JP2018005180A - Electrochromic module, lighting control film, lighting control lens and lighting control glasses - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochromic module excellent in transmissivity and a color change contrast, with less power consumption and excellent durability.SOLUTION: An electrochromic module includes a configuration with a lamination of at least two layers of electrochromic cells each having: first and second substrates arranged facing each other at an interval; first and second electrodes disposed on the first and second substrates; a first electrochromic layer containing an oxidation type electrochromic compound formed on the first electrode; a second electrochromic layer containing a reduction type electrochromic compound formed on the second electrode; and an electrolyte disposed between the first electrode and the second electrode. Each substrate on the upper and lower surfaces is the first substrate. At least one of the first substrates on the upper and lower surfaces is transparent. A substrate other than the first substrates on the upper and lower surfaces is transparent. An electrode disposed on a transparent substrate is transparent.SELECTED DRAWING: Figure 2

Description

  The present invention relates to an electrochromic module, a light control film, a light control lens, and light control glasses.

  A phenomenon in which a redox reaction occurs reversibly and a color changes reversibly by applying a voltage is called electrochromism. Electrochromism is generally formed between two electrodes facing each other, and undergoes a redox reaction in a configuration in which an electrolyte layer capable of ion conduction is filled between the electrodes. When a reduction reaction occurs in the vicinity of one of the two electrodes facing each other, an oxidation reaction that is a reverse reaction occurs in the vicinity of the other electrode.

  In an electrochromic element using electrochromism, when a light control device for controlling the light transmittance is to be obtained, three color layers of cyan (C), magenta (M), and yellow (Y) are provided. When constructing a device having a laminated structure, it is important that the device is composed of a reduced electrochromic material whose neutral state is transparent or an oxidized electrochromic material whose neutral state is transparent. . Among them, an organic electrochromic material that has high coloring efficiency and can have various colors depending on substituents is suitable.

As an application of electrochromic materials, development has been carried out for application to a light control device for controlling transmittance with electricity and a light control lens. (See Patent Document 1)
In such a light control device and light control lens, it is important to realize a high contrast ratio in a transparent state (decolored state) and a colored state. For that purpose, it is preferable that one of the pair of electrodes is formed with a layer containing an oxidized electrochromic material, and the other is formed with a layer containing a reduced electrochromic material. This is because when an electric current is passed through the element, both the oxidized electrochromic material and the reduced electrochromic material develop color, whereby a deeper color density can be obtained.

In view of the above, an electrochromic device in which an oxidized electrochromic layer and a reduced electrochromic layer are formed on electrodes, and an electrochromic module with high transmittance contrast and vivid color development are realized with low power consumption. It becomes possible.
However, in general, organic electrochromic materials have poor durability, which is a problem for practical use. In particular, in a light resistance test in which sunlight is irradiated in a colored state, the transmittance is hardly changed due to the influence of ultraviolet rays contained in sunlight or absorption of visible light, and the YI value increases.
The present invention has been made in view of the above points, and an object of the present invention is to provide an electrochromic module that is excellent in transmittance and color change contrast, consumes less power, and has excellent durability.

The electrochromic module of the present invention is
A first support and a second support provided opposite each other at an interval;
A first electrode and a second electrode provided so as to face the first support and the second support, respectively;
A first electrochromic layer containing an oxidized electrochromic compound provided on a surface of the first electrode on the second electrode side;
A second electrochromic layer containing a reduced electrochromic compound provided on the first electrode side surface of the second electrode;
An electrolyte provided between the first electrode and the second electrode;
Having an electrochromic cell having a structure in which at least two or more are stacked,
Supports that are the upper and lower surfaces are all first supports, and at least one of the first supports that are the upper and lower surfaces is transparent and supports other than the first support that is the upper and lower surfaces The body is transparent, and the electrode provided on the transparent support is required to be transparent.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the electrochromic module which is excellent in the transmittance | permeability and the contrast of a color change, has little power consumption, and was excellent in durability.

It is sectional drawing which illustrates the electrochromic cell which concerns on this invention. It is sectional drawing which illustrates the electrochromic module which concerns on this invention. It is a perspective view of an example of the light control glasses concerning the present invention.

  Hereinafter, the present invention will be described with reference to the drawings. In addition, in each drawing, the same code | symbol is attached | subjected to the same component and the overlapping description may be abbreviate | omitted.

