WO2019073789A1 - Electrochromic element, optical filter, lens unit, imaging device, and window material - Google Patents

Electrochromic element, optical filter, lens unit, imaging device, and window material Download PDF

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WO2019073789A1
WO2019073789A1 PCT/JP2018/035400 JP2018035400W WO2019073789A1 WO 2019073789 A1 WO2019073789 A1 WO 2019073789A1 JP 2018035400 W JP2018035400 W JP 2018035400W WO 2019073789 A1 WO2019073789 A1 WO 2019073789A1
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ec
compound
electrochromic
element
cathodic
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PCT/JP2018/035400
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French (fr)
Japanese (ja)
Inventor
亘 久保
山田 憲司
井川 悟史
祐斗 伊藤
功 河田
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キヤノン株式会社
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Priority to JP2017-196988 priority
Priority to JP2018-149516 priority
Priority to JP2018149516A priority patent/JP2019070788A/en
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Publication of WO2019073789A1 publication Critical patent/WO2019073789A1/en

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    • EFIXED CONSTRUCTIONS
    • E06DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06BFIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/66Units comprising two or more parallel glass or like panes permanently secured together
    • EFIXED CONSTRUCTIONS
    • E06DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06BFIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B9/00Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
    • E06B9/24Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
    • GPHYSICS
    • G02OPTICS
    • G02FDEVICES OR ARRANGEMENTS, THE OPTICAL OPERATION OF WHICH IS MODIFIED BY CHANGING THE OPTICAL PROPERTIES OF THE MEDIUM OF THE DEVICES OR ARRANGEMENTS FOR THE CONTROL OF THE INTENSITY, COLOUR, PHASE, POLARISATION OR DIRECTION OF LIGHT, e.g. SWITCHING, GATING, MODULATING OR DEMODULATING; TECHNIQUES OR PROCEDURES FOR THE OPERATION THEREOF; FREQUENCY-CHANGING; NON-LINEAR OPTICS; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/15Devices 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
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03BAPPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B11/00Filters or other obturators specially adapted for photographic purposes

Abstract

The present invention provides, as one example of an electrochromic (EC) element in which orthogonal colour separation is inhibited, an EC element provided with a pair of electrodes, a solvent, an anodic EC compound, and a cathodic EC compound. The EC element is characterized in that an anodic EC compound having an oxidized form for which the difference between the solvation free energy in water and the solvation free energy in octanol is 35 kcal/mol or higher, and a cathodic EC compound having a substituent including any element from among the halogens, sulfur, boron, phosphorus, and silicon, are used therein.

Description

Electrochromic element, optical filter, lens unit, imaging device, and window material

The present invention relates to an electrochromic device, an optical filter, a lens unit, an imaging device, and a window material.

A compound whose optical properties (absorption wavelength, absorbance, etc.) of a substance are changed by an electrochemical redox reaction is referred to as an electrochromic (hereinafter, "electrochromic" may be described as "EC") compound. EC devices using EC compounds are applied to display devices, variable reflectance mirrors, variable transmission windows, and the like.

Some EC devices use a solution layer containing an anodic EC compound colored by oxidation and a cathodic EC compound colored by reduction as the EC layer. The phenomenon that the anodic EC compound and the cathodic EC compound are separated in the EC layer when such an EC element is driven vertically for a long time so that the in-plane direction of the electrode of the EC element is vertical. Separation) may occur. When segregation occurs, the color components that make up the color of the colored EC element are separated, and the color of the EC element may be separated between vertically above and below (hereinafter referred to as "vertical color separation" Have to do).

Patent Document 1 describes an EC element in which the viscosity of a solution containing an EC compound is increased by using a thickener. By increasing the viscosity of the solution containing the EC compound, the migration of substances in the solution can be suppressed, and the occurrence of vertical color separation can be suppressed.

JP-A-10-138832

However, as in Patent Document 1, when the viscosity of the solution containing the EC compound is increased, the movement of the substance is suppressed even when changing the coloring state of the EC element. There is a risk of In addition, for example, when driving at a high coloring density for a long time, there are cases where suppression of vertical color separation is insufficient only by increasing the viscosity of the EC layer.

The present invention is directed to suppressing vertical color separation in an EC device with an EC compound. An electrochromic device as one aspect of the present invention has a first electrode, a second electrode, and an electrochromic layer disposed between the first electrode and the second electrode. An electrochromic device in which the electrochromic layer comprises a solvent, an anodic electrochromic compound and a cathodic electrochromic compound, and the cathodic electrochromic compound is halogen, sulfur, boron, phosphorus, silicon It has a substituent containing any one of the elements, and is characterized by satisfying the following formula (1).
G A + H2O -G A + OcOH ≧ 35 ··· formula (1)

(Wherein, in Formula (1), G A + H 2 O represents the solvation free energy (kcal / mol) in water of the oxidized form of the anodic electrochromic compound, and G A + OcOH is an oxidation of the anodic electrochromic compound Solvation free energy (kcal / mol) of the body in octanol.

According to the present invention, an EC device in which vertical color separation is suppressed can be provided.

It is a figure which shows an example of EC element typically. It is a figure showing the relationship between the solvation free energy difference of the oxidant of an anodic EC compound, and the degree of vertical color separation. It is a graph which shows the result of having measured the time-dependent change of vertical color separation about three kinds of EC elements which used the cathodic EC compound in which substituents differ, respectively. It is a figure for demonstrating the evaluation method of vertical color separation. It is a figure showing the relationship between the density | concentration of EC compound, and the extent of vertical color separation. It is a figure which shows an example of an imaging device and a lens unit typically. It is a figure which shows an example of an imaging device and a lens unit typically. It is a figure which shows an example of a window material typically. It is a figure which shows an example of a window material typically.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the following embodiments, and appropriate modifications may be made to the following embodiments based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Those to which improvements and the like have been added are also included in the scope of the present invention.

[Electrochromic device]
The EC element 1 according to the present embodiment will be described with reference to FIG. The EC element 1 takes in light from the outside and passes at least a part of the taken-in light to at least a part of the EC layer 12 to make the characteristic of the outgoing light, typically the intensity of the light, at least in a predetermined wavelength range. It is a device to be changed.

FIG. 1 is a view schematically showing the configuration of the EC element 1 according to the present embodiment. The EC element 1 of the present embodiment has a first electrode 11a, a second electrode 11b, and an electrochromic layer 12 disposed between the first electrode 11a and the second electrode 11b. doing. The electrochromic layer 12 has a solvent, an anodic EC compound, and a cathodic EC compound. The difference between the solvation free energy in water and the solvation free energy in octanol of the oxidized form of the anodic EC compound is 35 kcal / mol or more. The cathodic electrochromic compound has a substituent containing an element of any of halogen, sulfur, boron, phosphorus and silicon.

The difference between the solvation free energy and the solvation free energy in octanol is an indicator of the affinity to a solvent, such as hydrophobicity represented by a partition coefficient. If this value is 35 kcal / mol or more, it indicates that the affinity to the solvent is low, and if the solvent is water, it can be expressed as hydrophobic.

In addition, EC element of FIG. 1 is an example of EC element structure of this invention, and EC element of this invention is not limited to these. For example, a layer of an antireflective film may be provided between the substrate 10 and the electrode 11 or between the electrode 11 and the EC layer 12.

The components of the EC element 1 will be described below.

<Substrate 10>
The EC element 1 may have a substrate 10 (a first substrate 10a and a second substrate 10b). The substrate 10 is preferably a substrate (transparent substrate) at least one of which is transparent. The term "transparent" as used herein means that the light transmittance is 50% to 100%, more preferably 70% to 100%. Moreover, "light" in the present specification is light in a wavelength range to which the EC element is used. For example, if EC element is used as an optical filter of an imaging device in the visible light region, light of the visible light region is used, and if it is used as an optical filter of an imaging device in the infrared region, light of infrared region is used Say

Specifically, colorless or colored glass or transparent resin can be used as the substrate 10. Examples of the glass include optical glass, quartz glass, white plate glass, blue plate glass, borosilicate glass, non-alkali glass, chemically strengthened glass and the like. Examples of the transparent resin include polyethylene terephthalate, polyethylene naphthalate, polynorbornene, polyamide, polysulfone, polyether sulfone, polyether ether ketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate and the like.

<Electrode 11>
The constituent material of the electrode 11 (the first electrode 11a and the second electrode 11b) is stably present in the operating environment of the EC element 1 and causes the redox reaction to rapidly proceed in response to the application of an external voltage. Possible materials are preferably used. As a constituent material of the electrode 11, for example, a transparent conductive material, metal or the like described later can be used.

Preferably, at least one of the first electrode 11a and the second electrode 11b is a transparent electrode. The term "transparent" as used herein indicates that the light transmittance is 50% or more and 100% or less. Since at least one of the first electrode 11a and the second electrode 11b is a transparent electrode, light is efficiently taken in from the outside of the EC element 1, and interacts with the EC compound in the EC layer 12, The optical properties of the compound can be reflected in the emitted light.

