not the resonance positions of the phenazine skeleton, even if a substituent is provided in any of them, the electronic state of the phenazine derivative remains. The effect is small. Therefore, the phenazine derivative according to the embodiment of the present invention can reduce the influence of the substituent on the HOMO of phenazine, and can further shorten the wavelength of neutral absorption. On the other hand, if a substituent is introduced at two positions at the resonance position, it is considered that the energy of HOMO changes significantly due to the influence of the two substituents and the neutral wavelength becomes longer. Since the phenazine derivative according to the embodiment of the present invention has substituents at the 2- and 7-positions which have a small effect on the phenazine skeleton, the absorption in the neutral state in which the phenazine derivative is dissolved becomes more transparent. be able to.

In addition, as a result of diligent studies, the present inventors have found the position of a substituent of the phenazine derivative in which the absorption wavelength in the radical cation state becomes a longer wavelength.

As described above, since the organic compound according to the embodiment of the present invention has a structure represented by the general formula (1), it is a compound having high transparency when dissolved in a solvent. Further, the organic compound according to the embodiment of the present invention is a compound that absorbs light having a longer wavelength than before in an oxidized state. In addition, in this specification, it may be expressed as coloring the need for light. A compound that is colored in the oxidized state is a compound in which the transmittance of visible light in the oxidized state is lower than the transmittance of visible light in the neutral state. The skeleton of phenazine may be provided with a substituent that adjusts the solubility in a solvent.

When a substituent is introduced at an arbitrary position of the phenazine derivative as in the organic compound according to the embodiment of the present invention, first, a means for synthesizing the phenazine skeleton with the substituent can be taken. A method of synthesizing a phenazine skeleton from an aniline derivative and a nitrobenzene derivative is known, but when synthesizing a phenazine derivative having a substituent at the 2,7-position by this route, it is replaced with the 1,6-position. A phenazine derivative having a group is produced at the same time. Since it may be difficult to separate the phenazine derivative having a substituent at the 2,7-position and the phenazine derivative having a substituent at the 1,6-position, it can be easily separated by devising the provided substituent. It is preferable to synthesize the above. In the present specification, as an example, a phenazine derivative having a substituent at the 2,7-position was selectively synthesized by introducing a steric hindrance group into the substituent at the 2-position.

The method for producing the organic compound according to the embodiment of the present invention is not particularly limited, and for example, it can be produced by the method shown below.

Intermediate 1 can be synthesized by performing a coupling reaction between 3-halogenoaniline and a phenylboronic acid derivative having the desired substituents A ₁ , A ₂ and R ₃ . It can be synthesized Intermediate 2 by the intermediate 1 and the para-position carry out the reaction of nitrobenzene derivatives with the desired substituent A _3.

When the cyclization reaction of intermediate 2 is carried out, intermediate 3 and intermediate 4 are obtained. It is considered that the intermediate 3 and the intermediate 4 obtained here are difficult to separate because they have similar polarities. Here, by introducing the steric hindrance of the substituent A1 and the substituent A2, it becomes difficult to generate the intermediate 4, and the selectivity of the intermediate 3 is improved. Further, when a mixture of the intermediate 3 and the intermediate 4 is obtained, the formation of the compound (2) is suppressed due to the steric hindrance of the substituent A ₁ and the substituent A ₂ during the alkylation reaction of the nitrogen atom. The selectivity of 1) can be improved. Again, since the polarities of compound (1) and compound (2) are similar, it is considered difficult to separate them, but compound (1) can be isolated by reducing the formation of compound (2) due to steric hindrance. It will be easier.

That is, from the viewpoint of synthesis, it is preferable that at least one of A ₁ and A ₂ is preferably a substituent, not a hydrogen atom. More preferably, at least one of A ₁ and A ₂ is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.

The specific structural formula of the organic compound according to the embodiment of the present invention is illustrated below. However, the compound according to the present invention is not limited to these.

The organic compound according to one embodiment of the present invention is an electrochromic material that exhibits stable coloring, and can be used for an EC element, an optical filter using the same, a lens unit, an image pickup device, and the like.

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

The EC element 1 of FIG. 1 has a pair of transparent substrates 10, a pair of electrodes 11, and an EC layer 12 arranged between the pair of electrodes. The distance between the pair of electrodes is constant due to the spacer 13.