[Structure of electrochromic module]
FIG. 1 is a cross-sectional view illustrating an electrochromic cell according to this embodiment.
FIG. 2 is a cross-sectional view illustrating the electrochromic module according to this embodiment.
In the present invention, a first support body and a second support body provided to face each other at an interval;
A first electrode and a second electrode provided so as to face the first support and the second support, respectively;
A first electrochromic layer containing an oxidized electrochromic compound provided on a surface of the first electrode on the second electrode side;
A second electrochromic layer containing a reduced electrochromic compound provided on the first electrode side surface of the second electrode;
An electrolyte provided between the first electrode and the second electrode;
In an electrochromic module in which at least two electrochromic cells having a plurality of layers are provided, the supports that are the upper and lower surfaces are all the first supports, and the first support that is the upper and lower surfaces is at least Either one is transparent, the support other than the first support serving as the upper and lower surfaces is transparent, and the electrode provided on the transparent support is transparent.
It has been found that with the above-described configuration, an element having excellent transmittance and color change contrast, low power consumption, and excellent durability can be obtained.
With such a structure, in addition to improving the contrast, the diffusion of the electrochromic material can be suppressed, so that it is possible to develop a memory property that retains the charge injected from the electrode into the electrochromic material. . The charge held in the electrochromic material is controlled mainly by injection and extraction of charges from an external circuit. This is the same operation model as a so-called secondary battery charging / discharging phenomenon. The advantage of an electrochromic element having memory characteristics as compared with a self-decoloring type electrochromic element such as the invention exemplified in Japanese Patent No. 2672083 is that power consumption can be greatly reduced. Particularly in portable applications and applications that require battery driving, power consumption is an important issue.

  The first electrochromic layer includes an oxidized electrochromic compound that is colored by an oxidation reaction, and the oxidized electrochromic compound includes, but is not limited to, a radically polymerizable compound having a triarylamine structure, and the triarylamine. It is preferable from the viewpoint of contrast and repetition durability that the electrochromic composition containing another radical polymerizable compound different from the radical polymerizable compound having a structure is crosslinked.

The second electrochromic layer includes a reduced electrochromic compound that is colored by a reduction reaction. Examples of reduced electrochromic compounds include viologen compounds and dipyridine compounds. As for the reduced electrochromic compound, a structure supported on a conductive or semiconducting nanostructure through an adsorbing group is preferable from the viewpoints of responsiveness, contrast, and repeated durability.
Details of these materials will be described later.

When the durability of the electrochromic cell by light irradiation was evaluated, it was found that the durability was different depending on the direction in which light was incident. Specifically, when light is incident from the first electrochromic layer and when light is incident from the second electrochromic layer, the case where light is incident from the first electrochromic layer is more durable. Excellent in properties. In particular, it has a great influence on the amount of light in a short wavelength region of 420 nm or less.
This is considered to be due to the fact that the conductive or semiconducting nanostructure contained in the electrochromic layer on the reduction side exhibits a photocatalytic effect by absorbing light.
For this reason, it is necessary to reduce the influence by providing a UV cut layer or the like. However, if the wavelength region of 420 nm or less is completely cut, it is not realistic because it is colored yellow.
Therefore, in the present invention, in an electrochromic module in which at least two electrochromic cells are stacked, the supports that are the upper and lower surfaces are all the first support, and the first surface that is the upper and lower surfaces. At least one of the supports was transparent, the supports other than the first support serving as the upper and lower surfaces were transparent, and the electrodes provided on the transparent support were arranged to be transparent. That is, the electrochromic layer closest to the upper and lower surfaces is the first electrochromic layer.
From the above, an electrochromic module having excellent transmittance and color change contrast, low power consumption, and excellent durability was obtained.

Hereinafter, each component of the electrochromic module will be described in detail.
(First support, second support)
The first support has a function of supporting the first electrode and the first electrochromic layer, and the second support has a function of supporting the second electrode and the second electrochromic layer. Have
As the first support and the second support (hereinafter, these supports may be simply referred to as a support), any known organic material or inorganic material may be used as long as it is a transparent material capable of supporting each layer. Can be used as they are.
As the support, for example, a glass substrate such as alkali-free glass, borosilicate glass, float glass, or soda lime glass can be used.
As the support, for example, a resin substrate such as polycarbonate resin, acrylic resin, polyethylene, polyvinyl chloride, polyester, epoxy resin, melamine resin, phenol resin, polyurethane resin, polyimide resin, or a resin film may be used. By using a resin film, it is possible to obtain a thin, light and flexible electrochromic module.
The support may be coated with a transparent insulating layer, a UV cut layer, an antireflection layer or the like in order to improve water vapor barrier properties, gas barrier properties, ultraviolet resistance, and visibility.
In addition, by using an opaque support for irregularly reflecting or specularly reflecting light for any one of the first supports, it can be used as a coloring device or a mirror for controlling reflectivity. As the opaque support, a fine particle layer for irregularly reflecting light, or a material in which bubbles or the like are appropriately mixed can be used. As the fine particles, metal oxides such as titanium oxide can be suitably used. As the layer for specular reflection, various metal materials such as Al, Pt, Mo, Ag, and Ni can be suitably used.