As the transparent electrode, a film formed of a transparent conductive material on the substrate 10, a transparent electrode in which a metal wire is partially disposed on a transparent substrate, or the like can be used. Here, although the metal wires themselves are not transparent, those in which the light transmittance is in the above range by disposing the metal wires partially are referred to as transparent electrodes in the present invention.

Examples of transparent conductive materials include transparent conductive oxides and carbon materials such as carbon nanotubes. As transparent conductive oxides, for example, tin-doped indium oxide (ITO), zinc oxide, gallium-doped zinc oxide (GZO), aluminum-doped zinc oxide (AZO), tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), niobium-doped titanium oxide (TNO) and the like. Among these, FTO or ITO is preferable.

When forming the electrode 11 by a transparent conductive oxide, it is preferable that the film thickness of the electrode 11 is 10 nm or more and 10000 nm or less. In particular, by using FTO or ITO formed in a film thickness range of 10 nm or more and 10000 nm or less as the electrode 11, both high transparency and chemical stability can be achieved.

When the electrode 11 is formed of a transparent conductive oxide, the electrode 11 may have a structure in which sublayers of the transparent conductive oxide are stacked. This makes it easy to realize high conductivity and high transparency.

The metal as a constituent material of the electrode 11 is not particularly limited, but an electrochemically stable metal such as silver (Ag), gold (Au), platinum (Pt), titanium (Ti), etc. It is preferably used. In addition, a grid shape is preferably used as the arrangement pattern of the metal wires. The electrode having a metal wire is typically a flat electrode, but a curved electrode can also be used if necessary.

As described above, it is preferable that at least one of the first electrode 11a and the second electrode 11b is a transparent electrode, but when one electrode is a transparent electrode, the other electrode is used for the application of the EC element Depending on the situation, preferred ones can be selected. For example, in the case where the EC element is a transmission type EC element, both of the first electrode 11a and the second electrode 11b are preferably transparent electrodes. On the other hand, when the EC element is a reflection type EC element, one of the first electrode 11a and the second electrode 11b is a transparent electrode, and the other is an electrode that reflects light taken in by the EC element. Is preferred. Further, by forming a reflective layer or a scattering layer between the first electrode 11a and the second electrode 11b, the degree of freedom of the optical characteristics of the other electrode described above can be improved. For example, in the case where a reflective layer or a scattering layer is introduced between the first electrode 11a and the second electrode 11b, an opaque electrode or an electrode that absorbs the light of interest is used as the other electrode described above. It can also be used.

As the arrangement of the first electrode 11a and the second electrode 11b, an arrangement method generally known as an electrode arrangement of EC elements can be used. As a representative example, the first electrode 11a formed on the first substrate 10a and the second electrode 11b formed on the second substrate 10b are different from the first electrode 11a and the second electrode 11b. There is a method in which the electrodes 11b are disposed to face each other with the EC layer 12 interposed therebetween. At this time, the distance (inter-electrode distance) between the first electrode 11a and the second electrode 11b is preferably 1 μm to 500 μm, and more preferably 10 μm to 100 μm. By increasing the distance between the electrodes, the thickness of the EC layer 12 can be increased, and a sufficient amount of EC compound can be disposed in the EC layer 12 to function effectively as an EC element. As a result, it is advantageous in that the transmittance at the time of coloring can be easily lowered. On the other hand, reducing the distance between electrodes is advantageous in that the response speed of the EC element can be easily increased. As described above, by setting the inter-electrode distance to 10 μm or more and 100 μm or less, it becomes easy to realize low transmittance and quick response at the time of coloring.

<Sealing material>
The sealing material 13 is disposed between the first electrode 11a and the second electrode 11b, and bonds the first electrode 11a and the second electrode 11b.

The sealing material 13 is preferably made of a material that is chemically stable, hardly transmits gas and liquid, and does not inhibit the redox reaction of the EC compound. For example, inorganic materials such as glass frit, organic materials such as epoxy resin and acrylic resin, metals and the like can be used. The sealing material 13 may have a function of holding a distance between the first electrode 11a and the second electrode 11b by containing a spacer material or the like. In this case, a space for arranging the EC layer 12 between the electrodes can be formed by the first electrode 11 a, the second electrode 11 b, and the sealing material 13.

When the sealing material 13 does not have the function of defining the distance between the first electrode 11a and the second electrode 11b, a spacer having the function of defining and maintaining the distance between the two electrodes is separately disposed. The distance between the two electrodes may be maintained. As materials for the spacer, inorganic materials such as silica beads and glass fibers, and organic materials such as polyimide, polytetrafluoroethylene, polydivinylbenzene, fluororubber, epoxy resin and the like can be used.

<Electrochromic layer>
The EC layer 12 has a solvent, an anodic EC compound, and a cathodic EC compound. The EC layer 12 is preferably a solution layer in which the anodic EC compound and the cathodic EC compound are dissolved in a solvent. The EC layer 12 may further contain additives such as a supporting electrolyte and a thickener.

(solvent)
The solvent can be appropriately selected according to the application in consideration of the solubility of the solute such as the anodic EC compound and the cathodic EC compound to be used, the vapor pressure, the viscosity, the potential window and the like. As the solvent, those capable of dissolving the anodic EC compound and the cathodic EC compound to be used are preferable. Moreover, as a solvent, it is preferable that it is a solvent which has polarity. Specifically, organic polar solvents such as ether compounds, nitrile compounds, alcohol compounds, dimethylsulfoxide, dimethoxyethane, sulfolane, dimethylformamide, dimethylacetamide, methyl pyrrolidinone and the like, and water can be mentioned. Among these, solvents containing cyclic ethers such as propylene carbonate, ethylene carbonate, γ-butyrolactone, valerolactone and dioxolane are preferable. The solvent containing these cyclic ethers is preferable from the viewpoint of solubility of EC compound, boiling point, vapor pressure, viscosity and potential window. Among cyclic ethers, a solvent containing propylene carbonate is particularly preferred. Moreover, an ionic liquid can also be used as a solvent.

Moreover, a polymer, a gelling agent, and a thickener may be further contained in the above-mentioned solvent to increase the viscosity of the EC layer 12 or to make it into a gel. A polymer electrolyte or gel electrolyte may be used as the solvent or the electrolyte. The polymer is not particularly limited. For example, polyacrylonitrile, carboxymethylcellulose, polyvinyl chloride, polyethylene oxide, polypropylene oxide, polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, polyester, Nafion (registered trademark) And derivatives thereof. When the viscosity of the EC layer 12 is increased or gelled, the migration of the EC compound in the EC layer 12 is suppressed. This can further suppress the occurrence of vertical color separation.

The viscosity of the EC solution may be 10 cP or more and 5000 cP or less, and may be 50 cP or more and 1000 cP or less. The viscosity of the EC solution may be 150 cP or less, preferably 100 cP or less, and more preferably 65 cP or less. Moreover, 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, where the weight of the electrochromic layer is 100 wt%. Preferably, it is 1 wt% or more and 15 wt% or less, and more preferably 5 wt% or more and 10 wt% or less.

The EC layer 12 may further have a supporting electrolyte. The supporting electrolyte is not particularly limited as long as it is an ion dissociative salt and exhibits good solubility in a solvent. The supporting electrolyte is preferably a substance stable at the operating potential of the EC element 1. As the supporting electrolyte, a suitable one can be selected from various cations and anions, and a combination of both can be used. Examples of the cation include metal ions such as alkali metal ions and alkaline earth metal ions, and organic ions such as quaternary ammonium ions. Specific examples thereof include Li + , Na + , K + , Ca 2+ , Ba 2+ , tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium and the like. Examples of the anion include anions of various fluorine compounds, halide ions and the like. Specifically, ClO 4 , SCN , BF 4 , AsF 6 , CF 3 SO 3 , CF 3 SO 2 NSO 2 CF 3 , PF 6 , I , Br , and Cl are listed. Be In addition, by using a salt compound as the EC compound, the EC compound may also function as a supporting electrolyte. Examples of EC compounds that are also salt compounds include viologen derivatives and the like.

The method of forming the EC layer 12 is not particularly limited. For example, the solvent and EC may be formed by a vacuum injection method, an air injection method, a meniscus method, or the like in the gap provided between the first electrode 11a and the second electrode 11b. There may be mentioned a method of injecting a liquid containing the compound. Specifically, for example, a liquid containing a solvent and an EC compound is injected from an opening (not shown) formed in a part of the electrode 11 or the sealing material 13 into a cell formed of the pair of electrodes 11 and the sealing material 13 And the opening is sealed by the sealing member.

(EC compound)
In the present specification, the “EC compound” is a kind of oxidation-reduction substance, and is a compound whose optical characteristics change in the target light wavelength region of the EC element by the oxidation-reduction reaction. The optical properties include light absorption properties and light reflection properties, and are typically light absorption properties. The "redox substance" as used herein means a substance capable of causing a redox reaction repeatedly in a predetermined potential range. The EC compound can also be said to be a compound whose light transmittance changes in the light wavelength region targeted by the EC element by a redox reaction. Furthermore, “the optical characteristics change” mentioned here typically indicates that the light absorption state and the light transmission state are switched. In this case, the EC compound can also be said to be a compound that switches between the light absorption state and the light transmission state by the redox reaction.

