JP2018024624A - Organic compound, and electrochromic element, optical film, lens unit, and imaging device having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic compound that shows yellow in a colored state, has high transparency in a decolorized state and high reversibility of redox reaction, allows reduced power consumption, and has an electrochromic function.SOLUTION: The present invention provides an organic compound represented by formula (1) [R-Rindependently represent H, halogen, alkyl, alkoxy or the like. X and Y are alkyl, alkoxy, aryl, aralkyl or heteroaryl; Aand Aare anions].SELECTED DRAWING: Figure 4

Description

  The present invention relates to an organic compound, and an electrochromic element, an optical film, a lens unit, and an imaging device having the organic compound.

  An electrochromic element is an element having a pair of electrodes and an electrochromic layer disposed therebetween, and the transmittance of light transmitted through the element can be changed by an oxidation-reduction reaction at the electrodes.

  Various materials are known as electrochromic (hereinafter sometimes abbreviated as “EC”) materials in which the properties of optical absorption (colored state and light transmittance) of substances change due to electrochemical redox reactions. ing. Known organic EC materials include conductive polymers such as polythiophene and polyaniline, and organic low-molecular compounds such as oligothiophene.

  Examples of the organic low-molecular EC compound include a viologen derivative that is colored by reduction (cathodic compound), a phenazine derivative that is colored by oxidation (anodic compound), and the like.

  In Patent Documents 1 to 3, an organic compound of the following structural formula A having a phenylene group between two pyridines, an organic compound of the following structural formula B having a pyrazylene group between two pyridines, and between the two pyridines An organic compound of the following structural formula C having a pyrimidylene group is described. These are organic compounds in which the absorption wavelength during reduction of viologen is increased.

Japanese Patent Laying-Open No. 2015-124228 JP2013-193991A US Patent Application Publication No. 2012-0069418 Specification

  The organic compounds described in Patent Documents 1 to 3 have room for improvement in at least one of the magnitude of the reduction potential, the stability against repeated redox, and the transparency during decoloring.

  The organic compound represented by Structural Formula A described in Patent Document 1 is an organic compound having a large absolute value of the reduction potential. When the absolute value of the reduction potential of the EC compound is large, the power consumption of the organic EC element having it is large.

  The organic compound represented by Structural Formula B described in Patent Documents 2 and 3 is an organic compound having low stability against repeated redox. This is because these organic compounds have low stability in a colored state. The same applies to an organic compound having a pyridazylene group between two pyridines.

  The organic compound represented by Structural Formula C described in Patent Document 3 is an organic compound having low transparency during decoloring.

  This is because a planar structure is easily formed between the pyrimidylene group and the pyridine ring.

  An object of the present invention is to provide an organic compound having a small absolute value of a reduction potential, high stability against repeated redox, and high transmittance during decoloring.

  Therefore, the present invention provides an organic compound represented by the following general formula (1).

In the general formula (1), R _{1 to} R ₁₁ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, substituted Alternatively, each is independently selected from an unsubstituted aralkyl group. In R _{1 to} R ₁₁ , adjacent substituents may be bonded to each other to form a ring.

  When the aryl group or the aralkyl group has a substituent, the substituent is selected from a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, and an aralkyl group. It is.

  In the general formula (1), X and Y are an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, Each is independently selected from a substituted or unsubstituted heteroaryl group.

When the aryl group, the aralkyl group and the hetaryl group have a substituent, the substituent is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, Selected from aralkyl groups. A ₁ ⁻ and A ₂ ⁻ represent anions.

  ADVANTAGE OF THE INVENTION According to this invention, the absolute value of a reduction potential is small, the stability with respect to repetition of oxidation reduction is high, and the organic compound with the high transmittance | permeability at the time of decoloring can be provided.

It is the ultraviolet-visible absorption spectrum of the coloring state of Example Compound B-1, and the ultraviolet-visible absorption spectrum of a decoloring state. It is a cross-sectional schematic diagram of an example of the electrochromic element which concerns on this embodiment. It is a cross-sectional schematic diagram of the lens unit which concerns on this embodiment. It is a cross-sectional schematic diagram of the imaging device which concerns on this embodiment.

  The organic compound according to the present invention is an organic compound having electrochromic properties (EC properties). Since it has a structure represented by the following general formula (1), it has the properties that the absolute value of the reduction potential is small, the stability against repeated redox is high, and the transmittance during decoloring is high. The organic compound represented by the general formula (1) has an absorption band near 500 nm in the reduced state (colored state) and shows yellow.

  Here, the EC property is a property in which the property of optical absorption (colored state and light transmittance) of a substance is changed by an electrochemical redox reaction. The color tone to be changed can be controlled by the type of wavelength of light whose transmittance changes. In this embodiment, coloring means that the transmittance at a specific wavelength is lowered. In the present embodiment, the organic compound having EC property is also referred to as an electrochromic compound (EC compound).

  The organic compound according to the present invention is an electrochromic compound represented by the following general formula (1).