There is no restriction | limiting in particular as a shape of the said support body, According to the objective, it can select suitably, For example, a rectangle or a round shape may be sufficient.
The support may be a plurality of stacked layers. For example, by providing a structure in which an electrochromic module is sandwiched between two glass substrates, it is possible to improve water vapor barrier properties and gas barrier properties.

  The support may be a lens having a spherical shape. Thereby, there is little disorder of the image seen through the electrochromic module, and the improvement of a high viewing angle and design property can be expected. For example, when used for a light control lens for spectacles or a window of an automobile, it is preferable to form an electrochromic light control element on a spherical structure, particularly from the viewpoint of lightness and workability in spectacle use. A form in which all elements of the electrochromic light control device are formed on the spherical surface is preferable.

The material of the lens is not particularly limited as long as it functions as a lens for spectacles, and can be appropriately selected according to the purpose. However, a material having high transparency, thin thickness, and light weight is preferable. Moreover, the one where expansion | swelling by a heat history is as small as possible is preferable, and a material with a high glass transition temperature (Tg) and a small linear expansion coefficient are preferable.
Specifically, in addition to glass, any of those described in the technical summary document on high refractive index eyeglass lenses of the JPO can be used. For example, episulfide resin, thiourethane resin, methacrylate resin , Polycarbonate resin, urethane resin, or a mixture thereof. Furthermore, if necessary, a primer for improving the hard coat and adhesion may be formed.
In the present invention, the lens includes a lens whose power (refractive index) is not adjusted (such as a simple glass plate).

(First electrode, second electrode)
The material for the first electrode and the second electrode is not particularly limited, and a commonly used conductor can be used. As described above, the first electrode and the second electrode provided on the transparent support are transparent electrodes. However, the transparent electrode is not particularly limited as long as it is a transparent material having conductivity, depending on the purpose. Can be selected as appropriate. For example, indium oxide doped with tin (hereinafter sometimes referred to as “ITO”), tin oxide doped with fluorine (hereinafter sometimes referred to as “FTO”), tin oxide doped with antimony (hereinafter referred to as “ In some cases, inorganic materials such as zinc oxide may be used. Among these, InSnO, GaZnO, SnO, In ₂ O ₃ and ZnO are preferable.
Further, by using a mirror-reflecting layer as an opaque electrode material for any one of the first electrodes, a mirror capable of controlling the reflectance can be obtained. Various metal materials such as Al, Pt, Mo, Ag, and Ni can be suitably used as the electrode layer for specular reflection.

  In addition, carbon nanotubes with transparency and other highly conductive non-permeable materials such as Au, Ag, Pt, and Cu are formed in a fine network to improve conductivity while maintaining transparency. You may use the electrode which did. The thickness of each of the first electrode and the second electrode can be adjusted as appropriate so that the electric resistance value necessary for the oxidation-reduction reaction of the first electrochromic layer and the second electrochromic layer can be obtained.

  For example, when ITO is used as the material for the first electrode and the second electrode, the average thickness of each of the first electrode and the second electrode is preferably about 50 nm to 500 nm.

  As a manufacturing method of each of the first electrode and the second electrode, for example, a vacuum evaporation method, a sputtering method, an ion plating method, or the like can be used. However, there is no particular limitation as long as each material of the first electrode and the second electrode can be formed by coating, for example, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, Roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet Various printing methods such as a printing method can be used.

(First electrochromic layer)
The oxidized electrochromic compound used for the first electrochromic layer includes a radical polymerizable compound having a triarylamine structure and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure. It is more preferable from the viewpoint of the solubility and durability of a polymer that it is a crosslinked product obtained by crosslinking the first electrochromic composition containing.

  Here, as an aspect of the first electrochromic layer, a radical polymerizable compound having a triarylamine structure and a radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure are included. A mode in which a first electrochromic layer made of a crosslinked product obtained by crosslinking one electrochromic composition is stacked on the first electrode, and two or more layers of the first electrochromic layer are stacked on the first electrode. And a mode in which the first electrochromic layer is laminated on a part of the first electrode.

<< First Electrochromic Composition >>
The first electrochromic composition preferably contains a radical polymerizable compound having a triarylamine structure and contains another radical polymerizable compound other than the radical polymerizable compound having the triarylamine structure, More preferably, it contains a polymerization initiator, and further contains other components as required.