In the present specification, the “anode EC compound” refers to an EC compound whose optical characteristics change in the target light wavelength region of the EC element due to an oxidation reaction when the EC element 1 is driven. The oxidation reaction is usually a reaction in which electrons are removed from the EC compound. Further, in the present specification, the “cathode type EC compound” refers to an EC compound whose optical characteristics change in the light wavelength region targeted by the EC element due to a reduction reaction when the EC element 1 is driven. The reduction reaction is usually a reaction in which electrons are imparted to the EC compound. As a typical example of the anodic EC compound, a compound which changes from the light transmitting state to the light absorbing state by the oxidation reaction when the EC element 1 is driven can be mentioned. Further, as a typical example of the cathodic EC compound, a compound which changes from the light transmitting state to the light absorbing state by the reduction reaction when the EC element 1 is driven can be mentioned. The present invention is not limited to this, and may be a compound which changes from the light absorption state to the light transmission state by an oxidation reaction or a reduction reaction when the EC element 1 is driven. In the following description, in order to make it easy to image changes in the light absorption characteristics of the EC compound, a typical example is the light transmission state (decoloring state) to the light absorption state when the EC element 1 is driven. Take an example that changes to (colored state) and describe.

Both the anodic EC compound and the cathodic EC compound control the voltage applied between the first electrode 11a and the second electrode 11b, or switch the EC element 1 on / off to perform an oxidation reaction or reduction. The reaction takes place and takes at least two different states. In this specification, a state in which an EC compound is oxidized by an oxidation reaction of one or more electrons is referred to as an "oxidant" of the EC compound, and a state reduced by a reduction reaction of one or more electrons is referred to as "an oxidation compound". It is called a reductant. That is, the anodic EC compound is a reductant when the EC element 1 is not driven, but is an oxidant when the EC element 1 is driven. In addition, the cathodic EC compound is an oxidant when the EC element 1 is not driven, but is a reductant when the EC element 1 is driven.

In some documents, as an expression indicating the state of the EC compound, there is an expression that it changes from an oxidized form to a reduced form (or vice versa) via a neutral form. However, in the following description, basically, the reductant is generated when the oxidant is reduced, and the oxidant is generated when the reductant is oxidized: The descriptions of oxidant and reductant are adopted. For example, ferrocene containing divalent iron (neutral as a whole molecule) is a reductant of ferrocene (anodic redox compound) when ferrocene functions as an anodic redox compound. The reductant is oxidized to form iron in a trivalent state (ferrocenium ion), which is an oxidized form of ferrocene (anode redox compound), particularly a first oxidized form. When the dication salt of viologen functions as the cathodic EC compound, the dication salt is an oxidized form of the cathodic EC compound. Further, the monocationic salt obtained by subjecting the dicationic salt to one-electron reduction is a reductant of the cathodic EC compound, in particular, a first reductant.

The EC compound according to the present embodiment is an organic compound. The EC compound may be a low molecular weight organic compound or a high molecular weight organic compound, but is preferably a low molecular weight organic compound having a molecular weight of 2000 or less. Moreover, it is preferable that an anodic EC compound and a cathodic EC compound are both compounds which change from a decoloring body to a colored body by driving of the EC element 1. In addition, as an EC compound, multiple types of anodic EC compounds and cathodic EC compounds may be contained, respectively.

As described later, the anodic EC compound may be a compound in which the difference between the solvation free energy in water and the solvation free energy in octanol of the oxidized form of the anodic EC compound is 35 kcal / mol or more. There is no particular limitation. Examples of anodic EC compounds include thiophene derivatives, amines having an aromatic ring (for example, phenazine derivatives, triallylamine derivatives), pyrrole derivatives, thiazine derivatives, triallylmethane derivatives, bisphenylmethane derivatives, xanthene derivatives, fluoran derivatives And spiropyran derivatives. Among these, as the anodic EC compound, amines having a low molecular weight aromatic ring are preferable, and a dihydrophenazine derivative is most preferable.

This is because by using these compounds as EC compounds, it is easy to provide an EC element having a desired absorption wavelength profile, and have high durability to repeated use. These compounds have an absorption peak in the ultraviolet region in the neutral state (reductant), have no absorption in the visible light region, and take a decolored state with high transmittance in the visible light region. Then, when these molecules become radical cations (oxidant) by the oxidation reaction, the absorption peak shifts to the visible light region to be in a colored state. The absorption wavelength of these molecules can be arbitrarily designed by scaling the π conjugated length and changing the substituent to change the π conjugated system. The low molecule referred to here is 2000 or less, preferably 1000 or less in molecular weight.

The cathodic EC compound is not particularly limited as long as it is a compound having a substituent containing any of halogen, sulfur, boron, phosphorus and silicon as described later. Examples of the cathodic EC compound include pyridine derivatives such as viologen derivatives, and quinone compounds. Among these, pyridine derivatives such as viologen derivatives are most preferably used.

Therefore, the cathodic EC compound is preferably a compound having a pyridine skeleton or a quinone skeleton and having a substituent containing any of halogen, sulfur, boron, phosphorus, and silicon. The cathodic EC compound is more preferably a compound having a viologen skeleton and having a substituent containing any of halogen, sulfur, boron, phosphorus and silicon.

Furthermore, the cathodic EC compound is more preferably a compound represented by the following general formula (11).

Figure JPOXMLDOC01-appb-C000002

In the above general formula (11), X 1 and X 2 are each independently selected from an alkyl group, an aralkyl group and an aryl group. The alkyl group, the aralkyl group and the aryl group may have a substituent. Each of R 11 to R 18 independently represents a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryl group, a heterocyclic group, a substituted amino group, a halogen atom or an acyl group. The alkyl group, the alkoxy group, the aralkyl group, the aryl group, and the heterocyclic group may have a substituent. A 1 - and A 2 - each independently represents a monovalent anion. At least one of X 1 and X 2 and R 11 to R 18 is a substituent containing any element of halogen, sulfur, boron, phosphorus and silicon.

Furthermore, in the above general formula (11), X 1 and X 2 are particularly preferably a substituent containing any element of halogen, sulfur, boron, phosphorus and silicon.

<Cause of vertical color separation>
The present inventors have synthesized a large number of EC materials, measured under various conditions, and analyzed the vertical color separation that occurs in the EC device. As a result, the present inventors revealed that this vertical color separation occurs due to the combination of the following two causes. Hereinafter, these two types of causes will be described.

(I) Formation of Assemblies by Reduction of Affinity to Solvent EC compounds undergo an oxidation-reduction (typically, decoloring and decoloring) reaction when the EC device is driven, and the ion valence changes. Specifically, the anodic EC compound is oxidized when the EC element is driven, the ion valence changes in the positive direction, and the cathodic EC compound is reduced when the EC element is driven. The ion valence changes in the negative direction. Due to the increase and decrease of the ion valence number associated with the oxidation-reduction reaction, the EC compound changes its affinity for the solvent between the oxidized form and the reduced form, typically, the colored form and the decolored form.

The EC compound is preferably a compound having high solubility in a solvent. In general, the solubility (affinity) of an EC compound in a solvent is often evaluated in a state where the EC device is not driven, typically in a decolored state. Accordingly, EC compounds having an anodic EC compound with high affinity to the solvent in the reductant, and cathodic EC compounds with an oxidant having high affinity to the solvent are often selected.

However, for the reasons described above, even when the EC compound has high affinity to the solvent when the EC device is not driven (typically, the decoloring state), the EC device is driven (typically) In the colored state, the affinity to the solvent may be low. For example, when the solubility of the EC compound in the solvent is optimized in a state where the EC element is not driven (typically, the decoloring state), the ion valence number of the EC compound when the EC element is driven As the changes in, the affinity to the solvent decreases. When the affinity to the solvent is lowered, the EC compound will form an aggregate with the anodic EC compound and the cathodic EC compound to be energetically stabilized in the solvent. When each of the anodic EC compound and the cathodic EC compound form an assembly, the uniformity of the distribution of the EC compound in the EC layer is reduced, and the distribution tends to be biased.

The oxidant and reductant of the EC compound are sometimes referred to as a colored body and a decolorant due to a change in transmittance due to the redox reaction. In addition, it may be expressed as cationization that the ion valence changes in the positive direction. However, changing the ion valence in the positive direction includes changing the ion valence from -2 to -1.

(Ii) There is a difference in the density of the aggregate between the anodic EC compound and the cathodic EC compound. Generally, the organic compound increases in density when the ion valence changes in the positive direction (cationizes). It is known. As described in (i), the EC compound changes its ion valence when the EC element is driven, so that the density of the oxidant and the reductant, typically, the colorant and the decolorizer, Changes. Specifically, when the EC element is driven, the anodic EC compound changes in the positive ion valence direction, so the density increases, and the cathodic EC compound changes in the negative ion valence direction. Because the density decreases. When there is a difference in density between EC compounds, gravity causes the larger density to settle and the smaller density to float more easily.