In the general formula (1), R _{1 to} R ₁₁ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, substituted Alternatively, each is independently selected from an unsubstituted aralkyl group. In R _{1 to} R ₁₁ , adjacent substituents may be bonded to each other to form a ring.

  When the aryl group or the aralkyl group has a substituent, the substituent is selected from a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, and an aralkyl group. It is.

  In the general formula (1), X and Y are an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, Each is independently selected from a substituted or unsubstituted heteroaryl group.

When the aryl group, the aralkyl group and the hetaryl group have a substituent, the substituent is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, Selected from aralkyl groups. A ₁ ⁻ and A ₂ ⁻ represent anions.

Examples of the halogen atom represented by R _{1 to} R ₁₁ include fluorine, chlorine, bromine and iodine.

The alkyl group represented by R _{1 to} R ₁₁ may be linear, branched or cyclic. Further, a hydrogen atom may be replaced with a fluorine atom or an ester group, and a methyl group may be replaced with a cyano group. Specific examples 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.

  Moreover, the terminal of the alkyl group may have an adsorptive group for adsorbing to an electrode such as a porous electrode. Specific examples of the adsorbing group include a carboxyl group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, and a trialkoxysilyl group.

The alkoxy group represented by R _{1 to} R ₁₁ may be linear, branched or cyclic. Further, a hydrogen atom may be replaced with a fluorine atom. Specific examples 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 aryl groups represented by R _{1 to} R ₁₁ are phenyl group, biphenyl group, terphenyl group, fluorenyl group, naphthyl group, fluoranthenyl group, anthryl group, phenanthryl group, pyrenyl group, tetracenyl group, pentacenyl group, triphenylenyl. Group, perylenyl group and the like.

Examples of the aralkyl group which may have a substituent represented by R _{1 to} R ₁₁ include a benzyl group and a phenethyl group.

The substituents represented by R _{1 to} R ₁₁ may be bonded to each other to form a ring. The ring formed may be monocyclic or polycyclic. Preferably, a benzene ring and a pyridine ring are mentioned. The organic compound represented by the general formula (1) becomes an organic compound having quinoline or naphthyridine by forming a benzene ring or a pyridine ring as described above.

The alkyl group, alkoxy group, aryl group, and aralkyl group represented by X and Y in the general formula (1) are the same as the specific examples represented by R _{1 to} R ₁₁ .

  Examples of the heteroaryl group represented by X and Y include a pyridyl group and a pyrimidyl group.

The aryl group, aralkyl group and heteroaryl group represented by the above R _{1 to} R _11, X or Y may have a substituent. These substituents include methyl groups, ethyl groups, propyl groups, isopropyl groups, tertiary butyl groups, cyclohexyl groups and other alkyl groups, benzyl groups, phenethyl groups and other aralkyl groups, phenyl groups, biphenyl groups and other aryl groups, and thienyls. Group, pyrrolyl group, hetaryl group such as pyridyl group, dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group, ditolylamino group, dianisolylamino group and other substituted amino groups, methoxyl group, ethoxyl group, propoxyl Groups such as alkoxyl groups, aryloxyl groups such as phenoxyl groups, aralkyl groups such as benzyl groups and phenethyl groups, acyl groups such as acetyl groups and benzoyl groups, ester groups such as methyl ester groups and ethyl ester groups, fluorine, chlorine , Halogen atoms such as bromine and iodine, Group, and the like.

A ₁ ⁻ and A ₂ ⁻ are anions such as PF ₆ ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , and Br ^{-, Cl -,} I ^- selected from a halogen anion such as. Preferably, it is selected from BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ^−, and may be the same or different. A ₁ ⁻ and A ₂ ⁻ are preferably the same anion.

  Although there is no restriction | limiting in particular about the method of manufacturing the organic compound which concerns on this invention, For example, it can manufacture by the method shown below. Here, the three pyridines in the general formula (1) may be referred to as a tricyclic structure.

  When X and Y are an alkyl group, an alkoxy group, and an aralkyl group, the organic compound represented by the general formula (1) first contains an organic compound (intermediate 1) represented by the following general formula (2) and a halide. The reaction is carried out in a predetermined solvent. Here, although there is no restriction | limiting in particular about a solvent, Polar solvents, such as acetonitrile and N, N- dimethylformamide, are preferable.

  Thereafter, it can be obtained by an anion exchange reaction with a salt containing a desired anion in a predetermined solvent. Here, it is preferable to use a solvent that can dissolve both the halogen compound and the salt containing the desired anion.

  When X and Y are aryl groups, it can be obtained by reacting with 2,4-dinitrophenyl halide, then reacting with arylamine, and anion exchange reaction with a salt containing an anion in a predetermined solvent.

  When X and Y are heteroaryl groups, they are reacted with a halide having a heteroaryl group in an alcohol solvent. Thereafter, it can be obtained by an anion exchange reaction with a salt containing a desired anion in a predetermined solvent. In these reactions, by selecting a solvent and a reaction temperature, only one of the imines outside the tricyclic structure can be reacted. By repeating the reaction, the remaining two imines of the tricyclic structure can be provided with the same substituent or different substituents.