-Radical polymerizable compound having triarylamine structure-
The radically polymerizable compound having the triarylamine structure is important for imparting an electrochromic function having a redox reaction on the surface of the first electrode.
Examples of the radical polymerizable compound having a triarylamine structure include compounds represented by the following general formula 1.
[General Formula 1]
_An −B _m
However, n is 1 or 2, m is 0 when n = 2, and m is 0 or 1 when n = 1. At least one of A and B has a radical polymerizable functional group. The A is a structure represented by the following general formula 2, and is bonded to the B at any position from R ₁ to R ₁₅ . The B has a structure represented by the following general formula 3, and is bonded to the A at any position from R ₁₆ to R ₂₁ .
However, R ₁ to R ₂₁ are all monovalent organic groups, which may be the same or different, and at least one of the monovalent organic groups is a radical polymerizable functional group. .

-Monovalent organic group-
The monovalent organic group in the general formula 2 and the general formula 3 may each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, or a substituent. An alkoxycarbonyl group, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, an amide group, a substituent; Optionally having a monoalkylaminocarbonyl group, optionally having a dialkylaminocarbonyl group, optionally having a monoarylaminocarbonyl group, optionally having a substituent. Diarylaminocarbonyl group, sulfonic acid group, alkoxysulfonyl group which may have a substituent, aryl which may have a substituent Xylsulfonyl group, optionally substituted alkylsulfonyl group, optionally substituted arylsulfonyl group, sulfonamide group, optionally substituted monoalkylaminosulfonyl group, substituted A dialkylaminosulfonyl group which may have a group, a monoarylaminosulfonyl group which may have a substituent, a diarylaminosulfonyl group which may have a substituent, an amino group and a substituent A monoalkylamino group which may have a substituent, a dialkylamino group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkynyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryl which may have a substituent Oxy group which may have a substituent alkylthio group which may have a substituent arylthio group, and a heterocyclic group which may have a substituent.
Among these, an alkyl group, an alkoxyl group, a hydrogen atom, an aryl group, an aryloxy group, a halogen atom, an alkenyl group, and an alkynyl group are particularly preferable from the viewpoint of stable operation and light durability.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
Examples of the aryl group include a phenyl group and a naphthyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.
Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methoxyphenoxy group, and a 4-methylphenoxy group.
Examples of the heterocyclic group include carbazole, dibenzofuran, dibenzothiophene, oxadiazole, thiadiazole, and the like.

  Examples of the substituent further substituted with the substituent include an alkyl group such as a halogen atom, a nitro group, a cyano group, a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, and an aryloxy group such as a phenoxy group. Group, aryl group such as phenyl group and naphthyl group, and aralkyl group such as benzyl group and phenethyl group.

-Radically polymerizable functional group-
The radical polymerizable functional group may be any group as long as it has a carbon-carbon double bond and is capable of radical polymerization.
Examples of the radical polymerizable functional group include a 1-substituted ethylene functional group and a 1,1-substituted ethylene functional group shown below.

(1) As 1-substituted ethylene functional group, the functional group represented by the following general formula (i) is mentioned, for example.
In the general formula (i), X ₁ is a single bond, an arylene group which may have a substituent, an alkenylene group which may have a substituent, a —CO— group, a —COO— group, — CON (R ₁₀₀ ) -group [R ₁₀₀ represents hydrogen, an alkyl group, an aralkyl group or an aryl group. Or -S- group.

Examples of the arylene group of the general formula (i) include a phenylene group and a naphthylene group which may have a substituent.
Examples of the alkenylene group include an ethenylene group, a propenylene group, and a butenylene group.
Examples of the alkyl group include a methyl group and an ethyl group.
Examples of the aralkyl group include a benzyl group, a naphthylmethyl group, and a phenethyl group.
Examples of the aryl group include a phenyl group and a naphthyl group.

  Specific examples of the radical polymerizable functional group represented by the general formula (i) include a vinyl group, a styryl group, a 2-methyl-1,3-butadienyl group, a vinylcarbonyl group, an acryloyl group, an acryloyloxy group, and an acryloyl group. Examples include amide groups and vinyl thioether groups.

(2) Examples of the 1,1-substituted ethylene functional group include functional groups represented by the following general formula (ii).
However, in the general formula (ii), Y represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, cyano. Group, nitro group, alkoxy group, —COOR ₁₀₁ group [R ₁₀₁ may have a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. An aryl group, or CONR ₁₀₂ R ₁₀₃ (R ₁₀₂ and R ₁₀₃ may have a hydrogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or a substituent. Represents an aryl group and may be the same or different from each other. X ₂ represents the same substituent and alkylene group as X _{1 in the} general formula (i). However, at least one of Y and X ₂ is an oxycarbonyl group, a cyano group, an alkenylene group, or an aromatic ring.