The synergetic occurrence of these two causes, that is, the distribution of EC compounds is apt to be biased due to the formation of aggregates, and the difference in the density of aggregates among EC compounds is apt to cause sedimentation and floating. By doing so, vertical color separation will occur. Specifically, when the EC element is continuously driven for a long time, the colored body color of the anodic EC compound is downward in the vertical direction, while the colored body of the cathodic EC compound whose density is low in the vertical direction The color will be strongly expressed.

<Solution of vertical color separation>
The inventors of the present invention have a solution of “(i) formation of an aggregate due to a reduction in affinity to a solvent” among the two causes to the anodic EC compound, “(ii) there is a difference in the density of the aggregate 'Solutions were applied to cathodic EC compounds to suppress vertical color separation. That is, an anodic EC compound having high affinity to a solvent even in a state where an EC device is driven (typically, a colored state), and a cathodic EC compound having a small density difference from the solvent even in the same state I thought about combining. Specifically, with regard to the anodic EC compound, when the EC element is driven, it is oxidized and hydrophilized to decrease its affinity to the solvent. Compounds with high hydrophobicity were selected. In addition, as for the cathodic EC compound, when the EC element is driven, it is reduced and the ion valence changes in the negative direction and the density decreases, so that the floating of the reductant of the cathodic EC compound in the EC layer is suppressed In order to do this, a dense cathode EC compound was selected. More specifically, a cathodic EC compound having a substituent containing an element that increases the density of the organic compound was selected. As a result, for the anodic EC compound, the present inventors ensure the affinity of the EC compound for the solvent even in the driven state of the EC element (typically in the colored state), and suppress the formation of aggregates. And considered that vertical color separation can be suppressed. In addition, for the cathodic EC compound, the difference in density between the aggregate that can be formed when the EC element is driven (typically in the colored state) and the solvent is reduced, and the vertical color separation is suppressed. I thought I could. Based on this idea, the present inventors synthesize a large number of anodic EC compounds and cathodic EC compounds and combine them to evaluate the EC element, thereby highly suppressing vertical color separation by the above method. The present invention has been completed.

The above requirement found by the present inventors is to satisfy both of the following two conditions.
(A) The difference between the solvation free energy in water and the solvation free energy in octanol of the oxidized form of the anodic EC compound ((solvation free energy in water)-(solvation free energy in octanol)) is 35 kcal / be more than mol.
(B) The cathodic EC compound has a substituent containing any element of halogen, sulfur, boron, phosphorus and silicon.

In other words, among the above requirements, the requirement of (a) is to satisfy the following formula (1).
G A + H2O -G A + OcOH ≧ 35 ··· formula (1)

However, in formula (1), G A + H 2 O represents the solvation free energy (kcal / mol) in water of the oxidized form of the anodic electrochromic compound, and G A + OcOH represents the oxidized form of the anodic electrochromic compound Solvation free energy (kcal / mol) in octanol.

In the above conditions, "an oxidized form of the anodic EC compound" can be read as "a colored body of the anodic EC compound".

The present inventors have found the above requirements based on the following experimental results.

Figure 2 is a solvation free energy difference G A + H2O -G A + OcOH of anodic EC compound is a graph representing the degree of relationship between the vertical color separation in EC element using the anodic EC compound. FIG. 2 shows an experimental result of measuring the degree of vertical color separation by preparing an EC device using a solution of an anodic EC compound and a cathodic EC compound in propylene carbonate as a solvent as the EC layer 12 Is a graph based on At this time, the concentration of the anodic EC compound and the cathodic EC compound in the EC layer 12 was 0.1 mol / L, respectively. Further, a compound represented by Formula (C3) described later was used as the cathodic EC compound, and a compound represented by Formulas (A1) to (A9) described later was used as the anodic EC compound. In FIG. 2, the abscissa of the graph represents the difference between the solvation free energy in water and the solvation free energy in octanol of the oxidized form of the anodic EC compound (solvation free energy in water)-(solvation freedom in octanol) Represents energy)). Further, in FIG. 2, the vertical axis of the graph represents the degree of vertical color separation, and indicates that the smaller the index d (ΔOD), the more the vertical color separation is suppressed. The method of evaluating the degree of vertical color separation will be described later.

From FIG. 2, according to the solvation of the oxidant free energy difference G A + H2O -G A + OcOH of anodic EC compound increases, the degree of vertical color separation was found to tend to decrease. Then, by the solvation free energy difference G A + H2O -G A + OcOH to or greater than a predetermined value, was found to be significantly inhibited vertical color separation. Specifically, by setting the solvation free energy difference to 35 kcal / mol or more, the degree of vertical color separation can be significantly reduced, and by setting the solvation free energy difference to 44 kcal / mol or more, the degree of vertical color separation is further remarkable It has been found that it can be reduced to Therefore, it is more preferable to further satisfy the following formula (2) in addition to the above formula (1).
G A + H2O -G A + OcOH ≧ 44 ··· formula (2)

However, when the present inventors repeated studies, simply select the anodic EC compound in view of solvation as described above free energy difference G A + H2O -G A + OcOH is the suppression of the vertical color separation It turns out that there is a limit. This is because, even if a compound which is difficult to form aggregates during oxidation (typically during coloring) is used as the anodic EC compound, the assembly during cathodic EC compounds during reduction (typically during decoloring) Vertical color separation occurs as a whole of the EC element if it is easy to form Accordingly, the present inventors have also studied cathodic EC compounds, and investigated the degree of vertical color separation when an element that increases the density of the organic compound is introduced into the substituent.

FIG. 3 is a graph showing the results of measuring the time-dependent change in the degree of vertical color separation for three types of EC elements each using a cathodic EC compound with different substituents. FIG. 3 shows an experimental result of measuring the degree of vertical color separation by preparing an EC element using a solution of an anodic EC compound and a cathodic EC compound dissolved in propylene carbonate as a solvent as the EC layer 12. Is a graph based on At this time, the concentration of the anodic EC compound and the cathodic EC compound in the EC layer 12 was 0.1 mol / L. As an anodic EC compound, the compound represented by Formula (A1) mentioned later was used. As the anodic EC compound, compounds represented by formulas (C1), (C2) and (C4) described later were used. The compound represented by the formula (C1) plotted by the legend に お い て in FIG. 3 and the compound represented by the formula (C2) plotted by the legend 、 are fluorine, which is an element that increases the density of the organic compound. It has a substituent which it contains. On the other hand, the compound represented by the formula (C4) plotted in legend in FIG. 3 does not have a substituent containing an element that increases the density of the organic compound, and has a comparison with an unsubstituted alkyl. Cathodic EC compound. In FIG. 3, the horizontal axis of the graph represents the elapsed time from the start of continuous coloring drive, and the vertical axis of the graph represents the degree of vertical color separation, and the smaller the value of d (ΔOD), the more vertical color separation Indicates that it is suppressed.

From the figure, it was found that the degree of vertical color separation is reduced by introducing an element that increases the density of the organic compound into the substituent of the cathodic EC compound.

Here, as an element for increasing the density of the organic compound, halogen, sulfur, boron, phosphorus and silicon can be mentioned. Among these, halogen is preferable, and fluorine is more preferable.

According to the above study, a compound which hardly forms an aggregate when driving an EC element is adopted as the anodic EC compound, and a compound having a substituent which increases the density of the compound is adopted as the cathodic EC compound For the first time, vertical color separation can be highly suppressed to the extent that the maximum value of d (ΔOD) is less than 0.01. More specifically, by satisfying both of the above two conditions (a) and (b), the degree of vertical color separation is controlled to a high degree so that the value of d (ΔOD) becomes 0.01 or less for the first time. It was possible.

<Method of evaluating degree of vertical color separation>
A method of evaluating the degree of vertical color separation will be described with reference to FIG.

In the transmission type EC element, light was transmitted to the driven EC element, and the spectrum of the transmission light was measured two-dimensionally in the element surface of the EC element, that is, at each point of the element surface of the EC element. When the spectrum of this transmitted light was measured over time, the average spectrum obtained by averaging the spectra of all points in the element plane of the EC element at each time does not depend on the time (regardless of the passage of time) It turned out that it hardly changed. Therefore, in this specification, the average spectrum of all in-plane points is used as a reference spectrum, and the degree of vertical color separation is evaluated based on the deviation from the reference spectrum of the spectrum at each point in-plane.

Specifically, first, in order to remove the influence of concentration unevenness of the entire EC compound (does not affect vertical color separation) in the element in-plane direction in the EC layer, both the reference spectrum and the spectrum at each point in the plane Each was standardized. The normalization was performed such that the average optical density change amount (ΔOD) became 1 in a predetermined wavelength range (here, 425 nm to 700 nm). For each of the normalized spectra of each in-plane point, the difference from the normalized reference spectrum is D (λ), and the value of d (ΔOD) is calculated from the following equation (5).

Figure JPOXMLDOC01-appb-M000003

Here, in the equation (5), λ 0 represents the lower limit (nm, here, 425 nm) of the wavelength range of light of interest, and λ 1 represents the upper limit (nm, 700 nm here) of the wavelength range of light of interest Represents The d (ΔOD) value represents the average deviation width from the reference spectrum of the spectrum of each point in the plane normalized as described above, and the larger the value, the spectrum of the transmitted light at that point It shows that it deviates from the reference spectrum. Therefore, at each time (elapsed time), the above d (ΔOD) was calculated for the spectrum of each point in the plane, and the average value was calculated. Then, the degree of vertical color separation of the EC element was evaluated at the maximum value of the average value of d (ΔOD) calculated at each time during the evaluation time (typically during 24 hours).