  Although the manufacturing method of the intermediate body 1 does not have a restriction | limiting in particular, For example, it can manufacture by the method shown below. An example of the synthesis route for intermediate 1 is shown below.

R _{1 to} R ₉ in the synthesis route of the intermediate 1 represent the same substituents as in the general formula (1). Intermediate 1 is a coupling reaction between a halogenated pyridine having substituents R ₃ , R ₄ and R ₉ and 4-pyridylboronic acid having substituents R ₁ , R ₂ , R ₇ and R ₈ . _after, it can be synthesized by coupling reaction of 4-pyridyl boronic acid having a substituent group _{R 5, R 6, R 10} , R 11.

  Specific structural formulas of the organic compound represented by the general formula (1) are exemplified below. However, the organic compound represented by the general formula (1) according to the present invention is not limited to these.

The organic compounds exemplified below are classified into groups A to C.
In the exemplary compounds of Group A, X and Y in the general formula are both alkyl groups.
In the exemplary compounds of Group B, X and Y in the general formula are both aralkyl groups.
In the exemplary compounds of Group C, X and Y are substituents different from each other. Especially, the compound whose X or Y is an aryl group and heteroaryl group can adjust the absorption wavelength at the time of coloring.

  Since the organic compound according to the present invention has a structure represented by the general formula (1), it is a compound having high transparency when dissolved in a solvent.

  The organic compound represented by the general formula (1) is a cathodic EC compound that is colored in a reduced state. That is, the organic compound represented by the general formula (1) undergoes an electrochemical redox reaction reversibly, and has optical absorption properties (colored state and light transmittance) in a reduced state and a neutral state. It is a compound that changes.

  The organic compound represented by the general formula (1) is preferably used for an electrochromic element (EC element) because it has high transparency during decoloring and high reversibility of the oxidation-reduction reaction and can reduce power consumption. Can do. The EC device having the organic compound according to the present invention has high durability stability and transparency during decoloring and low power consumption.

  The EC element according to this embodiment will be described below with reference to the drawings. The EC element according to the present embodiment is an element having a pair of electrodes and an electrochromic layer disposed between the pair of electrodes.

  FIG. 1 is a schematic cross-sectional view of an example of an EC element according to this embodiment. It is an EC element having a pair of transparent electrodes 11 and an EC layer 12 having an electrolyte disposed between the pair of electrodes and the EC organic compound according to the present invention. The distance between the electrodes of the pair of electrodes is constant by the spacer 13. In this EC element, a pair of electrodes is disposed between a pair of transparent substrates 10.

  The EC layer 12 includes the organic compound according to the present invention and an electrolyte. This EC layer may be a solid layer or a solution layer.

  If it is a solid layer, the EC layer may be a single layer. Multiple layers may be used. When the EC layer is composed of a plurality of layers, it may have a layer made of an EC compound and a layer made of an electrolyte. Moreover, you may have a some EC layer.

  When the EC layer is a solution layer, it can be formed by dissolving an EC compound in an electrolyte solution or the like. The electrolyte solution may have a plurality of types of EC compounds. The EC element according to this embodiment is preferably an EC element in which the EC layer is a solution.

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

  The electrolyte is not limited as long as it is an ion dissociable salt and has good solubility in a solvent and high compatibility in a solid electrolyte. Among them, 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 , LiBF ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiPF ₆ , LiI, NaI, NaClO ₄ , NaBF ₄ , NaAsF ₆ , alkali metal salts of Na, K such as KCl, 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 H 5) 4 NBr, Quaternary ammonium salts and cyclic quaternary ammonium salts such as (C ₂ H ₅ ) ₄ NClO ₄ and (n-C ₄ H ₉ ) ₄ NClO ₄ can be mentioned.

  The solvent for dissolving the EC organic compound and the electrolyte is not particularly limited as long as it can dissolve the EC organic compound and the electrolyte, but a solvent having polarity is particularly preferable.

  Specifically, water, methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, γ-butyrolactone, γ-valerolactone, sulfolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, acetonitrile, propiononitrile, benzonitrile, Organic polar solvents such as dimethylacetamide, methylpyrrolidinone, dioxolane and the like can be mentioned.

  Furthermore, the EC medium may further contain a polymer or a gelling agent to make it highly viscous or gelled.

  The polymer is not particularly limited, and examples thereof include polyacrylonitrile, carboxymethylcellulose, polyvinyl chloride, polyethylene oxide, polypropylene oxide, polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, polyester, and Nafion (registered trademark). It is done.

  Next, the transparent substrate and the transparent electrode will be described. As the transparent substrate 10, for example, colorless or colored glass, tempered glass, or the like is used, or a colorless or colored transparent resin is used. In the present embodiment, the term “transparent” means that the transmittance of visible light is 80% or more.