The EC layer has an organic compound according to the present invention. This EC layer may have a layer made of an EC compound and a layer made of an electrolyte. Further, the EC layer may be provided as a solution containing the EC compound and the electrolyte. It can be said that the EC layer is a solution layer in such a form. In the EC element according to the embodiment of the present invention, the EC layer is preferably a solution layer. When the EC layer is a solution layer, EC-based organic compounds, solutions, and other lysates may be collectively referred to as an EC medium.

Next, the members constituting the EC element according to the embodiment of the present invention will be described.

The electrolyte is not limited as long as it is an ion-dissociable salt, has good solubility in a solvent, and exhibits high compatibility with a solid electrolyte. Of these, an electrolyte having an electron donating property 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. Specifically, _{LiClO 4, LiSCN, LiBF 4,} LiAsF 6, LiCF 3 SO 3, LiPF 6, LiI, NaI, NaSCN, NaClO 4, NaBF 4, NaAsF 6, KSCN, the KCl like Li, Na, K alkaline Metal salts, etc., (CH ₃ ) ₄ NBF ₄ , (C ₂ H ₅ ) ₄ NBF ₄ , (n-C ₄ H ₉ ) ₄ NBF ₄ , (n-C ₄ H ₉ ) ₄ NPF ₆ , (C ₂₎ Examples thereof include quaternary ammonium salts such as H ₅ ) ₄ NBr, (C ₂ H ₅ ) ₄ NClO ₄ , (n-C ₄ H ₉ ) ₄ NClO _4, and cyclic quaternary ammonium salts.

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 those having polarity are particularly preferable. Specifically, water, methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, γ-butyrolactone, γ-valerolactone, sulfolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, acetonitrile, propionnitrile, benzonitrile, Examples thereof include organic polar solvents such as dimethylacetamide, methylpyrrolidinone and dioxolane.

Further, the EC medium may contain a polymer or a gelling agent to be highly viscous or gelled. These polymers and gelling agents can also be called thickeners. By having a thickener and increasing the viscosity of the EC solution, it becomes difficult for the organic compounds to form aggregates, and the temperature dependence of the absorption spectrum can be reduced. Therefore, the EC solution preferably has a thickener.

The viscosity of the EC solution may be 10 cP or more and 5000 cP or less, and may be 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, preferably 50 cP or more.

The thickener may have a weight ratio of 20 wt% or less when the total weight of the EC solution is 100 wt%. It is preferably 1 wt% or more and 15 wt% or less, and more preferably 5 wt% or more and 10 wt% or less.

The polymer is not particularly limited, and examples thereof include polyacrylonitrile, carboxymethyl cellulose, polyvinyl chloride, polyalkylene oxide, polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, polyester, and Nafion (registered trademark). Polymethylmethacrylate, polyethylene oxide and polypropylene oxide are preferable.

When the viscosity of the EC solution is high, the movement of molecules in the EC solution can be suppressed, so that association may be suppressed. On the other hand, since the movement of electrons in the EC solution is suppressed, the response speed of the EC element is reduced, so that it is not preferable that the viscosity is too high.

Next, the transparent substrate and the transparent electrode will be described. As the transparent substrate, for example, colorless or colored glass, tempered glass or the like is used, or a colorless or colored transparent resin is used. In one embodiment of the present invention, "transparent" means that the transmittance of visible light is 90% or more. Specific examples thereof include polyethylene terephthalate, polyethylene naphthalate, polynorbornene, polyamide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polycarbonate, polyimide, polymethylmethacrylate and the like.

Materials for the transparent electrode include, for example, indium tin oxide alloy (ITO), fluorine-doped tin oxide (FTO), tin oxide (NESA), zinc indium oxide (IZO), silver oxide, vanadium oxide, molybdenum oxide, gold, and silver. , Metals and metal oxides such as 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. Further, a conductive polymer whose conductivity has been improved by a doping treatment or the like, for example, polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, a complex of polyethylenedioxythiophene (PEDOT) and polystyrene sulfonic acid, and the like are also preferably used.

Further, 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 lot shape, and a wire shape. As the material of the porous electrode, for example, metal, metal oxide, carbon and the like can be applied. More preferably, it is a metal oxide 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.

The spacer is arranged between the pair of transparent electrodes and provides a space for accommodating the EC layer containing the EC compound of the present invention. Specifically, polyimide, polytetrafluoroethylene, fluororubber, epoxy resin and the like can be used. With this spacer, it is possible to maintain the distance between the electrodes of the EC element.