Examples of applications of the EC device 1 according to the present embodiment include a display device, a variable reflectance mirror, a variable transmission window, an optical filter, and the like. When vertical color separation occurs in these applications, the color balance of the transmitted light or the reflected light is unintentionally changed above and below the EC element surface, which is not preferable in any application.

As an example, consider the case where this EC element is used as an optical filter of a camera, in particular, an ND filter, for this value of d (ΔOD). When vertical color separation occurs in the EC element used as the ND filter, the tint changes between the upper side and the lower side of the image obtained by imaging. Specifically, when each EC compound is colored by driving the EC element, typically, the colored color of the cathodic EC compound appears strongly above the filter, and the colored color of the anodic EC compound is colored below the filter. It will appear strongly. As a result, in the image to be imaged, the coloring color of the cathodic EC compound strongly appears below, and the coloring color of the anodic EC compound strongly appears above the image. This is because the imaging device reads the light that passes through the lens and forms an image, so the top and bottom are opposite to the filter. As a result, when the degree of vertical color separation is large, the quality of the obtained image is significantly reduced, which is not preferable.

As cathodic EC compounds, viologen compounds are known, and as anodic EC compounds, dihydrophenazine compounds are known. When these are used as EC compounds, in the image in which the vertical color separation has occurred, green to blue appear strongly below the image, and red strongly appears above the image. That is, the image quality is significantly reduced.

Thus, when the EC element is used for applications such as an optical filter, it is required that the degree of vertical color separation be suppressed. Specifically, if the value of d (ΔOD) can be made 0.01 or less by the approach regarding the EC compound, the quality of the acquired image can be maintained even when the EC element is used as an optical filter become able to. As a result, for example, it can be suppressed that a person's complexion looks blue in the lower part of the screen or that an empty image is purpleish in the upper part of the screen.

<Concentration of EC compounds>
FIG. 5 is a graph showing the relationship between the concentration C (mol / L) of the anodic EC compound and the cathodic EC compound and the degree of vertical color separation. FIG. 5 shows a compound represented by the formula (A1) described later as the anodic EC compound and a compound represented by the formula (C3) described later as the cathodic EC compound, dissolved in propylene carbonate as a solvent It is a graph regarding EC element which used the solution as EC layer. Here, the concentration of the anodic EC compound and the cathodic EC compound in the EC layer is C (mol / L), respectively. In FIG. 5, the horizontal axis of the graph represents the concentration C (mol / L) of each of the anodic EC compound and the cathodic EC compound, and the vertical axis of the graph represents the degree of vertical color separation described above.

It can be seen from FIG. 5 that when the concentration C of the anodic EC compound and the cathodic EC compound is 0.05 mol / L or more, vertical color separation significantly occurs. As described above, it is considered that one of the causes of vertical color separation is that the affinity of the EC compound to the solvent decreases when the EC element is driven, and the EC compound forms an aggregate. The concentration of the components forming the assembly strongly influences the formation of the assembly. Specifically, the higher the concentration of the components forming the assembly, the easier it is to form the assembly, and it is conceivable that the formation of the assembly rapidly proceeds when the concentration exceeds the threshold. Here, in the region where the concentration of the EC compound in the EC layer is 0.05 mol / L or more, it is considered that the degree of formation of aggregates becomes high, and vertical color separation appears strongly.

In the EC element, when the concentration of the EC compound in the EC layer is increased, it is easy to increase the amount of change in optical characteristics when the EC element is driven and not driven. However, as described above, when the concentration of the EC compound in the EC layer is high, the formation of aggregates tends to occur, and thus the vertical color separation also tends to occur. However, according to this embodiment, the formation of aggregates can be suppressed by appropriately selecting the affinity of the anodic EC compound and the cathodic EC compound to the solvent. Therefore, even when the concentration of the anodic EC compound and the cathodic EC compound is as high as 0.05 mol / L or more, the formation of aggregates at the time of driving the EC element can be suppressed, and the vertical color separation can be suppressed. .

<Method of calculating solvation free energy>
The method for calculating the solvation free energy of the oxidized form or reduced form (typically, colored form) of the EC compound is described below.

Solvation free energy when a molecule A is dissolved in a solvent composed of molecule B can be sampled by the following three types of equilibrium states by molecular dynamics calculation and then using an energy display method It can be calculated.
(I) Sampling of isothermal constant pressure equilibrium state of solution system X composed of one molecule A and many molecules B (ii) Sampling of isothermal constant pressure equilibrium state of solvent system Y composed of a large number of molecules B (iii ) Sampling of the constant temperature equilibrium state of the system Z consisting of one molecule A

(Sampling of equilibrium state by molecular dynamics calculation)
In the sampling of the equilibrium state by molecular dynamics calculation, the target molecule is placed in a unit cell with periodic boundary conditions imposed, the force acting between atoms contained in each molecule is calculated for each time, and all atoms for time evolution It can be obtained by calculating the locus of. Molecular dynamics calculation is described in the technical literature 1 (Susumu Okazaki, "Basics of Computer Simulation", Dojin (2000)). Sampling of the equilibrium state by molecular dynamics calculation can be performed using molecular dynamics simulation software GROMACS-5.1.

In order to carry out molecular dynamics calculations, it is necessary to set in advance a parameter called “force field parameter” for defining the interaction between atoms. Force field parameters are composed of two types: electrostatic force field parameters and non-electrostatic force field parameters.

As electrostatic force field parameters, the assigned charge of each atom is used. The assigned charge of each atom can be obtained by performing charge fitting on the electrostatic potential calculated by quantum chemical calculation. The Corn-Sham method can be used as the quantum chemical calculation for calculating the electrostatic potential, and B3LYP can be used as the exchange correlation functional at that time, and 6-31 G * can be used as the basis function. The 6-31 G * is the 6-31 G plus a polarization function. Charge fitting can be performed using a score based on the Merz-Singh-Kollman method. In addition, the above-mentioned quantum chemistry calculation is described in Gaussian 09 Revision D. 01 (M. J. Frisch, et al., Gaussian, Inc., Wallingford CT, 2013.). Also, for the Merz-Singh-Kollman method, technical literature 2 (B. H. Besler, et al., J. Comp. Chem. 11, 431 (1990).) And technical literature 3 (U. C. Singh, et al., J. Comp. Chem. 5, 129 (1984).).

As a non-electrostatic force field parameter, general Amber force field (GAFF, GAFF) generally used for organic molecules is used.

Molecular dynamics calculation consists of three steps: compression process, equilibration process, and Production Run. The compression process is performed to form an appropriate molecular assembly. The equilibration process is performed to bring the computational system into thermodynamic equilibrium. In Production Run, sampling of equilibrium is performed.

The calculation conditions used for the compression process are a simulation time of 40 ps, a temperature of 700 K, a compression ratio set value of 0.000045, an atmospheric pressure set value of 10000 atm, and a constant temperature constant pressure simulation using the Berendsen method.

The calculation conditions used for the equilibration process are a simulation time of 5 ns, a temperature of 300 K, a compression ratio set value of 0.000045, an atmospheric pressure set value of 1 atm, and a constant temperature constant pressure simulation using the Berendsen method.

The calculation conditions used for Production Run are a simulation time of 20 ns, a compression ratio set value of 0.000045, and an air pressure set value of 1 atm, and are constant temperature constant pressure simulations using the Berendsen method.

(Calculation of free energy by the energy display method)
In the energy display method performed after sampling of the equilibrium state by molecular dynamics calculation, the interaction acting between the solvent molecule B and the solute molecule A is evaluated, and finally the molecule A is dissolved in the solvent composed of the molecule B You can calculate the solvation free energy when you For the energy display method, see Technical Literature 4 (N. Matubayasi et al., J. Chem. Phys. 113, 6070-6081 (2000).), Technical Literature 5 (S. Sakuraba, et al., J. Comput. Chem. . 35, 1592-1608 (2014).). The calculation of free energy by the energy display method can be performed using ERmod-0.3 which is free energy calculation software.

<Drive method of EC element>
Although the drive means of the EC element according to the present embodiment is not particularly limited, a means for controlling the transmittance of the EC element by pulse width modulation is preferably used. As an example, the transmittance of the EC element is maintained without changing the peak value of the pulse voltage waveform, and the transmittance of the EC element is controlled by changing the ratio of the application period of the applied voltage to one cycle of the pulse voltage waveform. The method is mentioned.