  Specific examples include polyethylene terephthalate, polyethylene naphthalate, polynorbornene, polyamide, polysulfone, polyether sulfone, polyether ether ketone, polyphenylene sulfide, polycarbonate, polyimide, and polymethyl methacrylate.

  Examples of the electrode material 11 include indium tin oxide alloy (ITO), fluorine-doped tin oxide (FTO), tin oxide (NESA), indium zinc oxide (IZO), silver oxide, vanadium oxide, molybdenum oxide, gold, silver, Examples thereof include metals such as platinum, copper, indium and chromium, metal oxides, silicon-based materials such as polycrystalline silicon and amorphous silicon, and carbon materials such as carbon black, graphite and glassy carbon.

  In addition, a conductive polymer whose conductivity is improved by doping treatment, for example, a polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyethylenedioxythiophene (PEDOT) and polystyrene sulfonic acid complex is also preferably used.

  Furthermore, you may have a porous electrode on an electrode. The porous electrode is preferably made of a material having a large surface area such as a porous shape having a fine pore on the surface and inside, a lot shape, and a wire shape.

  As the material for the porous electrode, for example, metal, metal oxide, carbon, or the like can be applied. 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.

  The spacer 13 is disposed between the pair of electrodes 11 and provides a space for accommodating the solution 12 having the EC organic compound of the present invention. Specifically, polyimide, polytetrafluoroethylene, fluororubber, epoxy resin, or the like can be used. With this spacer, the distance between the electrodes of the EC element can be maintained.

  The EC element according to the present embodiment may have a liquid inlet formed by a pair of electrodes and a spacer. After the composition having the EC organic compound is sealed from the liquid injection port, the injection port is covered with a sealing member, and further sealed with an adhesive or the like.

  The sealing member also plays a role of isolating the adhesive and the EC organic compound so as not to contact each other. The shape of the sealing member is preferably a tapered shape such as a wedge shape.

  In the EC element forming method according to this embodiment, for example, a liquid 12 containing an EC organic compound is injected into a gap provided between a pair of electrode substrates by a vacuum injection method, an atmospheric injection method, a meniscus method, or the like. The method of doing is mentioned.

  The EC element according to the present embodiment may include the organic compound according to the present invention and a second organic compound different from the organic compound. The second organic compound may be one type or a plurality of types, and may be a compound colored in an oxidized state, a compound colored in a reduced state, or both. In particular, it is preferable that a compound coloring in an oxidized state is included.

  The compound colored in the oxidized state is a compound whose visible light transmittance in the oxidized state is lower than the visible light transmittance in the reduced state. A compound colored in an oxidized state can also be referred to as an anodic compound.

  Examples of the anodic compound include phenazine compounds, ferrocene compounds, metallocene compounds, phenylenediamine compounds, and pyrazoline compounds.

  The organic compound according to the present invention can absorb a desired color as an EC element by being combined with coloring materials of other colors. The absorption wavelength region of other EC compounds at the time of coloring is preferably in the range of 400 nm to 800 nm, more preferably 420 nm to 700 nm. By combining a plurality of the materials of the present invention and other materials, an EC element that absorbs the entire visible region and is colored black can be manufactured.

  Examples of other EC compounds according to this embodiment include the following compounds.

  Other EC compounds colored in the oxidized state include phenazine compounds such as 5,10-dihydro-5,10-dimethylphenazine and 5,10-dihydro-5,10-diethylphenazine, ferrocene, tetra-t-butyl. Examples thereof include metallocene compounds such as ferrocene and titanocene, phenylenediamine compounds such as N, N ′, N, N′-tetramethyl-p-phenylenediamine, and pyrarizone compounds such as 1-phenyl-2-pyrazoline.

  Examples of compounds colored in the 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'-di Benzylbipyridinium ditetrafluoroborate, N, N′-dibenzylbipyridinium dihexafluorophosphate, N, N′-diphenylbipyridinium diperchlorate, N, N′-diphenylbipyridinium ditetrafluoroborate, , N′-diphenylbipyridinium dihexafluorophosphate and other viologen compounds, 2-ethylanthraquinone, 2-t-butylanthraquinone, anthraquinone compounds such as octamethylanthraquinone, ferrocenium tetrafluoroborate, ferrocenium hexafluorophosphate And ferrocenium salt compounds, styryl compounds, and the like.

  The EC element according to this embodiment can be used for an optical filter, a lens unit, and an imaging device. The optical filter includes an EC element according to this embodiment and an active element connected to the EC element.

  The lens unit includes an optical unit having a plurality of lenses and an EC element. The EC element may be disposed outside the lens unit or may be disposed between the lenses. The arrangement position is not limited as long as the amount of light passing through the lens unit is controlled by the EC element.

  The imaging apparatus includes an optical unit having a plurality of lenses, an imaging element that receives light that has passed through the optical unit, and an EC element. The arrangement position is not limited as long as the amount of light received by the image sensor is controlled by the EC element. The imaging device may be an imaging device having an optical filter, an imaging element that receives light that has passed through the optical filter, and a housing that houses the optical filter and the imaging element. The housing includes a joint portion to which an optical unit having a plurality of lenses is attached.