Examples of the aryl group of the general formula (ii) include a phenyl group and a naphthyl group.
Examples of the alkyl group include a methyl group and an ethyl group.
Examples of the alkoxy group include a methoxy group and an ethoxy group.
Examples of the aralkyl group include a benzyl group, a naphthylmethyl group, and a phenethyl group.

  Specific examples of the radical polymerizable functional group represented by the general formula (ii) include an α-acryloyl chloride group, a methacryloyl group, a methacryloyloxy group, an α-cyanoethylene group, an α-cyanoacryloyloxy group, an α- A cyanophenylene group, a methacryloylamino group, etc. are mentioned.

Examples of the substituent further substituted on the substituents for X ₁ , X ₂ and Y include, for example, a halogen atom, a nitro group, a cyano group, a methyl group, an alkyl group such as an ethyl group, a methoxy group, and an ethoxy group. And aryloxy groups such as a phenoxy group, aryl groups such as a phenyl group and a naphthyl group, and aralkyl groups such as a benzyl group and a phenethyl group.

  Among the radical polymerizable functional groups, an acryloyloxy group and a methacryloyloxy group are particularly preferable.

  Preferred examples of the radically polymerizable compound having a triarylamine structure include compounds represented by the following general formulas (1-1) to (1-3).

In the general formulas (1-1) to (1-3), R ₂₇ to R ₈₉ are all monovalent organic groups, which may be the same or different from each other. At least one of the groups is a radically polymerizable functional group.
Examples of the monovalent organic group and the radical polymerizable functional group include the same as those in the general formula 1.

  Examples of the compounds represented by the general formula 1 and the compounds represented by the general formulas (1-1) to (1-3) include those shown below. The radical polymerizable compound having the triarylamine structure is not limited thereto.

-Other radical polymerizable compounds-
Unlike the radical polymerizable compound having a triarylamine structure, the other radical polymerizable compound is a compound having at least one radical polymerizable functional group.
Examples of the other radical polymerizable compound include a monofunctional radical polymerizable compound, a bifunctional radical polymerizable compound, a trifunctional or higher functional radical polymerizable compound, a functional monomer, and a radical polymerizable oligomer. Among these, a bifunctional or higher radical polymerizable compound is particularly preferable.
The radical polymerizable functional group in the other radical polymerizable compound is the same as the radical polymerizable functional group in the radical polymerizable compound having the triarylamine structure, and among these, an acryloyloxy group and a methacryloyloxy group are included. Particularly preferred.

  Examples of the monofunctional radically polymerizable compound include 2- (2-ethoxyethoxy) ethyl acrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, 2 -Ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, cyclohexyl acrylate, isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol Acrylate, phenoxytetraethylene group Call acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, styrene monomer. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the bifunctional radically polymerizable compound include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1 , 6-hexanediol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, neopentyl glycol diacrylate, and the like. These may be used individually by 1 type and may use 2 or more types together.

Examples of the tri- or higher functional radical polymerizable compound include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, and caprolactone-modified trimethylolpropane. Triacrylate, HPA modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH modified glycerol triacrylate, EO modified glycerol triacrylate, PO modified glycerol triacrylate, Tris (acryloxy) Ethyl) isocyanurate, dipentaerythritol hex Acrylate (DPHA), caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, alkyl-modified dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol triacrylate, dimethylolpropane tetraacrylate ( DTMPTA), pentaerythritol ethoxytetraacrylate, EO-modified phosphoric acid triacrylate, 2,2,5,5-tetrahydroxymethylcyclopentanone tetraacrylate, and the like. These may be used individually by 1 type and may use 2 or more types together.
In the above, EO modification refers to ethyleneoxy modification, and PO modification refers to propyleneoxy modification.

  Examples of the functional monomer include those substituted with fluorine atoms such as octafluoropentyl acrylate, 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl methacrylate, 2-perfluoroisononylethyl acrylate, and the like. No.-60503, JP-B-6-45770, acryloyl polydimethylsiloxane ethyl, methacryloyl polydimethylsiloxane ethyl, acryloyl polydimethylsiloxane propyl, acryloyl polydimethylsiloxane butyl, diacryloyl poly having 20 to 70 siloxane repeating units Examples thereof include vinyl monomers having a polysiloxane group such as dimethylsiloxane diethyl, acrylates and methacrylates. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the radical polymerizable oligomers include epoxy acrylate oligomers, urethane acrylate oligomers, and polyester acrylate oligomers.