At this time, the ratio of the voltage application period to one cycle is defined as the duty ratio. When the pulse duty ratio is maintained, coloring of the EC material increases in the application period of the voltage, and coloring of the EC material decreases in the idle period. When the EC element is driven with a fixed duty ratio under a constant voltage of the drive power supply, the change in absorbance is saturated through a transient state, and the saturated absorbance is maintained. In order to reduce the absorbance, the duty ratio may be fixed at a smaller duty ratio than the immediately preceding duty ratio, and in order to increase the absorbance, the duty ratio may be fixed at a greater duty ratio than the immediately preceding duty ratio. At this time, if one cycle of the control signal is late, an increase or decrease in absorbance change may be visually recognized. Therefore, one cycle is preferably 100 milliseconds or less, and more preferably 10 milliseconds or less.

<Effect>
According to the EC element according to the present embodiment, when the EC element is driven, the formation of an aggregate of the anodic EC compound contained in the EC layer can be suppressed. In addition, when the EC element is driven, the cathodic EC material can be prevented from rising due to the density difference in the EC layer. Therefore, vertical color separation in which the anodic EC compound and the cathodic EC compound are separated in the vertical direction can be suppressed even in the case where the EC element is vertically arranged and arranged to be continuously driven for a long time. According to the present embodiment, since vertical color separation can be suppressed without significantly increasing the viscosity of the EC layer, vertical color separation can be suppressed while suppressing deterioration in element responsiveness. In addition, vertical color separation can be further suppressed by appropriately increasing the viscosity of the EC layer, and vertical color separation can be further suppressed while securing element responsiveness.

[Optical filter, imaging device, lens unit]
The EC element 1 can be used for an optical filter. An optical filter 101 according to another embodiment of the present invention shown in FIG. 6 includes an EC element 1 and an active element connected to the EC element 1. An active element is an element which adjusts the light quantity which permeate | transmits EC element, and, specifically, the switching element for controlling the transmittance | permeability of EC element is mentioned. As a switching element, a TFT and a MIM element are mentioned, for example. The TFT is also called a thin film transistor, and a semiconductor or an oxide semiconductor is used as a constituent material thereof. Specifically, amorphous silicon, low temperature polysilicon, a semiconductor having InGaZnO as a constituent material, and the like can be given.

The EC element 1 can be used for an imaging device and a lens unit. An imaging device 103 according to another embodiment of the present invention shown in FIG. 6 includes the above-described optical filter 101 having the EC element 1 and a light receiving element 110 for receiving light that has passed through the optical filter 101.

A lens unit 102 according to another embodiment of the present invention includes the above-described optical filter 101 having the EC element 1 and an imaging optical system. The imaging optical system is preferably a lens group having a plurality of lenses. The optical filter 101 may be disposed such that the light passing through the optical filter 101 passes through the imaging optical system, or even if the light passing through the imaging optical system passes through the optical filter 102 Good. Also, the optical filter 102 may be disposed between a plurality of lenses and the lenses. The optical filter 102 is preferably provided on the optical axis of the lens. The optical filter 102 can adjust the amount of light passing through the imaging optical system or the amount of light passing through.

FIG. 6 is a view schematically showing an example of an imaging device and a lens unit using the optical filter 101. As shown in FIG. 6A shows an imaging apparatus having a lens unit 102 using an optical filter 101, and FIG. 6B shows an imaging apparatus 103 having an optical filter 101. As shown in FIG. 6A, 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. For example, in FIG. 6A, the lens unit 102 represents a rear focus zoom lens that performs focusing after the aperture stop. The lens unit 102 includes a first lens group 104 of positive refractive power, a second lens group 105 of negative refractive power, and a third lens group 106 of positive refractive power in order from the object side (left side in the drawing). , And a fourth lens group 107 of positive refractive power. The magnification change is performed by changing the distance between the second lens group 105 and the third lens group 106, and a part of the fourth lens group 107 is moved for focusing. The lens unit 102 has, for example, an aperture stop 108 between the second lens group 105 and the third lens group 106, and an optical filter between the third lens group 106 and the fourth lens group 107. It has 101. The light passing through the lens unit 102 is arranged to pass through each of the lens groups 102 to 107, the aperture stop 108 and the optical filter 101, and the light amount can be adjusted using the aperture stop 108 and the optical filter 101. .

Further, the configuration in the lens unit 102 can be changed as appropriate. For example, the optical filter 101 can be disposed in front (subject side) or back (imaging unit 103 side) of the aperture stop 108, or may be disposed in front of the first lens group 104, and the fourth lens group It may be arranged later than 107. If disposed at a position where light converges, there is an advantage that the area of the optical filter 101 can be reduced. Further, the form of the lens unit 102 can be appropriately selected, and in addition to the rear focus type, an inner focus type in which focusing is performed before the stop may be used, or any other type may be used. In addition to zoom lenses, special lenses such as fisheye lenses and macro lenses can also be selected as appropriate.

The imaging unit 103 has a glass block 109 and a light receiving element 101. The glass block 109 is a glass block such as a low pass filter, a face plate, or a color filter. The light receiving element 110 is a sensor unit that receives light passing through the lens unit 102, and an imaging element such as a CCD or a CMOS can be used. Further, it may be an optical sensor such as a photodiode, and one that acquires and outputs information on light intensity or wavelength can be used as appropriate.

As shown in FIG. 6A, when the optical filter 101 is incorporated in the lens unit 102, driving means such as an active element may be disposed in the lens unit 102 or may be disposed outside the lens unit 102. When the lens unit 102 is disposed outside the lens unit 102, the EC element inside and outside the lens unit 102 and the drive unit are connected through a wire to control the drive.

As shown in FIG. 6B, the imaging device itself may have the optical filter 101. The optical filter 101 may be disposed at an appropriate place inside the imaging unit 103, and the light receiving element 110 may be disposed to receive the light passing through the optical filter 101. In FIG. 6 (b), for example, the optical filter 101 is disposed immediately in front of the light receiving element 110. When the imaging device itself incorporates the optical filter 101, the connected lens unit 102 need not have the optical filter 101. Therefore, it is possible to configure a dimmable imaging device using an existing lens unit It becomes.

Such an imaging device is applicable to a product having a combination of light amount adjustment and a light receiving element. For example, it can be used for a camera, a digital camera, a video camera, and a digital video camera, and can also be applied to products incorporating an imaging device such as a mobile phone, a smartphone, a PC, and a tablet.

By using the optical filter according to this embodiment as a light control member, it is possible to appropriately change the light control amount with one filter, and there is an advantage such as reduction of the number of members and space saving.

According to the optical filter, the lens unit, and the imaging device of the present embodiment, vertical color separation in the EC element can be suppressed. Therefore, it is possible to suppress the deterioration of the quality of the image obtained by imaging the light transmitted through or reflected by the optical filter.

[Window material]
The window material according to another embodiment of the present invention has an EC element 1 and an active element connected to the EC element. FIG. 7 is a view schematically showing an example of the window member according to the present embodiment, FIG. 7A is a perspective view, and FIG. 7B is a cross-sectional view taken along line XX ′ of FIG. 7A.

The window member 111 in FIG. 7 is a light control window, and includes an EC element 1, a transparent plate 113 (a pair of substrates) sandwiching the EC element 1, and a frame 112 which surrounds and integrates the whole. The active element is an element that adjusts the amount of light passing through the EC element 1 and may be directly connected to the EC element 1 or may be connected indirectly. In addition, the active element may be integrated in the frame 112 or may be disposed outside the frame 112 and connected to the EC element 1 through a wire.

The transparent plate 113 is not particularly limited as long as it is a material having a high light transmittance, and is preferably a glass material in consideration of use as a window. In FIG. 7, the EC element 1 is a component independent of the transparent plate 113, but for example, the substrate 10 of the EC element 1 may be regarded as the transparent plate 113.

The frame 112 may be made of any material, but at least a part of the EC element 1 may be covered, and any frame having an integrated form may be regarded as the frame.

The light control window can also be referred to as a window material having an electronic curtain, a sufficient amount of transmitted light can be obtained for incident light when the EC element 1 is in the decolored state, and the incident light can be reliably blocked in the colored state. Modulated optical properties are obtained. The window material which concerns on this embodiment is applicable to the use which adjusts the incident amount of the sunlight to the room of the daytime, for example. Since the present invention can be applied to adjustment of the amount of heat as well as the amount of light of the sun, it can be used to control the brightness and temperature of the room. Moreover, it is applicable also as the use which shuts off the view from the outdoors to indoors as a shutter. Such a light control window can be applied not only to glass windows for buildings, but also to windows of vehicles such as cars, trains, airplanes and ships, and filters of the display surface of clocks and mobile phones.

Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples.

<Specific example of EC compound used for solution method of vertical color separation>
(Anode EC compound)
Hereinafter, specific examples of the anodic EC compound which can be used in the present invention will be shown. However, the anodic EC compound used in the present invention is not limited to these.

Figure JPOXMLDOC01-appb-C000004

Below, the specific example of the anodic EC compound which does not satisfy | fill the above-mentioned conditions (Formula (1)) is shown as a reference.

Figure JPOXMLDOC01-appb-C000005

Table 1 summarizes the difference between the solvation free energy in water and the solvation free energy in octanol of the oxidized product of the above-mentioned anodic EC compound. In all of the above anodic EC compounds (A1) to (A7), the oxidant is a colored body. Moreover, solvation free energy is calculated by the above-mentioned method.