  FIG. 2 is a schematic diagram illustrating the imaging apparatus of the present embodiment. The imaging apparatus of the present embodiment includes a lens unit 102 and an imaging unit 103, and the lens unit 102 is detachably connected to the imaging unit 103 via a mount member (not shown).

  The lens unit 102 is a unit having a plurality of lenses or lens groups, and is a rear focus type zoom lens that performs focusing after the stop.

  The lens unit 102 includes four lens groups, an aperture stop 108, and an optical filter 101. The four lens groups are, in order from the object side, a first lens group 104 having a positive refractive power, a second lens group 105 having a negative refractive power, a third lens group 106 having a positive refractive power, and a positive refractive power. The fourth lens group 107 is arranged. The aperture stop is disposed between the second lens group 105 and the third lens group 106. The optical filter is disposed between the third lens group 106 and the fourth lens group 107.

  By performing zooming by changing the distance between the second lens group 105 and the third lens group 106, focusing is performed by moving a part of the fourth lens group 107. The light passing through the lens unit is arranged to pass through the first to fourth lens groups, the aperture stop, and the optical filter, and the amount of light can be adjusted using the aperture stop and the optical filter.

  The imaging 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. The glass block may not be made of glass as long as it optically fulfills the above purpose.

  The image sensor 110 is a sensor unit that receives light that has passed through the lens unit 102. The sensor unit may include an optical sensor such as a photodiode. In addition, it is possible to appropriately use information that acquires and outputs information on light intensity or wavelength. The sensor unit may be connected to a signal processing unit such as a CCD or a CMOS.

  In the imaging device of the present embodiment, the optical filter 101 is disposed between the third lens group and the fourth lens group in the optical lens unit.

  The position of the optical filter 101 in the imaging apparatus according to the present embodiment is not limited to the position shown in the figure. For example, it may be arranged either before or after the aperture stop 108, or before any one of the first to fourth lens groups, between the lens groups. In addition, there exists an advantage that the area of an optical filter can be made small by arrange | positioning in the position where light converges.

  Further, in the imaging apparatus according to the present embodiment, the form of the lens unit can also be selected as appropriate. In addition to the rear focus type, an inner focus type that performs focusing before the aperture may be used, or other types may be used. Good. In addition to the zoom lens, a special lens such as a fisheye lens or a macro lens can be selected as appropriate.

  In FIG. 2, the optical filter 101 is disposed inside the lens unit 102. In the imaging apparatus according to the present embodiment, the EC element may be included in the lens unit, and the driving device for the EC element may be disposed outside the lens unit, for example, in the imaging unit. In such a case, the EC element in the lens unit and the drive device for the EC element are connected through the wiring to control driving.

  FIG. 3 is a schematic diagram of an imaging apparatus having a configuration in which the optical filter 101 is arranged inside the imaging unit 103.

  The optical filter 101 is disposed between the glass block 109 and the light receiving element 110 inside the imaging unit 103. When the imaging unit 103 itself includes the optical filter 101, the lens unit 102 to be connected does not need to have an optical filter, so that a dimmable imaging device using an existing lens unit can be configured.

  In FIG. 3, the optical filter 101 is disposed between the light receiving element 110 and the glass block 109. The image sensor 110 is an element that receives light that has passed through the optical filter 101. The optical filter 101 may be disposed at a position other than between the light receiving element 110 and the glass block 109 as long as it can control the amount of light received by the imaging element.

  Examples of such an imaging device 103 include a product having a combination of light amount adjustment and a light receiving element. For example, in an imaging part such as a camera, a digital camera, a video camera, a digital video camera, a mobile phone, a smartphone, a PC, or a tablet. There may be.

Example 1
<Synthesis of Exemplary Compound A-1>

  In the synthesis of Example Compound A-1, first, Intermediate 2 was synthesized. In a reaction vessel, 2,5-dibromopyridine (1.02 g, 4.3 mmol), 4-pyridylboronic acid (1.58 g, 12.9 mmol), tetrakis (triphenylphosphine) palladium (0.25 g, 0.22 mmol). ), Potassium carbonate (1.78 g, 12.9 mmol), dioxane (100 ml), and water (33 ml) were charged, and the mixture was stirred by heating under reflux for 8 hours under a nitrogen stream. After completion of the reaction, the reaction solution was concentrated. Thereafter, extraction was performed with chloroform. The organic layer was washed with water, dried over magnesium sulfate and then dried under reduced pressure. After purification by silica gel column chromatography (eluent: chloroform / methanol = 19/1), recrystallization was performed with ethanol / hexane to obtain 0.80 g of intermediate 2 (yield: 79.6%).

