WO2020004085A1 - Composé organique, élément électrochromique, filtre optique, unité de lentille, élément d'imagerie et fenêtre ayant ledit composé organique - Google Patents

Composé organique, élément électrochromique, filtre optique, unité de lentille, élément d'imagerie et fenêtre ayant ledit composé organique Download PDF

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WO2020004085A1
WO2020004085A1 PCT/JP2019/023738 JP2019023738W WO2020004085A1 WO 2020004085 A1 WO2020004085 A1 WO 2020004085A1 JP 2019023738 W JP2019023738 W JP 2019023738W WO 2020004085 A1 WO2020004085 A1 WO 2020004085A1
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substituent
electrochromic
group
organic compound
compound
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PCT/JP2019/023738
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English (en)
Japanese (ja)
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井川　悟史
山田　憲司
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キヤノン株式会社
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Priority claimed from JP2019084741A external-priority patent/JP7446719B2/ja
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Publication of WO2020004085A1 publication Critical patent/WO2020004085A1/fr
Priority to US17/129,068 priority Critical patent/US11940704B2/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
    • E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect

Definitions

  • the present invention relates to an electrochromic organic compound and an electrochromic device, an optical filter, a lens unit, an imaging device, and a window having the same.
  • Electrochromic (hereinafter sometimes abbreviated as “EC”) materials whose optical absorption properties (colored state and light transmittance) change due to electrochemical oxidation-reduction reactions are inorganic materials and organic polymers Various materials such as materials and organic low molecular weight materials are known.
  • low molecular organic EC materials include viologen derivatives which are colored by reduction (cathodic compounds) and oligothiophene derivatives which are colored by oxidation (anodic compounds).
  • a light control mirror for an automobile, electronic paper, and the like have been proposed.
  • These EC elements utilize the characteristic that various color tones can be displayed by selecting a material.
  • materials having various color tones can be applied to a wide range of applications.
  • a material that colors cyan, magenta, and yellow is required.
  • an EC material having various absorption wavelengths at the time of coloring is required. Therefore, an organic EC material capable of performing various color designs by molecular design has attracted attention.
  • Patent Document 1 describes that an organic compound of the following structural formula C-1 in which a benzene ring is bonded between two pyridine rings has light absorption at 570 nm during reductive coloring.
  • Patent Document 2 describes that an organic compound of the following structural formula C-2 has light absorption near 470 nm at the time of reductive coloring.
  • the electrochromic compounds described in Patent Literature 1 and Patent Literature 2 describe compounds that absorb light having a wavelength of 570 nm and compounds that absorb light having a wavelength of 600 nm when colored.
  • As one of the techniques for changing the absorption wavelength range at the time of coloring there is a technique for increasing or decreasing the ring structure in order to change the conjugate structure of the bipyridinium salt skeleton of the chemical structure.
  • an electrochromic compound having absorption at 450 to 540 nm has not been obtained simply by increasing or decreasing the ring structure.
  • the present invention has been made in view of the above problems, and has as its object to provide a cathodic electrochromic compound that absorbs light having a wavelength of 450 to 540 nm during coloring.
  • One embodiment of the present invention provides an organic compound represented by the following general formula [1].
  • Z 1 and Z 2 are each independently selected from an alkyl group which may have a substituent, an aryl group which may have a substituent, and an aralkyl group which may have a substituent. .
  • R 11 to R 17 are each independently selected from a hydrogen atom and a substituent.
  • the substituent may have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is either a heterocyclic group or a halogen atom.
  • R 21 and R 22 are each independently selected from a hydrogen atom and a substituent.
  • the substituent is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
  • Y 1 to Y 3 are each independently selected from a carbon atom, an N atom, and (N + -L) (X ⁇ ).
  • L is any of an alkyl group, an aryl group and an aralkyl group which may have a substituent.
  • a cathodic electrochromic compound that absorbs light having a wavelength of 450 to 540 nm during coloring can be provided.
  • FIG. 2 is a schematic diagram illustrating an example of a driving device connected to the electrochromic element according to the embodiment.
  • FIG. 1 is a schematic diagram illustrating an example of an imaging device according to an embodiment.
  • FIG. 1 is a schematic diagram illustrating an example of an imaging device according to an embodiment. It is a schematic diagram which shows an example of the window material which concerns on embodiment. It is a schematic diagram which shows an example of the window material which concerns on embodiment.
  • FIG. 13 is a view showing a transmittance spectrum of Exemplified Compound A-20 in Example 7 in a decolored state and a colored state.
  • 14 is an ultraviolet-visible absorption spectrum of the device produced in Example 11.
  • 9 is a transmittance spectrum in a decolored state and a colored state (reduced state) of Exemplified Compound B-20.
  • One embodiment of the present invention is an organic compound having electrochromic properties, which is an organic compound represented by the general formula [1].
  • Z 1 and Z 2 are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, and an aralkyl group which may have a substituent.
  • Z 1 and Z 2 are preferably an aryl group which may have a substituent.
  • the aryl group may be, for example, a phenyl group or a naphthyl group, and preferably has an alkyl group as a substituent.
  • This alkyl group may be substituted at the para-position to the basic skeleton of the general formula [1]. Further, the alkyl group may be substituted at the ortho position with respect to the basic skeleton of the general formula [1].
  • the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms.