Figure JPOXMLDOC01-appb-T000006

(Cathodic EC compound)
Similarly, specific examples of the cathodic EC compound that can be used in the present invention are shown. However, the cathodic EC compound used in the present invention is not limited to these.

Figure JPOXMLDOC01-appb-C000007

Figure JPOXMLDOC01-appb-C000008

The following is a specific example of a cathodic EC compound which does not satisfy the conditions described above, that is, has no substituent containing an element that increases the density of the organic compound, as a reference.

Figure JPOXMLDOC01-appb-C000009

Figure JPOXMLDOC01-appb-C000010

(Acquisition of EC compounds)
Among the above EC compounds, the anodic EC compound represented by the formula (A1) was synthesized with reference to the patent document (US Pat. No. 6,020,987). The anodic EC compounds represented by the formulas (A2) to (A5), (A8) and (A9) were synthesized using a reaction represented by the following formula (A). (The second step was used for (A9).)

Figure JPOXMLDOC01-appb-C000011

In formula (A), X is a halogen atom, R 1 is a hydrogen atom or an alkyl or phenoxy group, R 2 and R 3 are a hydrogen atom or an alkyl or alkoxy group, and R 4 is a methyl or isopropyl group . As a first step, a known Pd-catalyzed coupling reaction is carried out with a combination of a substituted or unsubstituted phenazine halogen and a phenylboronic acid or boronic acid ester compound having an alkyl group or an alkoxy group at the ortho position. It can be synthesized. Furthermore, the anodic EC compound represented by the formulas (A2) to (A5) and (A8) can be synthesized by performing reduction and alkylation of the phenazine ring in the second step.

With respect to the compounds represented by the formulas (A5), (A8) and (A9), it is necessary to introduce a phenoxy group derivative at the 2,7 position of the phenazine ring. The phenoxy group derivative can be introduced to a phenazine halogen by a known Cu-catalyzed coupling reaction using phenol. The synthesis scheme of the anodic EC compound represented by Formula (A5), including the meaning of the specific example of the reaction of Formula (A), is shown in the following Formula (B).

Figure JPOXMLDOC01-appb-C000012

The anodic EC compound represented by the formula (A5) can be synthesized, for example, by the following procedure. First, the first step intermediate is synthesized. 2,7-Dibromophenazine, phenol was mixed in DMSO and nitrogen was used to remove dissolved oxygen. Next, CuI / Spartein complex, potassium carbonate was added and refluxed for 8 hours. The reaction solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain a first step intermediate of a yellow solid.

Next, the first step intermediate, 2-isopropoxy-6-methoxyphenylboronic acid was mixed in a toluene / 1,4-dioxane mixed solvent, and nitrogen was used to remove dissolved oxygen. Add Pd (OAc) 2, 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (S-Phos), tripotassium phosphate and reflux for 15 hours. The reaction solution was concentrated under reduced pressure and separated and purified by silica gel chromatography to obtain a second intermediate of a yellow solid.

Subsequently, the second step intermediate, 2-iodopropane, was mixed in an acetonitrile / water mixed solvent, and nitrogen was used to remove dissolved oxygen. Add sodium hydrosulfite, potassium carbonate and reflux for 10 hours. The reaction solution was concentrated under reduced pressure and separated and purified by silica gel chromatography to obtain a solid anodic EC compound of the formula (A5). The results of 1 H-NMR measurement of the obtained anodic EC compound are as follows.
1 H-NMR (heavy acetone) δ (ppm): 7.35 (m, 2 H), 7.19 (t, 1 H), 7.06 (t, 1 H), 6.99 (d, 2 H), 6 8- 6.65 (m, 6 H), 6.49 (d, 1 H), 6.42 (dd, 1 H), 4.47 (sep, 1 H), 4.17 (sep, 1 H), 3. 97 (sep, 1 H), 3.71 (s, 3 H), 1.51 (d, 6 H), 1.46 (d, 6 H), 1.18 (d, 6 H).

The cathodic EC compounds represented by the formulas (C1) to (C4) were synthesized using a reaction represented by the following formula (C).

Figure JPOXMLDOC01-appb-C000013

In formula (C), X is a halogen atom, R 1 and R 2 are a hydrogen atom or an alkyl group, and R 3 is an alkyl group or a substituted alkyl group. A halogen salt of a target compound can be obtained by reacting a halogenated (substituted / unsubstituted) alkyl compound with a substituted or unsubstituted 4,4′-bipyridine. Furthermore, the target compound can be synthesized by salt exchange using lithium bis (trifluoromethanesulfonyl) imide.

The synthesis example of the cathodic EC compound represented by Formula (C1) is described below as an example.

4,4′-bipyridine and an excess of 4,4 ′, 4 ′ ′-trifluoroiodobutane were added to the reaction vessel and reacted at 110 ° C. for 19 hours with DMF as a solvent. The precipitate was collected, dissolved in water and lithium bis (trifluoromethanesulfonyl) imide was added in excess. The precipitate was collected by filtration and dried to obtain a cathodic EC compound represented by the formula (C1). The results of 1 H-NMR measurement of the obtained cathodic EC compound are as follows.
1 H-NMR (DMSO) δ (ppm): 9.36 (d, 4 H), 8.78 (d, 4 H), 4.75 (t, 4 H), 2.40 (m, 4 H), 25 (t, 4 H).

For the cathodic EC compound represented by the formula (C4), a synthesis step of the compound serving as a raw material is required prior to the reaction of the formula (C). The synthesis scheme of this raw material is shown in the following formula (D).

Figure JPOXMLDOC01-appb-C000014

The synthesis method of 9,9-dimethyl-2,7-diazafluorene which is this raw material is described.

Technical literature (E. Botana, et al., Angew. Chem. Int. Ed. 46, 198-201 (2007).) Was synthesized with reference. To a reaction vessel was added 3,8-phenanthroline, potassium hydroxide, water and heated at 90.degree. Thereafter, a solution in which water and potassium permanganate were mixed and heated to 90 ° C. was dropped to the reaction solution. After reacting for 1 hour, the precipitated solid was filtered, extracted with chloroform, washed with water and saturated brine, dried and concentrated to obtain a brown powder. This was separated and purified by silica gel chromatography to obtain a first intermediate which was a yellow solid.

The first intermediate, diethylene glycol, and hydrazine monohydrate were added to the reaction vessel, and reacted at 100 ° C. for 12 hours. Water was added to the obtained black-red suspension, extracted with dichloromethane, washed with water and saturated brine, dried and concentrated to obtain a black-yellow solid. This was separated and purified by silica gel chromatography to obtain a second intermediate which was a tan solid.

The second intermediate, DMF, was added to the reaction vessel and cooled in an ice bath. Thereafter, potassium tert-butoxide was added, and the mixture was stirred at the same temperature for 30 minutes, and iodomethane diluted in DMF was added dropwise. After further stirring for 30 minutes at the same temperature, the reaction was carried out at room temperature for 3 hours. The resulting reddish brown suspension was added to saturated aqueous sodium bicarbonate solution, extracted with ethyl acetate, washed with water and saturated brine, dried and concentrated to give a dark yellow solid. This was separated and purified by silica gel chromatography to obtain 9,9-dimethyl-2,7-diazafluorene as a beige solid.

The anodic EC compound represented by the formula (A6), which is an EC compound for reference, was a purchased product as it was. Moreover, the anodic EC compound represented by Formula (A7) was synthesize | combined with reference to patent document (US Patent 6020987).

(Production of EC element)
An anodic EC compound and a cathodic EC compound were respectively selected from the above-mentioned EC compounds, and an EC element having a structure shown in FIG. 1 was produced by the following method.

Two sheets of transparent conductive glass (10a, 10b) on which an indium-doped tin oxide (ITO) film (electrodes 11a, 11b) is formed are prepared, and arranged so that the ITO films face each other. Then, the outer periphery of the two sheets of transparent conductive glass was adhered using a sealing material 13 in which spacer beads having a particle diameter of 50 μm were mixed. The anodic EC compound represented by any one of formulas (A1) to (A7) and the cathodic EC compound represented by any one of formulas (C1) to (C4) are each 0.1 mol / L. Dissolved in propylene carbonate at concentration. The solution is injected into the transparent conductive glass 10 b from an injection port (not shown) formed in advance, whereby the solution is formed in the space formed by the two sheets of the transparent conductive glass (10 a, 10 b) and the sealing material 13. Was filled. Thereafter, the inlet (not shown) was sealed with a sealing agent to obtain an EC element.

(Evaluation of vertical color separation)
The EC element having a rectangular element surface was combined with an automatic XZ stage such that the long side was in the horizontal direction and the short side was in the vertical direction. Then, the transmission spectrum of each point in the element plane of the EC element was continuously measured for 24 hours using a spectrum measuring apparatus combining a light source, an optical fiber, a lens and a spectroscope. Using the average spectrum of all points in the plane as a reference spectrum, the deviation of the spectrum at each point in the plane was evaluated using the value of d (ΔOD). The value of d (ΔOD) is as described above.