At least one of the radical polymerizable compound having the triarylamine structure and the other radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure has two or more radical polymerizable functional groups. It is preferable from the point which forms a crosslinked material.
The content of the radical polymerizable compound having a triarylamine structure is preferably 10% by mass or more and 100% by mass or less, and more preferably 30% by mass or more and 90% by mass or less with respect to the total amount of the radical polymerizable compound.
When the content is 10% by mass or more, the electrochromic function of the first electrochromic layer can be sufficiently exhibited, the durability is good by repeated use with applied voltage, and the color development sensitivity is good.
Even when the content is 100% by mass, an electrochromic function is possible. In this case, the color development sensitivity to the thickness is the highest. Contrary to this, the compatibility with the ionic liquid necessary for charge transfer may be lowered, and therefore, repeated use due to applied voltage causes deterioration of electrical characteristics due to decrease in durability. The required electrical characteristics differ depending on the process to be used, so it cannot be said unconditionally, but considering the balance between both the color development sensitivity and the repetition durability, the content is particularly preferably 30% by mass or more and 90% by mass or less.

<< Polymerization initiator >>
The first electrochromic composition efficiently performs a crosslinking reaction between the radical polymerizable compound having the triarylamine structure and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure. In order to make it progress, it is preferable to contain a polymerization initiator as needed.
Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, and a photopolymerization initiator is preferable from the viewpoint of polymerization efficiency.

  The thermal polymerization initiator is not particularly limited and may be appropriately selected depending on the purpose. For example, 2,5-dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, benzoyl peroxide, t -Butyl cumyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoyl) hexyne-3, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide, etc. Peroxide initiators such as: azobisisobutyronitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, azobisisobutylamidine hydrochloride, azo initiators such as 4,4′-azobis-4-cyanovaleric acid, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.

  The photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy- Cyclohexyl-phenyl-ketone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2 -Hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o -Ethoxycarbonyl) oxime and other acetophenone or ketal photoinitiators; benzoin, benzoin methyl ether Benzoin ether photopolymerization initiators such as benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether; benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benbiphenyl, 4-benzoyl Benzophenone photopolymerization initiators such as phenyl ether, acrylated benzophenone, 1,4-benzoylbenzene; 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4- And thioxanthone photopolymerization initiators such as dichlorothioxanthone.

Examples of other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, and bis (2,4,6-trimethylbenzoyl) phenyl. Phosphine oxide, bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10-phenanthrene, acridine compound, triazine compound, imidazole compound, etc. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
In addition, what has a photopolymerization acceleration effect can also be used individually or in combination with the said photoinitiator. Examples thereof include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4,4′-dimethylaminobenzophenone, and the like.

  The content of the polymerization initiator is preferably 0.5 parts by mass or more and 40 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the radical polymerizable compound.

<< Other ingredients >>
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include solvents, plasticizers, leveling agents, sensitizers, dispersants, surfactants, antioxidants, fillers, and the like. Is mentioned.

<Method for Forming First Electrochromic Layer>
A first product comprising a crosslinked product obtained by crosslinking an electrochromic composition comprising the radical polymerizable compound having the triarylamine structure and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure; The electrochromic layer can be formed by the following method for forming the first electrochromic layer.
The method for forming the first electrochromic layer includes a coating step, preferably includes a crosslinking step, and further includes other steps as necessary.

-Application process-
The coating step includes an electrochromic including a radical polymerizable compound having a triarylamine structure and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure on the first electrode. It is a step of applying a composition.

  As the radical polymerizable compound having the triarylamine structure and the other radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure, those described above can be used.

A coating solution containing the radical polymerizable compound having the triarylamine structure and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure is applied. The coating solution is applied by diluting with a solvent as necessary.
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohol solvents such as methanol, ethanol, propanol and butanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ester solvents such as ethyl acetate and butyl acetate; Ether solvents such as tetrahydrofuran, dioxane and propyl ether; Halogen solvents such as dichloromethane, dichloroethane, trichloroethane and chlorobenzene; Aromatic solvents such as benzene, toluene and xylene; Methyl cellosolve And cellosolve solvents such as ethyl cellosolve and cellosolve acetate. These may be used individually by 1 type and may use 2 or more types together.
The dilution ratio with the solvent varies depending on the solubility of the first electrochromic composition, the coating method, the thickness of the target electrochromic layer, and the like, and can be appropriately selected.
The application can be performed, for example, by a dip coating method, a spray coating method, a bead coating method, a ring coating method, or the like.

-Crosslinking step-
The crosslinking step is a step of crosslinking by applying heating or light energy to the applied first electrochromic composition.

After applying the first electrochromic composition onto the first electrode, energy is applied from the outside and cured to form the first electrochromic layer.
Examples of the external energy include heat, light, and radiation.
The heat energy is applied by heating from the coating surface side or the support side using air, a gas such as nitrogen, steam, various heat media, infrared rays, or electromagnetic waves.
The heating temperature is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C. or higher and 170 ° C. or lower.