  • the basic skeleton refers to a structure in which Z 1 , Z 2 , R 11 to R 17 , R 21 and R 22 are all hydrogen atoms in the general formula [1].
  • the organic compound according to one embodiment of the present invention may be present together with a counter ion.
  • a counter ion Assuming that the counter ion is X ⁇ , it is represented by the following general formula [2].
  • R 11 to R 17 are each independently selected from a hydrogen atom and a substituent.
  • the substituent is an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or Any of halogen atoms.
  • R 16 and R 17 may combine with each other to form a ring.
  • R 21 and R 22 are each independently selected from a hydrogen atom and a substituent. These substituents are any of an alkyl group which may have a substituent, an aryl group which may have a substituent, and an aralkyl group which may have a substituent.
  • Y 1 to Y 3 are each independently selected from a carbon atom, an N atom, and (N + -L) (X ⁇ ).
  • L is any of an alkyl group, an aryl group and an aralkyl group which may have a substituent.
  • Y 1 and Y 2 may be represented by an N atom or (N + -L) (X ⁇ ), and Y 3 may be a carbon atom. Further, Y 1 may be an N atom or (N + -L) (X ⁇ ), and the other two may be carbon atoms. Y 1 to Y 3 may be all carbon atoms.
  • the alkyl group represented by Z 1 and Z 2 , R 11 to R 17 , R 21 and R 22 preferably has 1 to 8 carbon atoms, and may be linear, branched or cyclic. Further, a hydrogen atom may be replaced by a fluorine atom. Further, the carbon atom of the alkyl group may be replaced by an ester group or a cyano group.
  • alkyl group 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.
  • the terminal of the alkyl group represented by Z 1 and Z 2 may have an adsorbing group for adsorbing to the porous electrode or an acid ester group thereof.
  • the adsorptive group or its acid ester group include a carboxyl group and a carboxylester group, a sulfonic acid group and a sulfonic acid ester group, a phosphonic acid group and a phosphonic acid ester group, and a trialkoxysilyl group.
  • the terminal of the alkyl group may have a polar group such as a hydroxyl group or an amino group, or an ionic group such as ammonium, pyridinium, and quinolinium.
  • the aryl group represented by Z 1 and Z 2 , R 11 to R 17 , R 21 and R 22 is, for example, a phenyl group, a biphenyl group, a tolyl group, a fluorenyl group, a naphthyl group, a fluoranthenyl group, an anthryl group, Examples include a phenanthryl group, a pyrenyl group, and a perylenyl group. Preferably it is a phenyl group.
  • aryl group (heterocyclic group) containing a hetero atom examples include a pyridyl group, a thienyl group, an oxazolyl group, an oxadiazolyl group, a thiazolyl group, a thiadiazolyl group, and an indolyl group.
  • a pyridyl group Preferably it is a pyridyl group.
  • the aryl group has a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, an aralkyl group, a hydroxyl group, a substituted amino group, and a substituted silyl group as substituents. You may.
  • the hydrogen atom of the alkyl group or the alkoxy group may be replaced by a halogen atom, preferably a fluorine atom.
  • the aryl group represented by Z 1 and Z 2 has an alkyl group or an alkoxy group
  • its terminal may have an adsorption group for adsorbing to the porous electrode or an acid ester group thereof, It may have an ionic group in order to improve solubility in an organic solvent.
  • Adsorptive group or its ester group specific examples of the ionic group are the same as those mentioned in the alkyl groups represented by Z 1 and Z 2.
  • the aralkyl group represented by Z 1 and Z 2 , R 21 and R 22 includes a benzyl group, a phenethyl group and the like.
  • the aralkyl group may have a substituent, and specifically may have an alkyl group having 1 to 8 carbon atoms and an alkoxy group having 1 to 8 carbon atoms.
  • the hydrogen atom of the alkyl group or the alkoxy group may be replaced by a halogen atom, preferably a fluorine atom.
  • the aralkyl group represented by Z 1 and Z 2 has an alkyl group or an alkoxy group
  • its terminal may have an adsorbing group for adsorbing to the porous electrode or an acid ester group thereof, It may have an ionic group in order to improve solubility in an organic solvent.
  • Adsorptive group or its ester group specific examples of the ionic group are the same as those mentioned in the alkyl groups represented by Z 1 and Z 2.
  • the alkoxy groups represented by R 11 to R 17 may be linear, branched, or cyclic. This alkoxy group preferably has 1 to 8 carbon atoms. Further, a hydrogen atom of the alkoxy group may be replaced by a halogen atom.
  • a methoxy group, an ethoxy group and an isopropoxy group are particularly preferred.
  • halogen atom represented by R 11 to R 17 examples include fluorine, chlorine, bromine, iodine, and the like.
  • Y 1 to Y 3 are each independently selected from a carbon atom, an N atom, and (N + -L) (X ⁇ ).
  • L is any of an alkyl group, an aryl group and an aralkyl group which may have a substituent. Specific examples of the alkyl group, aryl group and aralkyl group represented by L are the same as the examples of the alkyl group, aryl group and aralkyl group represented by Z 1 and Z 2 .
  • anion represented by X ⁇ examples include anions such as PF 6 ⁇ , ClO 4 ⁇ , BF 4 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , CF 3 SO 3 ⁇ , and (CF 3 SO 2 ) 2 N ⁇ . It is selected from halogen anions such as Br ⁇ , Cl ⁇ and I ⁇ . Preferably PF 6 -, ClO 4 -, BF 4 -, CF 3 SO 3 -, (CF 3 SO 2) 2 N - is either. When a plurality of X - are included, they may be the same or different.