In addition to vertical color separation, electrode color separation may also occur as the color separation of EC elements due to the resistance of the transparent conductive glass. As a specific phenomenon, the coloring of the anodic EC compound and the cathodic EC compound may become strong near the feed bus bars of the anode and the cathode, respectively. At the time of evaluation measurement of vertical color separation, a four-terminal alternating drive method was used to remove the influence of the electrode color separation.

The four-terminal alternating drive method will be specifically described below. The feed bus bars of the EC element were provided along the long sides of the anode and the cathode, one for each of the two long sides (horizontal direction). In other words, the upper and lower two feed bus bars are disposed on each of the anode and the cathode. Then, the energization to the upper bus bar of the anode and the lower bus bar of the cathode and the energization to the lower bus bar of the anode and the upper bus of the cathode were alternately performed. In this study, the alternate application cycle was 1 Hz. The applied voltage was a value obtained by adding 0.15 V as an overvoltage to the difference between the half wave potential of the anodic EC material and the half wave potential of the cathodic EC compound.

The half-wave potential of each EC compound is obtained by performing cyclic voltammetry in a nitrogen atmosphere at 25 ° C. using an ITO electrode as a working electrode, a platinum wire as a counter electrode, and Ag / Ag + (PC, PF 6 ) as a reference electrode. It was measured. At this time, propylene carbonate was used as a solvent, 0.1 M tetrabutylammonium hexafluorophosphate was used as a supporting electrolyte, the concentration of the EC compound was 1 mmol / L, and the running speed was 0.1 Vs- 1 .

(Evaluation results)
Table 2 shows vertical color separation of EC elements using an anodic EC compound represented by any of Formulas (A1) to (A7) and a cathodic EC compound represented by Formula (C3). The results of measuring the degree of The results in Table 2 correspond to the graph in FIG. From this result, it was found that the degree of vertical color separation tends to decrease as the difference between the solvation free energy in water and the solvation free energy in octanol of the oxidized product of the anodic EC compound increases. Specifically, by setting the solvation free energy difference to 35 kcal / mol or more, the degree of vertical color separation can be significantly reduced, and by setting the solvation free energy difference to 44 kcal / mol or more, the degree of vertical color separation is further remarkable It can be reduced to

However, by simply selecting the anodic EC compound in view of the solvation free energy difference G A + H2O -G A + OcOH is the suppression of the vertical color separation was found that there is a limit. Specifically, it was difficult to reduce the value of d (ΔOD) to 0.01 or less.

Figure JPOXMLDOC01-appb-T000015

Table 3 shows vertical color separation of EC elements using the anodic EC compound represented by the formula (A1) and the cathodic EC compound represented by any of the formulas (C1) to (C4). The results of measuring the degree of Among the results of Table 3, the results regarding formulas (C1) and (C2) correspond to the graph of FIG. From this result, it was found that the degree of vertical color separation can be reduced by introducing an element that improves the density of the compound into the substituent of the cathodic EC compound. Specifically, it was found that the degree of vertical color separation can be reduced by introducing fluorine into the substituent of the cathodic EC compound.

According to the above-mentioned examination, for both of the anodic EC compound and the cathodic EC compound, the value of d (ΔOD) of vertical color separation is 0 for the first time by selecting the EC compound focusing on the solvation free energy difference described above It was possible to suppress to a high degree as low as .01 or less. More specifically, it is possible to suppress the vertical color separation to such an extent that the value of d (ΔOD) becomes 0.01 or less for the first time by satisfying both the above two conditions (a) and (b). The

Figure JPOXMLDOC01-appb-T000016

The present invention is not limited to the above embodiment, and various changes and modifications can be made without departing from the spirit and scope of the present invention. Accordingly, the following claims are attached to disclose the scope of the present invention.

The present application claims priority based on Japanese Patent Application No. 2017-196988 filed on Oct. 10, 2017 and Japanese Patent Application No. 2018-149516 filed on August 8, 2018, The entire contents of the description are incorporated herein.

Claims (15)

  1. A first electrode, a second electrode, and an electrochromic layer disposed between the first electrode and the second electrode, the electrochromic layer having a solvent, and an anodic property. An electrochromic device comprising an electrochromic compound and a cathodic electrochromic compound, comprising:
    The cathodic electrochromic compound has a substituent containing an element selected from halogen, sulfur, boron, phosphorus and silicon,
    Electrochromic device G A + H2O -G A + OcOH ≧ 35 ··· formula and satisfies the following formula (1) (1)
    (Wherein, in Formula (1), G A + H 2 O represents the solvation free energy (kcal / mol) in water of the oxidized form of the anodic electrochromic compound, and G A + OcOH is an oxidation of the anodic electrochromic compound Solvation free energy (kcal / mol) of the body in octanol).
  2. Furthermore, the following formula (2) is satisfy | filled, The electrochromic element of Claim 1 characterized by the above-mentioned.
    G A + H2O -G A + OcOH ≧ 44 ··· formula (2)
  3. The electrochromic device according to claim 1, wherein the cathodic electrochromic compound has a halogen-containing substituent.
  4. The electrochromic device according to any one of claims 1 to 3, wherein the cathodic electrochromic compound has a fluorine-containing substituent.
  5. 5. The electrochromic layer according to claim 1, wherein at least one of the concentration of the anodic electrochromic compound and the concentration of the cathodic electrochromic compound is 0.05 mol / L or more. An electrochromic device according to any one of the preceding claims.
  6. The electrochromic device according to any one of claims 1 to 5, wherein the anodic electrochromic compound is a dihydrophenazine derivative.
  7. The electrochromic device according to any one of claims 1 to 6, wherein the cathodic electrochromic compound is a pyridine derivative.
  8. The electrochromic device according to claim 7, wherein the cathodic electrochromic compound has a viologen skeleton.
  9. 9. The electrochromic device according to claim 8, wherein the cathodic electrochromic compound is a compound represented by the following general formula (11).
    Figure JPOXMLDOC01-appb-C000001

    In the general formula (11), X 1 and X 2 are each independently selected from an alkyl group, an aralkyl group and an aryl group. The alkyl group, the aralkyl group and the aryl group may have a substituent. Each of R 11 to R 18 independently represents a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryl group, a heterocyclic group, a substituted amino group, a halogen atom or an acyl group. The alkyl group, the alkoxy group, the aralkyl group, the aryl group, and the heterocyclic group may have a substituent. A 1 - and A 2 - each independently represents a monovalent anion.
    At least one of X 1 and X 2 and R 11 to R 18 is a substituent containing any element of halogen, sulfur, boron, phosphorus and silicon.
  10. The electrochromic device according to any one of claims 1 to 9, wherein the solvent is a cyclic ether.
  11. A first electrode, a second electrode, and an electrochromic layer disposed between the first electrode and the second electrode, the electrochromic layer having a solvent, and an anodic property. An electrochromic device comprising an electrochromic compound and a cathodic electrochromic compound, comprising:
    The difference between the solvation free energy in water and the solvation free energy in octanol of the colored body of the anodic electrochromic compound is 35 kcal / mol or more.
    The electrochromic device characterized in that the cathodic electrochromic compound has a substituent containing any of halogen, sulfur, boron, phosphorus and silicon.
  12. An optical filter comprising the electrochromic device according to any one of claims 1 to 11.
    And an imaging optical system having a plurality of lenses.
  13. An imaging optical system having a plurality of lenses,
    An optical filter comprising the electrochromic device according to any one of claims 1 to 11.
    And an imaging device for receiving light transmitted through the optical filter.
  14. An imaging apparatus to which an imaging optical system having a plurality of lenses can be attached,
    An optical filter comprising the electrochromic device according to any one of claims 1 to 11.
    And an imaging device for receiving light transmitted through the optical filter.
  15. A pair of substrates,
    And the electrochromic device according to any one of claims 1 to 11.
    The electrochromic device is disposed between the pair of substrates,
    A window material, characterized in that the amount of light transmitted through the pair of substrates is adjusted by the electrochromic element.
PCT/JP2018/035400 2017-10-10 2018-09-25 Electrochromic element, optical filter, lens unit, imaging device, and window material WO2019073789A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008521031A (en) * 2004-11-15 2008-06-19 ジェンテックス コーポレイション Electrochromic compounds and related media and devices
JP2012501007A (en) * 2008-08-25 2012-01-12 ジェンテックス コーポレイション Electrochromic compounds and related media and devices
JP2017021327A (en) * 2015-07-10 2017-01-26 キヤノン株式会社 Electrochromic element
JP2017146590A (en) * 2016-02-17 2017-08-24 キヤノン株式会社 Electrochromic element, drive method of the same, optical filter, lens unit and imaging apparatus

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008521031A (en) * 2004-11-15 2008-06-19 ジェンテックス コーポレイション Electrochromic compounds and related media and devices
JP2012501007A (en) * 2008-08-25 2012-01-12 ジェンテックス コーポレイション Electrochromic compounds and related media and devices
JP2017021327A (en) * 2015-07-10 2017-01-26 キヤノン株式会社 Electrochromic element
JP2017146590A (en) * 2016-02-17 2017-08-24 キヤノン株式会社 Electrochromic element, drive method of the same, optical filter, lens unit and imaging apparatus

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