As the energy of the light, a UV irradiation light source such as a high pressure mercury lamp or a metal halide lamp having an emission wavelength mainly in ultraviolet light (UV) can be used, but it is visible according to the absorption wavelength of the radical polymerizable substance or the photopolymerization initiator. A light source can also be selected.
Irradiation dose of UV is not particularly limited and may be appropriately selected depending on the intended purpose, 5 mW / cm ² or more 15,000 MW / cm ² or less.

  An electrochromic composition comprising, as the first electrochromic layer, a radical polymerizable compound having the triarylamine structure and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure. Examples of the composition other than the crosslinked product obtained by crosslinking the composition containing at least one selected from a Prussian blue complex and nickel oxide. As a method for forming the first electrochromic layer when these are used, for example, a vacuum deposition method, a sputtering method, an ion rating method, or the like can be used. Further, as long as the material of the first electrochromic layer can be applied and formed, for example, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, and a wire bar coating method. Various printing methods such as dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing method, etc. Can be used.

  The average thickness of the first electrochromic layer is preferably 0.1 μm or more and 30 μm or less, and more preferably 0.4 μm or more and 10 μm or less.

(Second electrochromic layer)
Examples of the reduced electrochromic compound used in the second electrochromic layer include azobenzene, anthraquinone, diarylethene, dihydroprene, dipyridine, styryl, styryl spiropyran, spirooxazine, spirothiopyran, Thioindigo, tetrathiafulvalene, terephthalic acid, triphenylmethane, triphenylamine, naphthopyran, viologen, pyrazoline, phenazine, phenylenediamine, phenoxazine, phenothiazine, phthalocyanine, fluorane And low molecular organic electrochromic compounds such as fulgide, benzopyran, and metallocene. These may be used individually by 1 type and may use 2 or more types together.

Among these, viologen compounds and dipyridine compounds are preferable from the viewpoint of low color development / discoloration potential and good color values.
Examples of the viologen compound include compounds described in Japanese Patent No. 39555641 and Japanese Patent Application Laid-Open No. 2007-171781.
The viologen-based compound is preferably used in combination with titanium oxide particles as described later. Thus, by using in combination with titanium oxide particles, there is an advantage that a high optical density and a high contrast ratio can be maintained.

Examples of the dipyridine-based compound include compounds described in JP 2007-171781 A and JP 2008-116718 A.
Among these, a dipyridine compound represented by the following general formula 4 is preferable from the viewpoint of exhibiting a good color value.

In the general formula 4, R 1 and R 2 each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group which may have a substituent, and at least one of R 1 and R 2 is COOH, PO ( OH) ₂ and Si (OC _k H _{2k + 1} ) ₃ (wherein k represents 1 to 20).
In the general formula 4, X represents a monovalent anion. The monovalent anion is not particularly limited as long as it forms a stable pair with the cation moiety, and can be appropriately selected depending on the purpose. For example, Br ion (Br ⁻ ), Cl ion (Cl ⁻⁾ ), ClO ₄ ions (ClO ₄ ⁻ ), PF ₆ ions (PF ₆ ⁻ ), BF ₄ ions (BF ₄ ⁻ ), and the like.
In the general formula 4, n, m, and l represent 0, 1 or 2. A, B, and C each independently represent a C 1-20 alkyl group, aryl group, or heterocyclic group that may have a substituent.

The second electrochromic layer may have a structure in which an organic electrochromic compound is supported on conductive or semiconductive particles. Specifically, it is a structure in which fine particles having a particle size of about 5 nm to 50 nm are sintered on the electrode surface, and an organic electrochromic compound having a polar group such as phosphonic acid, carboxyl group, silanol group or the like is adsorbed on the fine particle surface. .
In such a structure, electrons are efficiently injected into the organic electrochromic compound by utilizing the large surface effect of the fine particles, so that a high-speed response is possible as compared with a conventional electrochromic display element. Furthermore, since a transparent film can be formed as a display layer by using fine particles, a high color density of the electrochromic dye can be obtained. Also, a plurality of types of organic electrochromic compounds can be supported on conductive or semiconductive particles.