The EC element according to the embodiment of the present invention may have a liquid injection port formed by a pair of electrodes and a spacer. After encapsulating the composition having the EC compound from the liquid injection port, the injection port 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 of separating the adhesive and the EC compound from 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.

The method for forming the EC element according to the embodiment of the present invention is not particularly limited, and an EC compound prepared in advance by a vacuum injection method, an atmospheric injection method, a meniscus method, or the like is contained in a gap provided between a pair of electrode substrates. A method of injecting a liquid can be used.

The EC element according to the embodiment of the present invention may have an organic compound according to the embodiment of the present invention and an organic compound (second organic compound) different from the organic compound. The second organic compound may be one kind or a plurality of kinds, and may be a compound colored in an oxidizing state, a compound colored in a reducing state, or a compound having both properties. Since the organic compound represented by the general formula (1) is a compound that is colored in the reduced state, the second organic compound is preferably a compound that is colored in the oxidized state. A compound that is colored in the oxidized state is a compound in which the transmittance of visible light in the oxidized state is lower than the transmittance of visible light in the reduced state. The transmittance may change in any of the visible light regions, and the transmittance does not have to change in the entire visible light region. Specific examples thereof include 4,4'-bipyridine compounds and 4,4'-bipyridine compounds having an alkyl group, an aralkyl group, an aryl group, and a heterocyclic group. Further, the second organic compound may have the same anodic property as phenazine, and examples thereof include a phenazine compound, a metallocene compound, a phenylenediamine compound, and a pyrazoline compound.

The organic compound according to one embodiment of the present invention can absorb a desired color as an EC element by combining with a coloring material of another color. The other type of organic compound at the time of coloring preferably has an absorption wavelength in the range of 400 nm or more and 800 nm or less, and more preferably has an absorption wavelength in the range of 420 nm or more and 700 nm or less. Having an absorption wavelength in a specific range means that the peak of the absorption spectrum is in a specific range. By combining a plurality of the organic compound of the present invention with other materials, an EC element that absorbs the entire visible region and is colored black can also be produced.

The EC element according to the embodiment of the present invention preferably has five or more kinds of EC compounds in combination with the organic compound according to the present invention. This is because a filter having an EC element easily absorbs light of each wavelength uniformly.

Examples of other EC compounds according to one embodiment of the present invention include compounds having the following structural formulas.

Other EC compounds that are colored in the oxidized state include oligothiophene compounds, phenazine compounds such as 5,10-dihydro-5,10-dimethylphenazine, 5,10-dihydro-5,10-diisopropylphenazine, ferrocene, and the like. Metallocene compounds such as tetra-t-butylferrocene and titanocene, phenylenediamine compounds such as N, N', N, N'-tetramethyl-p-phenylenediamine, and pyrarizone compounds such as 1-phenyl-2-pyrazolin. And so on.

Compounds to be colored in the reduced state include N, N'-diheptylbipyridinium diparklolate, N, N'-diheptylbipyridinium ditetrafuofolobolate, N, N'-diheptylbipyridinium dihexafluorophosphate, N, N. '-Diethylbipyridinium diparklolate, N, N'-diethylbipyridinium ditetrafluoroborate, N, N'-diethylbipyridinium dihexafluorophosphate, N, N'-dibenzylbipyridinium diparklolate, N, N'-di Benzylbipyridinium ditetrafluoroborate, N, N'-dibenzylbipyridinium dihexafluorophosphate, N, N'-diphenylbipyridinium diparklolate, N, N'-diphenylbipyridinium ditetrafluoroborolate, N, N'-diphenylbipyridinium Viologen-based compounds such as dihexafluorophosphate, anthraquinone-based compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, and octamethylanthraquinone, ferrosenium salt-based compounds such as ferrosenium tetrafluoroborate and ferrosenium hexafluorophosphate. , Stylylated compounds and the like.

In one embodiment of the present invention, the phenazine-based compound is a compound containing a 5,10-dihydrophenazine skeleton in its chemical structure. Phenazine compounds include compounds having a substituent on 5,10-dihydrophenazine. For example, the hydrogen atom 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-based compound may be a compound having an alkyl group having 1 to 20 carbon atoms in 5,10-dihydrophenazine. Further, it may be a compound having an alkoxy group having 1 to 20 carbon atoms in 5,10-dihydrophenazine. Further, it may be a compound having an aryl group having 4 or more and 60 or less carbon atoms in 5,10-dihydrophenazine. The same applies to other compounds such as viologen compounds.