The structure of Intermediate 2 was confirmed by NMR measurement.
¹ H NMR (CDCl ₃ , 500 MHz) σ (ppm): 9.10 (s, 1H), 8.75 (m, 4H), 8.08 (m, 1H), 7.95 (m, 3H), 7.55 (m, 2H).

  Next, intermediate 3 was synthesized using intermediate 2. A reaction vessel was charged with Intermediate 2 (0.70 g, 3.00 mmol), 1-iodoheptane (3.39 g, 15.0 mmol), and 15 ml of N, N-dimethylformamide, and heated under reflux for 10 hours under a nitrogen stream. Stirring was performed. After completion of the reaction, the reaction solution was added dropwise to ethyl acetate, and the resulting precipitate was washed with ethyl acetate to obtain 1.50 g of intermediate 3 (yield: 73%).

The structure of intermediate 3 was confirmed by NMR measurement.
¹ H NMR (DMSO-d6,500 MHz) σ (ppm): 9.51 (d, 1H), 9.21 (m, 4H), 8.88 (d, 2H), 8.79 (m, 1H) , 8.70 (m, 3H), 4.62 (m, 4H), 1.95 (m, 4H), 1.25 (m, 16H), 0.85 (t, 6H).

  Next, Example Compound A-1 was synthesized using Intermediate 3. First, Intermediate 3 (500 mg, 0.73 mmol) was dissolved in water. An aqueous ammonium hexafluorophosphate solution was added dropwise, and the mixture was stirred at room temperature for 3 hours. The precipitated crystals were filtered and washed successively with isopropyl alcohol and diethyl ether to obtain 500 mg (yield: 95%) of Exemplary Compound A-1.

The structure of Exemplified Compound A-1 was confirmed by NMR measurement.
¹ H NMR (DMSO-d6,500 MHz) σ (ppm): 9.53 (d, 1H), 9.24 (m, 4H), 8.85 (d, 2H), 8.81 (m, 1H) , 8.73 (m, 3H), 4.65 (m, 4H), 1.95 (m, 4H), 1.30 (m, 16H), 0.85 (t, 6H).

  Under the following conditions, the oxidation-reduction potential of Exemplified Compound A-1 was measured. In addition, stability against repeated redox was evaluated.

The electrodes provided in the measuring apparatus and the solvents used are shown below.
Working electrode: Glassy carbon Counter electrode: Platinum reference electrode: Silver electrolyte: Tetrabutylammonium hexafluorophosphate propylene carbonate solution (0.1M)

  First, tetrabutylammonium hexafluorophosphate as an electrolyte was dissolved in propylene carbonate at a concentration of 0.1M. Then, Exemplified Compound A-1 was dissolved at a concentration of 0.5 mM to obtain an EC medium.

  Next, the redox potential of the EC compound was measured by cyclic voltammetry (CV) using a measuring device equipped with a working electrode, a counter electrode, and a reference electrode. The reduction potential was evaluated using ferrocene as a reference substance.

  As a result of CV measurement, the reduction potential of Exemplified Compound A-1 was −1.26V.

  The stability against repeated redox was evaluated by the CV measurement and the cyclic voltammogram shape.

  Evaluation of stability against repeated redox is “reversible” or “irreversible”. “Reversible” indicates high stability, and “irreversible” indicates low stability.

  A compound that showed good CV properties for repeated redox reactions was defined as “reversible”. Specifically, the IV characteristic does not substantially change even after repeated redox.

  On the other hand, compounds in which the areas on the oxidation side and the reduction side with respect to the baseline are different, or a compound in which the current value changes every cycle are defined as “irreversible”.

  Exemplified Compound A-1 exhibited reversible CV characteristics.

(Example 2)
<Synthesis of Exemplary Compound B-1>

  Exemplary Compound B-1 was synthesized using Intermediate 2. First, Intermediate 4 was synthesized using Intermediate 2. A reaction vessel was charged with intermediate 2 (0.60 g, 2.57 mmol), methyl 4- (bromomethyl) benzoate (2.96 g, 12.9 mmol), and 10 ml of N, N-dimethylformamide. Stirring was performed with heating under reflux for an hour. After completion of the reaction, the reaction solution was added dropwise to ethyl acetate, and the resulting precipitate was washed with ethyl acetate to obtain 1.30 g of intermediate 3 (yield: 73%).

The structure of the exemplary compound intermediate 4 was confirmed by NMR measurement.
¹ H NMR (CD ₃ OD, 500 MHz) σ (ppm): 9.44 (d, 1H), 9.21 (d, 4H), 8.92 (d, 2H), 8.69 (m, 1H) , 8.61 (m, 3H), 8.12 (d, 4H), 7.63 (d, 4H), 5.98 (s, 4H), 3.91 (s, 6H).

  Next, Example Compound B-1 was synthesized using Intermediate 4. First, Intermediate 4 (500 mg, 0.72 mmol) was dissolved in water. An aqueous ammonium hexafluorophosphate solution was added dropwise, and the mixture was stirred at room temperature for 3 hours. The precipitated crystals were filtered and washed successively with isopropyl alcohol and diethyl ether to obtain 500 mg (yield: 84%) of Exemplary Compound B-1.