  • the method for producing the organic compound according to one embodiment of the present invention is not particularly limited, but for example, it can be produced by the following method.
  • Z 1 and Z 2 are an alkyl group and an aralkyl group
  • the compound represented by the general formula [1] is reacted with an organic compound represented by the following general formula [2] and a halide in a predetermined solvent.
  • an anion exchange reaction can be performed with a salt containing a desired anion in a predetermined solvent.
  • Z 1 and Z 2 are aryl groups
  • an organic compound represented by the general formula [3] is reacted with 2,4-dinitrophenyl halide, and X 1 and X 2 are 2,4-dinitrophenyl groups.
  • the compound can be reacted with an arylamine and subjected to an anion exchange reaction with a salt containing an anion in a predetermined solvent.
  • an anion exchange reaction with a salt containing an anion in a predetermined solvent.
  • a solvent and a reaction temperature only one imine can be reacted. By repeating the reaction, it is also possible to introduce different substituents into two imines.
  • the production method of the general formula [3] is not particularly limited, but for example, it can be produced according to the following production method as an example.
  • Intermediate 1 can be synthesized by coupling an N, N-diethylnicotinamide derivative with a 4-halogeno-pyridylpyridine derivative.
  • the intermediate 2 can be synthesized by cyclizing the intermediate 1 using LDA (lithium diisopropylamide).
  • intermediate 3 can be synthesized by reducing Wolff-Kishner intermediate 2.
  • the organic compound represented by the general formula [3] can be synthesized by reacting the intermediate 3 with a desired alkyl halide in the presence of a base.
  • Y 1 to Y 3 are each independently selected from a carbon atom, an N atom, and (N + -L) (X ⁇ ). In any case, the compound can be synthesized by the above reaction route.
  • Compounds shown in Group A among the exemplified compounds are compounds in which Y 1 to Y 3 in the general formula [1] are all carbon atoms.
  • one of Y 1 to Y 3 in the general formula [1] is represented by N atom or (N + -L) (X ⁇ ), and the remaining two are carbon atoms. It is a structure consisting of
  • 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] is a compound whose properties of optical absorption (coloration state and light transmittance) change due to reversible electrochemical redox reaction. .
  • the organic compound according to one embodiment of the present invention has the structure represented by the general formula [1], it can absorb light having a wavelength of 450 to 540 nm during coloring.
  • the compound preferably has a low LUMO (lowest unoccupied orbital) level.
  • a low LUMO level can mean that the LUMO level is deep, farther from the vacuum level, and that the absolute value of LUMO is large.
  • the cathodic EC compound represented by the general formula [1] includes a heterocyclic ring in which a central aromatic ring connecting two pyridine rings contains an N atom. For this reason, the electron density is reduced, and the LUMO is stabilized (deep), so that electrons can be easily injected, that is, the reduction potential shifts in the positive direction.
  • the organic compounds (B-4, B-20, B-21) and (C-1, C-2, C-2) according to an embodiment of the present invention are compared.
  • -3) and Reference Example Compounds (Ref-1, Ref-2, Ref-3) were verified by molecular orbital calculation.
  • Compounds (B-4, B-20, B-21) have a single pyridine ring in which the N atom of the central aromatic ring is one, and compounds (C-1, C-2, C-3) have a central aromatic ring.
  • the N atom of the aromatic ring is two pyrazine rings.
  • the comparative compounds (Ref-1, Ref-2, Ref-3) are benzene rings in which the central aromatic ring does not contain an N atom, and the other chemical structures are the same as those of the organic compound according to one embodiment of the present invention ( B-4, B-20, B-21) and (C-1, C-2, C-3).
  • the reduction potentials determined from the molecular orbital calculations are summarized in Tables 1 to 3 below.
  • the reduction potentials of the compounds (B-4, B-20, B-21) and (C-1, C-2, C-3) according to one embodiment of the present invention are as follows. In each case, it was confirmed that the positive potential was shifted from the reduction potential of the reference compound (Ref-1, Ref-2, Ref-3).
  • the organic compound according to one embodiment of the present invention can contribute to lowering the voltage of the EC device than the reference compound.
  • the molecular orbital calculation was performed using Gaussian 03 * Revision D. This is a result of performing a ground state structure optimization calculation using 01. At that time, Density Functional Theory was adopted as a quantum chemical calculation method, and B3LYP was used as a functional.
  • the basis functions are Gaussian 03, Revision D. In 01, 6-31G * was used.
  • the organic compound according to one embodiment of the present invention can be used as an EC layer of an electrochromic device.
  • the EC device shown in FIG. 1 is an EC device having a pair of transparent electrodes 11 and an EC layer 12 having an electrolyte and an EC organic compound according to the present invention disposed between the pair of electrodes.
  • the distance between the electrodes of the pair of electrodes is fixed by the sealing material 13.
  • a pair of electrodes is arranged between a pair of transparent substrates 10.
  • the EC layer 12 has the organic compound according to the present invention.
  • the EC layer may have a layer made of an EC compound and a layer made of an electrolyte. Further, an EC layer may be provided as a solution containing an EC compound and an electrolyte.
  • the EC device according to the present embodiment is preferably an EC device in which the EC layer is a solution layer.