Among the above, the second organic compound is preferably any of a phenazine-based compound, a metallocene-based compound, a phenylenediamine-based compound, and a pyrazoline-based compound.

The compound contained in the EC layer of the EC element according to the embodiment of the present invention can be confirmed to be contained in the EC element by extracting and analyzing it by a known method. For example, it can be extracted by chromatography and analyzed by NMR. When the electrochromic layer is solid, it can be analyzed by TOF-SIMS or the like.

[Use of EC element]
The EC element according to the embodiment of the present invention can be used for an optical filter, a lens unit, an image pickup device, a window material, and the like.

<Optical filter>
The optical filter according to the embodiment of the present invention has an EC element and an active element connected to the EC element. The active element is an active element that drives the EC element and adjusts the amount of light passing through the EC element. Examples of the active element include a transistor and the like. The transistor may have an oxide semiconductor such as InGaZnO in the active region.

The optical filter has an EC element according to an embodiment of the present invention and a drive device connected to the EC element. FIG. 2 is a schematic view showing an example of the driving device 20 of the EC element and the EC element driven by the driving device 20. The drive device 20 of the EC element 1 according to the embodiment of the present invention includes a drive power supply 8, a resistance switch 9, and a controller 7.

The drive power supply 8 applies a voltage required for the EC material contained in the EC layer to cause an electrochemical reaction to the EC element. It is more preferable that the drive voltage is a constant voltage. This is because when the EC material is composed of a plurality of types of materials, the absorption spectrum may change due to the difference in the redox potential of the materials and the difference in the molar extinction coefficient, so that the voltage is preferably constant. Is. The voltage application of the drive power source 8 is started or the applied state is held by the signal of the controller 7, and the constant voltage applied state is held during the period of controlling the light transmittance of the EC element.

As a method of controlling the transmittance of the EC element by the controller 7, a method suitable for the element to be used is adopted. Specifically, a method of inputting a predetermined condition to the EC element 1 with respect to a desired transmittance setting value, or a method of comparing the transmittance setting value with the transmittance of the EC element 1 and setting the setting. One method is to select and enter a condition that matches the value. The parameters to 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.

In one embodiment of the present invention, known means can be used for voltage change, current change, and pulse width modulation. The pulse width can also be modulated as follows.

The resistor switch 9 switches the resistor R1 and the resistor R2 larger than the resistor R1 shown in the figure in a closed circuit including the drive power supply 8 and the EC element and connects them in series. The resistance value of the resistor R1 is preferably at least smaller than the maximum impedance of the element closing circuit, and is preferably 10Ω or less. The resistance value of the resistor R2 is preferably larger than the maximum impedance of the element closing circuit, and is preferably 1 MΩ or more. The resistor R2 may be air. In this case, strictly speaking, the closed circuit is an open circuit, but it can be considered as a closed circuit by regarding air as the resistor R2.

The controller 7 sends a switching signal to the resistor switch 9 to control switching between the resistors R1 and R2.

<Lens unit>
The lens unit according to the embodiment of the present invention 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 lenses. The optical filter is preferably provided on the optical axis of the lens.

<Imaging device>
The image pickup apparatus according to the embodiment of the present invention includes an optical filter and a light receiving element that receives light that has passed through the optical filter. Specific examples of the imaging device include a camera, a video camera, a camera-equipped mobile phone, and the like. The image pickup apparatus may have a form in which the main body having the light receiving element and the lens unit having the lens can be separated. Here, when the image pickup apparatus can be separated into the main body and the lens unit, the present invention also includes a form in which an optical filter separate from the image pickup apparatus is used at the time of imaging. In this case, the arrangement position of the optical filter includes the outside of the lens unit, between the lens unit and the light receiving element, between a plurality of lenses (when the lens unit has a plurality of lenses), and the like.

FIG. 3A is a schematic diagram of an example of an image pickup apparatus in which an optical filter is arranged in a lens unit, and FIG. 3B is a schematic diagram of an example of an image pickup apparatus in which an optical filter is arranged in the image pickup apparatus.

The image pickup device 100 is an image pickup device having a lens unit 102 and an image pickup unit 103. The lens unit 102 includes an optical filter 101 and an imaging optical system having a plurality of lenses or lens groups. The optical filter 101 is the optical filter of the above-described embodiment of the present invention.