The structure of exemplary compound B-1 was confirmed by NMR measurement.
¹ H NMR (CD3CN, 500 MHz) σ (ppm): 9.27 (d, 1H), 8.85 (d, 4H), 8.71 (d, 2H), 8.49 (m, 1H), 8 .39 (m, 3H), 8.08 (d, 4H), 7.56 (d, 4H), 5.82 (s, 4H), 3.86 (s, 6H).

  Measurement of the reduction potential of Exemplified Compound B-1 and stability against repeated redox were evaluated under the same conditions as Exemplified Compound A-1.

  An EC medium was obtained by replacing Exemplified Compound A-1 with Exemplified Compound B-1.

  As a result of CV measurement, the reduction potential of Exemplified Compound B-1 was -1.09V. Exemplified compound B-1 exhibited reversible CV characteristics.

(Example 3)
In this example, an EC element having an organic compound represented by the general formula (1) was produced, and its characteristics were evaluated. In this example, two types of devices having the example compound A-1 and the device having the example compound B-1 were produced as EC compounds. EC medium was obtained by dissolving tetrabutylammonium perchlorate as an electrolyte in propylene carbonate (propylene carbonate) at a concentration of 0.1 M, and then dissolving Exemplified Compound A-1 at a concentration of 40.0 mM. In addition, another type of EC medium was prepared by replacing Exemplified Compound A-1 with B-1.

In the EC element, a glass substrate with a transparent conductive film (transparent electrode film) as the electrode 11 was used as the substrate 10. An insulating layer (SiO ₂ ) was formed on the four ends of the glass substrate with a pair of transparent conductive films (ITO). A PET film (Melinex (registered trademark) S manufactured by Teijin DuPont Films, 125 μm thick) as a spacer for defining the substrate interval is placed between a pair of glass substrates with a transparent electrode film. Thereafter, the glass substrate and the PET film were adhered and sealed with an epoxy adhesive leaving an injection port for injecting the EC medium. As described above, an empty cell with an injection port was produced.

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

  When a voltage of 1.5 V was applied to the EC element of this example, the absorption derived from the reduced species of the organic compound contained in the EC element was shown. Furthermore, when a voltage of −0.5 V was applied, the color was erased, and reversibly colored and erased. That is, the EC element of this embodiment can reversibly change between a colored state and a decolored state, and has EC properties.

  In FIG. 4, the ultraviolet visible absorption spectrum in the coloring state and decoloring state of EC element produced using the exemplary compound B-1 of a present Example was shown. Exemplified Compound B-1 showed absorption at 506 nm and yellow in the reduced state. Similarly, Exemplified Compound A-1 also showed an absorption at 500 nm in the reduced state and showed yellow.

  Next, the absorption edge in the neutral state (decolored state) of the EC device prepared using Exemplified Compound A-1 and Exemplified Compound B-1 was investigated. The absorption edge is defined as the point appearing on the longest wavelength side among the points where the absorbance of the compound becomes 0 after the absorption peak appears in the decolored spectrum. The absorption edges of Exemplified Compound A-1 and Exemplified Compound B-1 were 387 nm and 385 nm, respectively. A compound having an absorption edge of less than 400 nm has high transparency when decolored.

(Comparative Example 1)
An EC device was produced in the same manner as in Example 3 except that Comparative Compound 1 represented by the following structure was used. Under the same conditions as in Example 3, the absorption in the reduced state and the absorption edge in the decolored state were measured. Comparative compound 1 is a compound in which a pyrimidylene group is introduced into a tricyclic structure.

  Comparative compound 1 in the reduced state showed absorption at 510 nm and developed yellow as in the case of exemplary compounds A-1 and B-1. However, the absorption edge of Comparative Compound 1 was 428 nm, and the absorption edge was made longer than that of Exemplary Compounds A-1 and B-1. A compound having an absorption edge of 428 nm has low transparency when decolored.

  In the case of having a pyridylene group as in Exemplified Compound A-1 and Exemplified Compound B-1, the hydrogen atom of the pyridylene group and the hydrogen atom of the outer pyridine ring are sterically repelled, so that the pyridylene group and both pyridine rings Twist occurs between the two. On the other hand, when it has a pyrimidylene group as in Comparative Compound 1, there is no repulsion between hydrogen atoms between the pyrimidylene group and the pyridine ring bonded to the carbon atom sandwiched between the heteroatoms of the pyrimidylene group, and twisting occurs. do not do.

  Exemplified Compound A-1 and Exemplified Compound B-1 are considered to be highly transparent because the pyridylene group twists with both outer pyridine rings and loses its planarity, thereby shortening the absorption edge.

  As described above, the organic compound according to the present invention is a compound having higher transparency during decoloring than Comparative Compound 1.