  • the electrolyte is not limited as long as it is an ion-dissociable salt, has good solubility in a solvent, and shows 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.
  • electrolyte examples include inorganic ion salts such as various alkali metal salts and alkaline earth metal salts, and quaternary ammonium salts and cyclic quaternary ammonium salts.
  • the solvent for dissolving the EC organic compound and the electrolyte is not particularly limited as long as the solvent can dissolve the EC organic compound and the electrolyte, but a polar solvent is particularly preferable.
  • the EC medium may further contain a polymer or a gelling agent to use a highly viscous one or a gelled one.
  • These polymers and gelling agents can also be called thickeners.
  • the EC solution preferably has a thickener.
  • the viscosity of the EC solution may be between 10 and 5000 cP, and between 50 and 1000 cP.
  • the viscosity of the EC solution may be 150 cP or less, preferably 100 cP or less, more preferably 65 cP or less. Further, 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 weight of the electrochromic layer is 100 wt%. Preferably it is 1 wt% or more and 15 wt% or less, more preferably 5 wt% or more and 10 wt% or less.
  • the polymer is not particularly limited and includes, for example, polyacrylonitrile, carboxymethylcellulose, polyvinyl chloride, polyethylene oxide, polypropylene oxide, polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, polyester, Nafion (registered trademark) and the like.
  • polyacrylonitrile carboxymethylcellulose
  • polyvinyl chloride polyethylene oxide
  • polypropylene oxide polyurethane
  • polyacrylate polymethacrylate
  • polyamide polyacrylamide
  • polyester Nafion (registered trademark) and the like.
  • the transparent substrate and the transparent electrode will be described.
  • the transparent substrate 10 for example, a colorless or colored glass, a tempered glass, or the like, or a colorless or colored transparent resin is used.
  • “transparent” indicates that the visible light transmittance is 70% or more.
  • polyethylene terephthalate polyethylene naphthalate, polynorbornene, polyamide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylenesulfide, polycarbonate, polyimide, polymethylmethacrylate, and the like can be given.
  • 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,
  • ITO indium tin oxide alloy
  • FTO fluorine-doped tin oxide
  • NESA tin oxide
  • IZO indium zinc oxide
  • silver oxide vanadium oxide, molybdenum oxide
  • gold silver
  • Examples 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.
  • a conductive polymer whose conductivity is improved by doping treatment or the like for example, polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, a complex of polyethylenedioxythiophene (PEDOT) and polystyrenesulfonic acid, and the like are suitably used.
  • PEDOT polyethylenedioxythiophene
  • the sealing material 13 is preferably used to hold the EC layer between the pair of electrodes and to keep the distance between the electrodes.
  • the sealing material 13 may have a function of maintaining the distance between the electrodes by, for example, containing a spacer material.
  • the sealing material 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.
  • the sealing material 13 is preferably a material that is chemically stable, hardly permeates gas and liquid, and does not inhibit the oxidation-reduction reaction of the EC compound.
  • an inorganic material such as a glass frit, a thermosetting or photocurable material such as an epoxy resin or an acrylic resin, polyimide, polytetrafluoroethylene, and fluororubber can be used.
  • the EC element according to the present embodiment may have a liquid injection port formed by a pair of electrodes and a spacer. After enclosing the composition having the EC organic 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 obtain an element.
  • the sealing member also has a role of isolating the adhesive and the EC organic compound so as not to come into contact with each other.
  • the method for forming the EC element according to this embodiment is not particularly limited, and a liquid containing an EC organic compound prepared in advance by a vacuum injection method, an air injection method, a meniscus method, or the like in a gap provided between a pair of electrodes. 12 can be used.
  • Each of the pair of electrodes may be an electrode substrate in which the electrode and the substrate are integrated.
  • the EC device 1 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 an anodic EC compound that is colored in an oxidized state, a cathodic EC compound that is colored in a reduced state, or a compound having both properties. Since the organic compound according to the present invention is a compound that is colored in a reduced state, the second organic compound is preferably an anodic EC compound that is colored in an oxidized state.
  • the electrochromic layer may have a structure in which the absorption spectrum is made nearly flat by having four or more kinds of electrochromic compounds.
  • the anodic EC compound that is colored in an oxidized state is a compound having a visible light transmittance in an oxidized state lower than that in a reduced state. It is sufficient that the transmittance of any of the visible light regions is changed, and the transmittance of the entire visible light region does not need to be changed.
  • a third organic compound may be further contained.
  • the third organic compound may be an anodic EC compound or a cathodic EC compound.
  • the absorption wavelength region of other EC compounds when decoloring is preferably 400 nm or less when decoloring. This is because an element having high transparency at the time of decoloring can be provided.
  • the absorption wavelength range during coloring is preferably in the range of 400 nm to 800 nm, more preferably 400 nm to 450 nm, or 600 nm to 700 nm.
  • an EC element having another EC compound absorbs light in the visible light region uniformly at each wavelength.
  • EC compounds according to the present embodiment include, for example, compounds having the following structural formula.
  • EC compounds that color in an oxidized state include oligothiophenes, phenazine-based compounds such as 5,10-dihydro-5,10-dimethylphenazine, 5,10-dihydro-5,10-diisopropylphenazine, ferrocene, and tetraphenylene.