The lens unit 102 represents, for example, a rear focus type zoom lens in which focusing is performed after the aperture in FIG. 3A. From the object side, the first lens group 104 with positive refractive power, the second lens group 105 with negative refractive power, the third lens group 106 with positive refractive power, and the fourth lens group with positive refractive power. It has four lens groups of 107. The distance between the second lens group 105 and the third lens group 106 is changed to perform magnification change, and a part of the lens groups of the fourth lens group 107 is moved to perform focusing.

The lens unit 102 has, for example, an aperture diaphragm 108 between the second lens group 105 and the third lens group 106, and between the third lens group 106 and the fourth lens group 107. It has an optical filter 101. The light passing through the lens unit is arranged so as to pass through each lens group 104 to 107, the diaphragm 108, and the optical filter 101, and the amount of light can be adjusted by using the aperture diaphragm 108 and the optical filter 101.

The lens unit 102 is detachably connected to the image pickup unit 103 via a mount member (not shown).

In one embodiment of the present invention, the optical filter 101 is arranged between the third lens group 106 and the fourth lens group 107 in the lens unit 102, but the image pickup apparatus 100 is limited to this configuration. Not done. For example, the optical filter 101 may be located in front of the aperture diaphragm 108 (subject side) or behind (imaging unit 103 side), and in front of any of the first to fourth lens groups 104 to 107. Later, it may be between the lens groups. If the optical filter 101 is arranged at a position where the light converges, there is an advantage that the area of the optical filter 101 can be reduced.

Further, the configuration of the lens unit 102 is not limited to the above configuration, and can be appropriately selected. For example, in addition to the rear focus type, an inner focus type in which focusing is performed before the aperture may be used, or another method may be used. In addition to the zoom lens, a special lens such as a fisheye lens or a macro lens can be appropriately selected.

The image pickup unit 103 includes 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. Further, the light receiving element 110 is a sensor unit that receives light that has passed through the lens unit, and an image pickup element such as a CCD or CMOS can be used. Further, an optical sensor such as a photodiode may be used, and a sensor that acquires and outputs information on the intensity or wavelength of light can be appropriately used.

When the optical filter 101 is incorporated in the lens unit 102 as shown in FIG. 3A, the driving device may be arranged inside the lens unit 102 or outside the lens unit 102. When it is arranged outside the lens unit 102, the EC element 1 inside the lens unit 102 and the drive device are connected through wiring to control the drive.

Further, in the configuration of the image pickup apparatus 100 described above, the optical filter 101 is arranged inside the lens unit 102. However, the present invention is not limited to this embodiment, and the optical filter 101 may be arranged at an appropriate position inside the image pickup apparatus 100, and the light receiving element 110 may be arranged so as to receive light that has passed through the optical filter 101.

For example, as shown in FIG. 3B, the imaging unit 103 may have an optical filter 101. FIG. 3B is a diagram for explaining the configuration of another example of the imaging device according to the embodiment of the present invention, and is a schematic diagram of the configuration of the imaging device having an optical filter in the imaging unit 103. In FIG. 3B, for example, the optical filter 101 is arranged immediately before the light receiving element 110. When the image pickup device itself has an optical filter 101 built-in, the connected lens unit 102 itself does not have to have the optical filter 101, so that a dimmable image pickup device using the existing lens unit 102 can be configured. It will be possible.

The image pickup apparatus 100 according to an embodiment of the present invention is applicable to a product having a combination of light intensity adjustment and a light receiving element. For example, it can be used for cameras, digital cameras, video cameras, and digital video cameras, and can also be applied to products with a built-in imaging device such as mobile phones, smartphones, PCs, and tablets.

According to the image pickup apparatus 100 according to the embodiment of the present invention, by using the optical filter 101 as a dimming member, the dimming amount can be appropriately changed by one filter, and the number of member points can be reduced and the space can be saved. There are advantages such as.

<Window>
A window according to an embodiment of the present invention has an EC element and an active element connected to the EC element. The active element is an active element that drives the EC element and adjusts the amount of light passing through the EC element. Examples of the active element include a transistor and the like. The transistor may have an oxide semiconductor such as InGaZnO in the active region. The window according to the embodiment of the present invention can also be referred to as a variable transmittance window.