(Comparative Example 2)
Measurement was carried out in the same manner as in Example 1 except that the following comparative compound 2 was used instead of the exemplified compound A-1. Comparative compound 2 is a compound in which a pyradylene group is introduced at the center of the tricyclic structure.

  The reduction potential of Comparative Compound 2 was −0.93 V, which was more positively shifted than that of Exemplary Compound B-1 due to the influence of the hetero atom of the pyrazylene group. Comparative compound 2 had irreversible CV characteristics and low stability against repeated redox.

(Comparative Example 3)
Measurement was carried out in the same manner as in Example 1 except that the following comparative compound 3 was used instead of the exemplified compound A-1. Comparative compound 3 is a compound in which a pyridazylene group is introduced at the center of the tricyclic structure.

  The reduction potential of Comparative Compound 3 was −0.98 V, which was more positively shifted than Example Compound B-1 due to the influence of the hetero atom of the pyridazylene group. Comparative compound 3 had irreversible CV characteristics and low stability against repeated oxidation and reduction.

(Comparative Example 4)
Measurement was carried out in the same manner as in Example 1 except that the following comparative compound 4 was used instead of the exemplified compound A-1. Comparative compound 4 is a compound in which a phenylene group is introduced at the center of the tricyclic structure.

  Comparative compound 4 exhibited good CV characteristics and high stability against repeated redox. The reduction potential of Comparative Compound 4 was −1.22 V, which was more negative than that of Exemplary Compound B-1 (−1.09 V).

  This is considered due to the introduction of a phenylene group, which is an arylene group having an electron density higher than that of a heteroarylene group.

  Since the reduction potential of the comparative compound 4 is more negative than the organic compound according to the present invention, the comparative compound 4 is a compound that consumes a large amount of power for reducing the compound, that is, for coloring.

  As described above, the organic compound according to the present invention is an organic compound having a small absolute value of the reduction potential, high stability against repeated redox, and high transmittance during decoloring. The EC element having the organic compound of the present invention is an element having a long element life and low power consumption.

10 Transparent substrate 11 Transparent electrode 12 Liquid containing EC compound 13 Spacer

Claims (14)

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

In the general formula (1), R _{1 to} R ₁₁ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, substituted Alternatively, each is independently selected from an unsubstituted aralkyl group. In R _{1 to} R ₁₁ , adjacent substituents may be bonded to each other to form a ring.
When the aryl group or the aralkyl group has a substituent, the substituent is selected from a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, and an aralkyl group. It is.
In the general formula (1), X and Y are an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, Each is independently selected from a substituted or unsubstituted heteroaryl group.
When the aryl group, the aralkyl group and the hetaryl group have a substituent, the substituent is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, Selected from aralkyl groups. A ₁ ⁻ and A ₂ ⁻ represent anions.   2. The organic compound according to claim 1, which has an absorption peak in a range of 400 nm to 800 nm in a reduced state. In the general formula (1), the alkyl group from _{R 1 R 11,} the alkoxy group of _{R 1} to _{R 11,} the aryl group of _{R 1} to _{R 11,} the aralkyl group of _{R 1} to _{R 11} is a substituent And the substituent is independently selected from a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, and an aralkyl group. Item 3. The organic compound according to Item 1 or 2.   In the general formula (1), when the alkyl group represented by X and Y and the aryl group represented by X and Y have a substituent, the substituent is a halogen atom, an alkyl having 1 to 6 carbon atoms. The organic compound according to any one of claims 1 to 3, wherein the organic compound is independently selected from a group, an alkoxy group having 1 to 6 carbon atoms, an aryl group, and an aralkyl group. The organic compound according to any one of claims 1 to 4, wherein the A ₁ ^- and the A ₂ ^- are the same anion. A pair of electrodes, and an electrochromic layer disposed between the pair of electrodes,
The electrochromic layer is characterized in that the electrochromic layer contains the organic compound according to any one of claims 1 to 5.   The electrochromic device according to claim 6, wherein the electrochromic layer includes an organic compound different from the organic compound.   The electrochromic device according to claim 6 or 7, wherein the different kind of organic compound is any one of a phenazine compound, a ferrocene compound, a metallocene compound, a phenylenediamine compound, and a pyrazoline compound.   The electrochromic device according to claim 6, wherein the electrochromic layer is a liquid having an electrolyte and the organic compound. The electrochromic device according to any one of claims 6 to 9,
And an active element connected to the electrochromic element.   The optical filter according to claim 10, wherein the active element adjusts an amount of light passing through the electrochromic element by driving the electrochromic element. An optical filter according to claim 10 or 11,
And an optical unit having a plurality of lenses. An optical unit having a plurality of lenses;
An optical filter according to claim 10 or 11,
An imaging device comprising: an imaging device that receives light that has passed through the optical filter. An image pickup apparatus comprising: the optical filter according to claim 10; an image pickup device that receives light that has passed through the optical filter; and a housing that houses the optical filter and the image pickup device.
The imaging apparatus according to claim 1, wherein the housing includes a joint portion to which an optical unit having a plurality of lenses is attached.

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