  • Metallocene compounds such as -t-butylferrocene and titanocene
  • phenylenediamine compounds such as N, N ', N, N'-tetramethyl-p-phenylenediamine
  • pyrazoline compounds such as 1-phenyl-2-pyrazoline, etc. Is mentioned.
  • Compounds that are 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'
  • the phenazine-based compound is a compound having a 5,10-dihydro-phenazine skeleton in a chemical structure.
  • Phenazine-based compounds include compounds having a substituent on 5,10-dihydrophenazine.
  • the hydrogen atoms at positions 5 and 10 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, a compound having an alkoxy group having 1 to 20 carbon atoms in 5,10-dihydrophenazine may be used. Further, a compound having an aryl group having 4 to 60 carbon atoms in 5,10-dihydrophenazine may be used. The same applies to other compounds, for example, viologen compounds.
  • the compound contained in the EC layer 12 of the EC device 1 according to the present embodiment can be confirmed to be contained in the EC device 1 by extracting and analyzing the compound by a known method. For example, extraction by chromatography and analysis by NMR can be mentioned. When the electrochromic layer is a solid, it can be analyzed by TOF-SIMS or the like.
  • the EC device according to the present embodiment has high transparency at the time of decoloring, gives high optical density at the time of coloring, and can reduce the transmittance, and greatly reduces the amount of light incident on an imaging device such as a camera. It can be suitably used when performing.
  • the EC element 1 according to the present embodiment can be used for an optical filter, a lens unit, an imaging device, a window material, and the like. Further, by providing the EC element according to the present embodiment and the light reflecting member having the EC element on the light reflecting surface, an electrochromic mirror can be obtained.
  • the light reflecting member may also serve as an electrode and a substrate.
  • the optical filter according to one embodiment of the present invention has an EC element 1 and an active element connected to the EC element 1.
  • the active element is an active element that drives the electrochromic element and adjusts the amount of light passing through the electrochromic element.
  • Examples of the active element include a transistor and an MIM element.
  • the transistor may include an oxide semiconductor such as InGaZnO in the active region.
  • the optical filter has the EC device 1 according to the present embodiment and a driving device connected to the EC device 1.
  • FIG. 2 is a schematic diagram illustrating an example of the driving device 20 of the EC device 1 and the EC device 1 driven by the driving device 20.
  • the drive device 20 for the EC element 1 according to the present embodiment includes a drive power supply 8, a resistance switch 9, and a controller 7.
  • the drive power supply 8 applies a voltage necessary for the EC material included in the EC layer 12 to cause an electrochemical reaction to the EC element 1.
  • a method suitable for the element to be used is adopted. More specifically, a method of inputting a predetermined condition to the EC element 1 with respect to a desired transmittance setting value, or a setting value by comparing the transmittance setting value with the transmittance of the EC element 1 There is a method of selecting and inputting a condition so as to match a value.
  • the parameters to be changed include a voltage, a current, and a duty ratio.
  • the controller 7 increases or decreases the voltage for the voltage control method, the current for the current control method, or the duty ratio for the pulse width modulation method to the EC element 1, thereby increasing or decreasing the corresponding EC.
  • the coloring density of the device can be increased or decreased, and consequently the incident light can be reduced or increased.
  • the resistance switch 9 switches between a resistor R1 (not shown) and a resistor R2 larger than the resistor R1 in a closed circuit including the drive power supply 8 and the EC element 1, and connects them in series.
  • the resistance value of the resistor R1 is preferably at least smaller than the largest impedance of the element closed circuit, and is preferably 10 ⁇ or less.
  • the resistance value of the resistor R2 is preferably larger than the largest impedance of the element closed circuit, and is preferably 1 M ⁇ or more.
  • the resistor R2 may be air. In this case, the closed circuit is strictly an open circuit, but it can be considered as a closed circuit by regarding the air as the resistance R2.
  • the controller 7 sends a switching signal to the resistance switch 9 to control the switching between the resistors R1 and R2.
  • the lens unit according to the present embodiment has a plurality of lenses and an optical filter having the EC element 1.
  • the optical filter may be provided between the plurality of lenses or outside the lenses.
  • the optical filter is preferably provided on the optical axis of the lens.
  • the imaging device includes an optical filter and a light receiving element that receives light that has passed through the optical filter.
  • the imaging device include a camera, a video camera, a camera-equipped mobile phone, and the like.
  • the imaging device may have a form in which a main body having a light receiving element and a lens unit having a lens can be separated.
  • the imaging device when the imaging device can be separated by the main body and the lens unit, a mode in which an optical filter separate from the imaging device is used at the time of imaging is also included in the present invention.
  • 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. 3 is a schematic diagram illustrating an example of a configuration of an imaging device 100 using the optical filter of the present embodiment.
  • the imaging device 100 is an imaging device including the lens unit 102 and the imaging unit 103.
  • the lens unit 102 includes the optical filter 101 and an imaging optical system having a plurality of lenses or lens groups.
  • the optical filter 101 is the above-described optical filter of the present embodiment.
  • the lens unit 102 represents, for example, a rear focus type zoom lens that performs focusing after the stop in FIG. 3A.
  • a first lens group 104 having a positive refractive power 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 fourth lens group having a positive refractive power It has 107 lens groups. Zooming is performed by changing the distance between the second lens group 105 and the third lens group 106, and focusing is performed by moving a part of the fourth lens group 107.