FIG. 4A is an overview view showing a dimming window as a window material using an EC element according to an embodiment of the present invention, and FIG. 4B is a cross section taken along the line XX'of FIG. 4A. It is a schematic which shows a figure. The dimming window 111 of the embodiment of the present invention includes an EC element 1 (optical filter), a transparent plate 113 sandwiching the EC element 1, and a frame 112 that surrounds and integrates the whole. The EC element 1 has a drive device (not shown), and the drive device may be integrated in the frame 112 or may be arranged outside the frame 112 and connected to the EC element 1 through wiring.

The transparent plate 113 is not particularly limited as long as it is a material having a high light transmittance, and is preferably a glass material in consideration of its use as a window. The material of the frame 112 is not limited, but a frame that covers at least a part of the EC element 1 and has an integrated form may be regarded as a frame. Although the EC element 1 is a component independent of the transparent plate 113 in FIG. 4, for example, the transparent substrate 10 of the EC element 1 may be regarded as the transparent plate 113.

Such a dimming window can be applied to, for example, an application for adjusting the amount of sunlight incident into a room during the daytime. Since it can be applied to adjust the amount of heat as well as the amount of sunlight, it can be used to control the brightness and temperature of a room. It can also be applied as a shutter to block the view from the outside to the inside. Such dimming windows can be applied not only to glass windows for buildings but also to windows of vehicles such as automobiles, trains, airplanes, and ships.

As described above, the EC element 1 containing the organic compound represented by the general formula (1) in the EC layer 12 can be used for an optical filter, a lens unit, an image pickup device, a window material, and the like. Each of the optical filter, the lens unit, the image pickup apparatus, and the window material according to the embodiment of the present invention can be obtained by using the organic compound represented by the general formula (1) alone or by combining it with an EC compound having color absorption in another wavelength band. , It is possible to provide various absorption colors. Further, since each of the optical filter, the lens unit, the image pickup apparatus, and the window material according to the embodiment of the present invention contains the organic compound represented by the general formula (1), the transparency in the decolorized state can be improved. ..

Further, an electrochromic mirror can be obtained by providing a reflecting member in one of the light paths of the electrochromic element. The electrochromic mirror may be provided in an automobile as an antiglare mirror.

Examples will be described below, but the present invention is not limited thereto.

[Example 1]
<Synthesis of Exemplified Compound A-16>

In a reaction vessel, 0.86 g of 3-bromoaniline (5.0 mmol) and 1.47 mg of 2-isopropoxy-6-methoxyphenylboronic acid (7.0 mmol) were added to toluene / 1,4-dioxane (12 ml / 12 ml). ) Mixing was performed in a mixed solvent, and dissolved oxygen was removed with nitrogen. Next, 45 mg of Pd (OAc) ₂ (0.20 mmol), 205 mg of 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl (S-Phos) (0.5 mmol), and 5.8 g of triphosphate. Potassium (25 mmol) was added to the reaction solution under a nitrogen atmosphere, and the mixture was heated under reflux at 100 ° C. and reacted for 8 hours. The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: toluene) to obtain Intermediate 11 (0.99 mg, 77% yield).

1.29 g of potassium tert-butoxide (11.6 mmol) and 20 ml of tetrahydrofuran were charged in a reaction vessel and cooled to −78 ° C. A solution prepared by dissolving 0.83 g of 4-nitrodiphenyl ether (3.86 mmol) in 5 ml of tetrahydrofuran was slowly added dropwise to this solution, and 0.99 g of intermediate 11 (3.86 mmol) was further dissolved in 5 ml of tetrahydrofuran. The solution was slowly added dropwise. After further stirring for about 1 hour, 6 ml of acetic acid was added dropwise. After raising the temperature of this solution to room temperature, an aqueous ammonium chloride solution was added to quench the reaction, and the solution was extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, and then dried under reduced pressure. Purification by silica gel column chromatography (eluent: hexane / toluene = 2/1) gave 0.98 g of Intermediate 12 (yield: 59%).

To the reaction vessel, 0.99 g of Intermediate 12 (2.26 mmol) and 2.81 g of acetonitrile 15, N, O-bis (trimethylsilyl) acetamide were added, and the mixture was stirred at room temperature for about 24 hours. The reaction solution was dried under reduced pressure using a rotary evaporator. Purification by silica gel column chromatography (eluent: hexane / toluene = 1/1) gave 0.80 g of Intermediate 13 (yield: 81%). At this time, no isomer of Intermediate 13 was observed.