  • the lens unit 102 has, for example, an aperture stop 108 between the second lens group 105 and the third lens group 106, and has an aperture stop 108 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 of the lens groups 104 to 107, the stop 108, and the optical filter 101, so that the light amount can be adjusted using the aperture stop 108 and the optical filter 101.
  • the lens unit 102 is detachably connected to the imaging unit 103 via a mount member (not shown).
  • the optical filter 101 is disposed between the third lens group 106 and the fourth lens group 107 in the lens unit 101, but the imaging device 100 is not limited to this configuration.
  • the optical filter 101 may be located either before (subject side) or after the aperture stop 108 (on the imaging unit 103 side), or before 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 light converges, there is an advantage that the area of the optical filter 101 can be reduced.
  • the configuration of the lens unit 102 is not limited to the above-described configuration, and can be appropriately selected.
  • an inner focus type in which focusing is performed before the stop may be used, or another type may be used.
  • a special lens such as a fisheye lens or a macro lens can be appropriately selected.
  • the imaging unit 103 has a glass block 109 and a light receiving element 110.
  • the glass block 109 is a glass block such as a low-pass filter, a face plate, and a color filter.
  • the light receiving element 110 is a sensor unit that receives light that has passed through the lens unit, and an imaging element such as a CCD or a CMOS can be used. Also, an optical sensor such as a photodiode may be used, and a sensor that acquires and outputs information on light intensity or wavelength may be used as appropriate.
  • the driving device may be arranged inside the lens unit 102 or outside the lens unit 102.
  • the drive is controlled by connecting the EC device 1 in the lens unit 102 and the driving device through wiring.
  • the optical filter 101 is disposed inside the lens unit 102.
  • the present invention is not limited to this mode, and the optical filter 101 may be arranged at an appropriate location inside the imaging device 100, and the light receiving element 110 may be arranged to receive light passing through the optical filter 101.
  • FIG. 3B is a schematic diagram of an example of an imaging device in which an optical filter is arranged in the imaging device.
  • the imaging unit 103 has the optical filter 101.
  • the optical filter 101 is disposed immediately before the light receiving element 110.
  • the lens unit 102 to be connected does not have to have the optical filter 101, so that a dimmable imaging device using the existing lens unit 102 can be configured. It becomes possible.
  • the imaging device 100 of the present embodiment is applicable to a product having a combination of light quantity adjustment and a light receiving element.
  • a camera can be used for a camera, a digital camera, a video camera, a digital video camera, and also applicable to a product having a built-in imaging device such as a mobile phone, a smartphone, a PC, and a tablet.
  • FIG. 4A is a schematic view showing a window using the EC element 1 according to the present embodiment
  • FIG. 4B is a schematic view showing a cross-sectional view taken along line X-X ′ of FIG. 4A.
  • the light control window 111 of the present invention includes the 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 optical filter has a driving device (not shown), and the driving 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 has a high light transmittance, and is preferably a glass material in consideration of use as a window.
  • the material of the frame 112 is not limited, but a resin such as polycarbonate, acrylonitrile butadiene styrene, polyalkylene furandicarboxylate, polylactic acid, polybutadiene terephthalate, or a mixture thereof may be used.
  • a resin such as polycarbonate, acrylonitrile butadiene styrene, polyalkylene furandicarboxylate, polylactic acid, polybutadiene terephthalate, or a mixture thereof may be used.
  • the frame may be any frame that covers at least a part of the optical filter and has an integrated form.
  • the EC element 1 is a component independent of the transparent plate 113.
  • the transparent substrate 10 of the EC element 1 may be regarded as the transparent plate 113.
  • Such a dimming window can be applied, for example, to an application for adjusting the amount of daylight sunlight entering a room. Since the present invention can be applied not only to the adjustment of the amount of heat but also the amount of heat of the sun, it can be used for controlling the brightness and temperature of a room. Also, the shutter can be applied to an application that blocks a view from the outside to the room. Such a light control window can be applied to a window of a vehicle such as an automobile, a train, an airplane, and a ship, in addition to a glass window for a building.
  • the electrochromic device may be used for an electrochromic mirror provided on a moving body such as an automobile.
  • the electrochromic mirror has a light reflecting member that reflects light dropped on the electrochromic element.
  • the EC element 1 including 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 imaging device, a window material, and the like.
  • Each of the optical filter, the lens unit, the imaging device, and the window material of the present embodiment can be variously formed by combining the organic compound represented by the general formula [1] alone or an EC compound having colored absorption in another wavelength band. It is possible to provide an excellent absorption color.
  • the imaging device 100 of the present embodiment by using the optical filter 101 as a light control member, it is possible to appropriately change the light control amount with a single filter, thereby reducing the number of members and saving space. There are advantages.
  • reaction solution was added to saturated aqueous sodium hydrogen carbonate, extracted with ethyl acetate, the organic layers were combined, washed sequentially with water and saturated saline, dried over anhydrous sodium sulfate and concentrated to obtain a black-yellow solid.
  • N, N-diethylnicotinamide (5.35 g, 30 mmol), triisopropyl borate (7.6 ml, 33 mmol) and tetrahydrofuran (25 ml) were charged and cooled to -50 ° C.
  • the previously prepared LDA solution was slowly dropped, and the mixture was stirred at 0 ° C. for 2 hours and concentrated under reduced pressure.
  • XX-1 (4.72 g, 30 mmol)
  • potassium phosphate (10.73 g, 75 mmol)
  • 1,4-dioxane / pure water 150 ml / 45 ml
  • Exemplified compound B-3 (261 mg, 0.41 mmol) was dissolved in water. An aqueous solution in which 320 mg of ammonium hexafluorophosphate was dissolved was added dropwise, and the mixture was stirred at room temperature for 3 hours. The precipitated crystals were filtered and washed successively with water, isopropyl alcohol, and diethyl ether to obtain 235 mg (yield: 85%) of Exemplified Compound B-4.
  • Exemplified compound B-4 (205 mg, 0.30 mmol) and dichloromethane (6 ml) were added to the reaction vessel, and further trimethyloxonium tetrafluoroborate (444 mg, 3.0 mmol) was added, followed by stirring at room temperature for 2 days. The precipitated solid was filtered and washed sequentially with dichloromethane, methanol and diethyl ether to obtain 75 mg of Exemplified Compound B-34 (yield: 30%).
  • Example 8 ⁇ Synthesis of Exemplified Compound B-6> XX-5 (104 mg, 0.38 mmol) synthesized in Example 5, bromoacetonitrile (228 mg, 1.90 mmol), and 4 ml of acetonitrile were added to the reaction vessel, and the mixture was heated at 90 ° C. and refluxed for 20 hours. . After completion of the reaction, the precipitated crystals were filtered and washed with ethyl acetate to obtain Exemplified Compound B-6 (140 mg, yield: 72%).
  • Exemplified Compound B-6 (140 mg, 0.27 mmol) was dissolved in 10 ml of water. An aqueous solution in which 160 mg of ammonium hexafluorophosphate was dissolved was added dropwise, and the mixture was stirred at room temperature for 3 hours. The precipitated crystals were filtered and washed successively with water, isopropyl alcohol and diethyl ether to obtain 120 mg of Exemplified Compound B-7 (yield: 69%). The structure of this compound was confirmed by NMR measurement.
  • Example 11 ⁇ Production of electrochromic device and evaluation of characteristics> As an electrolyte, tetrabutylammonium perchlorate was dissolved in propylene carbonate at a concentration of 0.1 M, and then Exemplified Compound A-20 of Example 2 was dissolved at a concentration of 40.0 mM to obtain an EC medium.
  • an insulating layer SiO 2
  • ITO transparent conductive films
  • a PET film (Melinex S (registered trademark, manufactured by Teijin DuPont Films, Inc., 125 ⁇ m thickness) that defines the substrate interval) was disposed between a pair of glass substrates with a transparent electrode film. Thereafter, the substrate and the PET film were bonded and sealed with an epoxy-based adhesive leaving an injection port for injecting the EC medium. As described above, an empty cell with an inlet was produced.
  • the EC medium obtained above was injected from the above-described injection port by a vacuum injection method, and the injection port was sealed with an epoxy-based adhesive to obtain an EC element.
  • the EC device immediately after fabrication exhibited a transmittance of about 80% over the entire visible light region, and had high transparency.
  • FIG. 5 is an ultraviolet-visible absorption spectrum of the device manufactured in Example 10.
  • a light source a DH-2000S deuterium, halogen light source manufactured by Ocean Optics was used.
  • Example 12 ⁇ Production of electrochromic device and evaluation of characteristics> A device was prepared in the same manner as in Example 11, except that Exemplified Compound A-18 was used instead of Exemplified Compound A-20.
  • FIG. 6 is an ultraviolet-visible absorption spectrum of the device produced in Example 12.
  • the measurement was performed using a solution in which the exemplified compound B-20 was dissolved (2.0 ⁇ 10 ⁇ 3 mol / L) in a propylene carbonate solution (0.1 mol / L) of tetrabutylammonium hexafluorophosphate as a supporting electrolyte. I went. This solution is placed in a glass cell having an optical path length of 1 mm, a mesh-shaped platinum electrode (working electrode) and a wire-shaped platinum electrode (counter electrode) are arranged, and a reference electrode RE (Ag / Ag + ) is arranged and measured. Was done.
  • the transmittance spectrum was measured using a transmitted light passing through a mesh electrode by performing a constant potential reduction on the solution at a reduction potential of the compound or higher.
  • a voltage was applied using a potentiostat (Cell Test 1470E) manufactured by Solartron, and a spectrometer (USB2000-UV-VIS) manufactured by Ocean Optics was used for spectroscopic measurement.
  • FIG. 7 shows transmittance spectra of Exemplified Compound B-20 in a decolored state and a colored state (reduced state).
  • Exemplified compound B-20 is a material having high transparency without absorption in the entire visible light region in the decolored state.
  • the transmittance changed in the visible region, and the wavelength ⁇ max of the absorption peak was 528 nm. This reduced coloring state returned to colorless and transparent again by oxidation, and reversible electrochromic characteristics associated with oxidation and reduction were confirmed.
  • the cathodic EC compound Ref-2 of the reference example is a compound having the same chemical structure except that the central pyridine ring of the exemplified compound B-20 is a benzene ring.
  • Ref-2 shows almost the same colored absorption wavelength ( ⁇ max to 536 nm) as the cathodic EC compound B-20 in the reduced state, but has a reduction potential of ⁇ 1.14 V, and is 150 mV more negative than the exemplary compound B-20. The reduction potential was indicated.
  • Table 4 The results are summarized in Table 4.