The structure of Intermediate 13 was confirmed by NMR measurement.

_{^{1 H NMR (CDCl 3, 500MHz}} ) σ (ppm): 8.24 (d, 1H), 8.18 (d, 1H), 8.15 (s, 1H), 7.83 (m, 1H), 7.77 (m, 1H), 7.47 (m, 2H), 7.43 (m, 1H), 7.33 (m, 2H), 7.25 (m, 2H), 6.71 (m) , 2H), 4.47 (m, 1H), 3.78 (s, 1H), 1.18 (d, 6H).

In a reaction vessel, 0.44 g of Intermediate 13 (1.0 mmol) and 3.4 g of 2-iodopropane (20 mmol) were mixed in an acetonitrile / water (10 ml / 1 ml) mixed solvent and dissolved in nitrogen. Oxygen was removed. Next, 1.0 g of sodium hydrosulfite (5.0 mmol) and 0.83 g of potassium carbonate (6.0 mmol) were added under a nitrogen atmosphere, and the mixture was heated under reflux at 90 ° C. and reacted for 9 hours. went. The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / toluene = 1/1) to obtain 470 mg of Exemplified Compound A-16 (yield 90%).

The structure of Exemplified Compound A-16 was confirmed by NMR measurement.
^{1 1} H NMR (acetone-d 6,500 MHz) σ (ppm): 7.35 (m, 2H), 7.18 (m, 1H), 7.06 (m, 1H), 6.99 (m, 2H) , 6.80 (m, 4H), 6.71 (m, 2H), 6.47 (d, 1H), 6.44 (m, 1H), 4.46 (m, 1H), 4.09 ( m, 1H), 3.73 (s, 1H), 1.49 (m, 12H), 1.18 (d, 6H).

[Example 2]
<Manufacturing and characterization of electrochromic devices>
As an electrolyte, tetrabutylammonium perchlorate was dissolved in propylene carbonate at a concentration of 0.1 M, and then the exemplary compound A-16 of Example 1 was dissolved at a concentration of 40.0 mM to obtain an EC medium.

Next, an insulating layer (SiO ₂ ) was formed on all four ends of a glass substrate with a pair of transparent electrodes (ITO). A PET film (Melinex S (registered trademark) manufactured by Teijin DuPont Film Co., Ltd., 125 μm) that regulates the substrate spacing was placed between a pair of glass substrates with transparent electrodes. Then, the substrate and the PET film were adhered and sealed with an epoxy adhesive, leaving an injection port for injecting an EC medium. As described above, an empty cell with an injection port was prepared.

Next, the EC medium obtained above was injected from the above-mentioned injection port by a vacuum injection method, and then the injection port was sealed with an epoxy adhesive to obtain an EC element.

Immediately after fabrication, this EC element showed a transmittance of about 80% over the entire visible light region and had high transparency.

When a voltage of 2.0 V was applied to this device, absorption (λmax = 570 nm) derived from the oxidized species of Exemplified Compound A-16 was exhibited, and the device was colored. After that, when -0.5 V was applied, the color disappeared. This element can reversibly change between a colored state and a decolored state.

[Comparative Example 1]

Comparative compound 1 in which the position of the substituent was different from that of Exemplified Compound A-16 was prepared and its characteristics were evaluated in the same manner as in Example 2. When a voltage of 2.0 V was applied to this device, absorption (λmax = 543 nm) derived from the oxidized species of Comparative Compound 1 was exhibited, and the device was colored.

FIG. 5A is an ultraviolet-visible absorption spectrum of the radical state of the devices produced in Example 2 and Comparative Example 1. As a light source, a DH-2000S deuterium or halogen light source manufactured by Ocean Optics Co., Ltd. was used. It can be seen that Exemplified Compound A-16 absorbs radicals at longer wavelengths. The spectrum disturbance appearing in the vicinity of 650 nm is due to the influence of the light source and is irrelevant to the absorption spectrum of the compound. The spectrum of the compound connects before and after the turbulence.

FIG. 5B is an ultraviolet-visible absorption spectrum of the neutral state of the device produced in Example 2 and Comparative Example 1. Both the EC element of Example 2 and the element of Comparative Example 1 have a peak in the ultraviolet region and do not have absorption in the visible light region. That is, it can be seen that it is transparent.