  • Example 14 ⁇ Evaluation of electrochromic characteristics> The measurement was carried out in the same manner as in Example 13, except that Exemplified Compound B-7 was used instead of Exemplified Compound B-20. The results are summarized in Table 4.
  • Example 15 ⁇ Evaluation of electrochromic characteristics> The measurement was carried out in the same manner as in Example 13, except that Exemplified Compound B-34 was used instead of Exemplified Compound B-20. The results are summarized in Table 4.
  • Example 16 ⁇ Evaluation of electrochromic characteristics> The measurement was carried out in the same manner as in Example 13, except that Exemplified Compound B-4 was used instead of Exemplified Compound B-20. The results are summarized in Table 4.
  • Example 17 ⁇ Preparation of electrochromic device and evaluation of characteristics>
  • Exemplified compound B-20 as a cathodic EC material and W-1 (5,10-diisopropyl-5,10-dihydrophenazine) having the following structure as an anodic EC material were dissolved in propylene carbonate at a concentration of 100 mM, respectively, and further increased.
  • An EC solution was prepared by adding 5 wt% of polymethyl methacrylate (PMMA) as a viscosity agent.
  • PMMA polymethyl methacrylate
  • two transparent conductive glasses on which an indium-doped tin oxide (ITO) film was formed were prepared, and arranged so that the ITO films faced each other.
  • the outer peripheries of the two transparent conductive glasses were bonded together using an epoxy-based sealing material in which spacer beads having a particle size of 50 ⁇ m were mixed.
  • a solution in which the anodic EC compound and the cathodic EC compound are dissolved is injected into the transparent conductive glass from an injection port formed in advance, so that the space formed by the two sheets of the transparent conductive glass and the sealing material is formed. was filled with the solution. Thereafter, the injection port was sealed with a UV-curable sealant to obtain an EC element.
  • the organic compound according to one embodiment of the present invention is a cathodic electrochromic compound that absorbs light having a wavelength of 450 to 540 nm when colored.
  • the present invention can be used for an EC element that absorbs light in this region, an optical filter using the same, a lens unit, an imaging device, and the like.

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Abstract

La présente invention concerne un composé organique caractérisé en ce qu'il est représenté par la formule générale [1]. Dans la formule, Z1 et Z2 sont chacun indépendamment choisis parmi des groupes alkyle éventuellement substitués, des groupes aryle éventuellement substitués, et des groupes aralkyle éventuellement substitués. R11 à R17, R21 et R22 sont chacun indépendamment choisis parmi un atome d'hydrogène ou un substituant. Y1 à Y3 sont chacun indépendamment choisis parmi un atome de carbone, un atome N, ou (N+-L)(X-). L est l'un quelconque d'un groupe alkyle, d'un groupe aryle ou d'un groupe aralkyle.
PCT/JP2019/023738 2018-06-28 2019-06-14 Composé organique, élément électrochromique, filtre optique, unité de lentille, élément d'imagerie et fenêtre ayant ledit composé organique WO2020004085A1 (fr)

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Citations (6)

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JPS62135474A (ja) * 1985-12-09 1987-06-18 Tokuyama Soda Co Ltd フオトクロミツク感光材料
WO2016147543A1 (fr) * 2015-03-13 2016-09-22 Ricoh Company, Ltd. Composé électrochromique, composition électrochromique, élément électrochromique et élément d'obscurcissement électrochromique
WO2017005824A1 (fr) * 2015-07-08 2017-01-12 Essilor International (Compagnie Generale D'optique) Composés électrochromes et articles optiques les contenant
WO2017154681A1 (fr) * 2016-03-10 2017-09-14 キヤノン株式会社 Composé organique, élément électrochromique, dispositif électrochromique, filtre optique, dispositif d'imagerie, unité de lentille et matériau de fenêtre
JP2017197477A (ja) * 2016-04-27 2017-11-02 キヤノン株式会社 有機化合物、及びそれを有するエレクトロクロミック素子、光学フィルタ、レンズユニット、撮像装置、窓材
JP2018024624A (ja) * 2016-08-12 2018-02-15 キヤノン株式会社 有機化合物及びそれを有するエレクトロクロミック素子、光学フィルム、レンズユニット、撮像装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62135474A (ja) * 1985-12-09 1987-06-18 Tokuyama Soda Co Ltd フオトクロミツク感光材料
WO2016147543A1 (fr) * 2015-03-13 2016-09-22 Ricoh Company, Ltd. Composé électrochromique, composition électrochromique, élément électrochromique et élément d'obscurcissement électrochromique
WO2017005824A1 (fr) * 2015-07-08 2017-01-12 Essilor International (Compagnie Generale D'optique) Composés électrochromes et articles optiques les contenant
WO2017154681A1 (fr) * 2016-03-10 2017-09-14 キヤノン株式会社 Composé organique, élément électrochromique, dispositif électrochromique, filtre optique, dispositif d'imagerie, unité de lentille et matériau de fenêtre
JP2017197477A (ja) * 2016-04-27 2017-11-02 キヤノン株式会社 有機化合物、及びそれを有するエレクトロクロミック素子、光学フィルタ、レンズユニット、撮像装置、窓材
JP2018024624A (ja) * 2016-08-12 2018-02-15 キヤノン株式会社 有機化合物及びそれを有するエレクトロクロミック素子、光学フィルム、レンズユニット、撮像装置

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