[Example 3]
As an example for comparing the correlation of substituents, the absorption wavelengths in the radical state and the absorption wavelengths in the neutral state are verified by molecular orbital calculation for the compound A-16 and the comparative compounds 1, 2 and 3 according to the present invention. It was. The characteristics of organic compounds can be inferred by molecular orbital calculation. The calculated value does not always match the measured value, but the order matches the measured value, so that a guideline for design can be obtained, and it is widely used.

As described above, it can be seen that among the compounds having the same substituent, the phenazine derivative having a substituent at the 2,7-position according to the embodiment of the present invention absorbs light having a longer wavelength. Further, since the 2nd and 7th positions of phenazine do not have a resonance positional relationship, the neutral absorption of the compounds having the same substituent is shorter than that of the other substitution positions, which improves the transparency of the solution. be able to.

The molecular orbital calculation is performed by Gaussian03 * Revision D.C., which is electronic state calculation software. The structure optimization calculation of the ground state was performed using 01. At that time, the density functional theory was adopted as the quantum chemistry calculation method, and B3LYP was used as the functional. The basis functions are Gaussian 03, Revision D. In 01, 6-31G * was used.

The program used to perform this calculation was Gaussian 09, Revision D. 01 (M. J. Frisch, GW Tracks, BB Schlegel, GE Scuseria, MA Robb, J. R. Cheeseman, G. SCALMANI, V. Cane, Barne, V. Barne, V. G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Broino, G. Zheng, J. L. Sonnenb. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Schlegel, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vrem, J. Vern, J. Peralta, F. Ogliaro, M. Bearpark, J. J. Heid, E. Brothers, K. N. Kudin, V. N. Schlegelov, T. Keith, R. Kaba, R. K. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Bakken, C. Adamo, J. Jaramillo, R. Gooperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, C. Pomerli, J. Schlegel, J. , K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniers, O. F. Far. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Walli ngford CT, 2013. ).

Claims (14)

An organic compound represented by the following general formula (1).

In the general formula (1), A ₁ and A ₂ are derived from a hydrogen 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. Each is chosen independently. However, at least one of A ₁ and A ₂ is the alkyl group or the alkoxy group.
R ₃ is independently selected from a hydrogen atom, 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 aryloxy group, respectively.
A ₃ is a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, each independently selected from substituted or unsubstituted aryloxy group. R ₁ and R ₂ are independently selected from substituted or unsubstituted alkyl groups and substituted or unsubstituted aralkyl groups, respectively. The organic compound according to claim 1, wherein at least one of A ₁ and A ₂ is a substituent having an oxygen atom. The organic compound according to claim 1 or 2, wherein both A ₁ and A ₂ are selected from the alkoxy groups. The organic compound according to any one of claims 1 to ₃ , wherein A3 is the aryloxy group. The organic compound according to any one of claims 1 to 4, wherein both R ₁ and R ₂ are selected from the alkyl groups. An electrochromic device having an organic compound arranged between the first electrode, the second electrode, the first electrode, and the second electrode.
An electrochromic device, wherein the organic compound is the organic compound according to any one of claims 1 to 5. The sixth aspect of claim 6, wherein the electrochromic device has an electrochromic layer between the first electrode and the second electrode, and the organic compound is contained in the electrochromic layer. Electrochromic element. The electrochromic device according to claim 7, wherein the electrochromic layer has an organic compound of a different type from the organic compound. The electrochromic element according to claim 8, wherein the other type of organic compound is any one of a phenazine compound, a metallocene compound, a phenylenediamine compound, and a pyrazoline compound. The electrochromic device according to any one of claims 7 to 9, wherein the electrochromic layer is a liquid having an electrolyte and the organic compound. An optical filter comprising the electrochromic element according to any one of claims 6 to 10 and an active element connected to the electrochromic element. The optical filter has an imaging optical system having a plurality of lenses and an optical filter that transmits or absorbs light transmitted through the imaging optical system, and the optical filter is the optical filter according to claim 11. Lens unit. The optical system has an imaging optical system having a plurality of lenses, an imaging element that receives light transmitted through the imaging optical system, and an optical filter arranged between the imaging optical system and the imaging element. An imaging device according to claim 11, wherein the filter is the optical filter. The present invention according to any one of claims 6 to 10, which has a first transparent substrate and a second transparent substrate and is arranged between the first transparent substrate and the second transparent substrate. A window material comprising the described electrochromic element and an active element connected to the electrochromic element.

Images