There is no restriction | limiting in particular as said electroconductive or semiconductive particle, Although it can select suitably according to the objective, A metal oxide is preferable. Examples of the metal oxide include titanium oxide, zinc oxide, tin oxide, zirconium oxide, cerium oxide, yttrium oxide, boron oxide, magnesium oxide, strontium titanate, potassium titanate, barium titanate, calcium titanate, and oxidation. Examples include metal oxides mainly composed of calcium, ferrite, hafnium oxide, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide, vanadium oxide, aluminosilicate, calcium phosphate, aluminosilicate, etc. It is done. These may be used individually by 1 type and may use 2 or more types together.
Among these, titanium oxide, zinc oxide, tin oxide, zirconium oxide, iron oxide, magnesium oxide, indium oxide, and tungsten oxide are particularly preferable from the viewpoint of electrical characteristics such as electrical conductivity and physical characteristics such as optical properties. preferable.

  The shape of the conductive or semiconductive particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, in order to efficiently carry the electrochromic compound, the surface area per unit volume (hereinafter referred to as specific surface area) A large shape is used. For example, when the fine particle is an aggregate of nanoparticles, it has a large specific surface area, so that the electrochromic compound is more efficiently supported and the display contrast ratio of color development and decoloration is excellent.

  As a method for forming the second electrochromic layer, for example, a vacuum deposition method, a sputtering method, an ion rating method, or the like can be used. Further, as long as the material of the second electrochromic layer can be formed by coating, for example, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method Various printing methods such as dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing method, etc. Can be used.

The average thickness of the second electrochromic layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.2 μm to 5.0 μm. When the average thickness is less than 0.2 μm, it may be difficult to obtain a color density, and when it exceeds 5.0 μm, the manufacturing cost increases and the visibility may be easily lowered by coloring.
The electrochromic layer and the conductive or semiconducting particle layer can be formed by vacuum film formation, but it is preferably coated and formed as a particle-dispersed paste from the viewpoint of productivity.

<Electrolyte>
The electrolyte is filled between the first electrode and the second electrode.
Examples of the electrolyte include inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acids, and supporting salts of alkalis. Specifically, LiClO ₄ , LiBF ₄ can be used. , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ COO, KCl, NaClO ₃ , NaCl, NaBF ₄ , NaSCN, KBF ₄ , Mg (ClO ₄ ) ₂ , Mg (BF ₄ ) _{2 and the} like.

An ionic liquid can also be used as the electrolyte material. Among these, the organic ionic liquid is preferably used because it has a molecular structure showing the liquid in a wide temperature range including room temperature.
As the molecular structure of the organic ionic liquid, examples of the cationic component include imidazole derivatives such as N, N-dimethylimidazole salt, N, N-methylethylimidazole salt, and N, N-methylpropylimidazole salt; Examples thereof include pyridinium derivatives such as N-dimethylpyridinium salt and N, N-methylpropylpyridinium salt; aliphatic quaternary ammonium compounds such as trimethylpropylammonium salt, trimethylhexylammonium salt and triethylhexylammonium salt.
As the anion component, it is preferable to use a compound containing fluorine in consideration of stability in the atmosphere. For example, BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , PF ₄ ⁻ , (CF ₃ SO ₂ ) ₂ N- ^{and the} like.
As the electrolyte material, it is preferable to use an ionic liquid in which the cation component and the anion component are arbitrarily combined.
The ionic liquid may be directly dissolved in any of photopolymerizable monomers, oligomers, and liquid crystal materials. If the solubility is poor, the solution may be dissolved in a small amount of solvent and mixed with any of photopolymerizable monomers, oligomers, and liquid crystal materials.

  Examples of the solvent include propylene carbonate, acetonitrile, γ-butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, and polyethylene glycol. , Alcohols, or a mixed solvent thereof.

The electrolyte need not be a low-viscosity liquid, and can take various forms such as a gel, a polymer cross-linked type, and a liquid crystal dispersion type. By forming the electrolyte in a gel or solid form, advantages such as improved element strength and improved reliability can be obtained.
As a solidification method, it is preferable to hold the electrolyte and the solvent in the polymer resin. This is because high ionic conductivity and solid strength can be obtained.
Further, the polymer resin is preferably a photocurable resin. This is because an electrochromic cell can be manufactured at a low temperature and in a short time as compared with a method of thinning by thermal polymerization or evaporation of a solvent.

  There is no restriction | limiting in particular in the average thickness of the electrolyte layer which consists of said electrolyte, Although it can select suitably according to the objective, 100 nm or more and 100 micrometers or less are preferable.

<Other members>
There is no restriction | limiting in particular as said other member, According to the objective, it can select suitably, For example, an insulating porous layer, a sealing material, etc. are mentioned.

-Insulating porous layer-
The insulating porous layer has a function of holding the electrolyte while isolating the first electrode and the second electrode so as to be electrically insulated.
The material of the insulating porous layer is not particularly limited as long as it is transparent and porous. However, organic materials and inorganic materials having high insulating properties and durability and excellent film forming properties, and their It is preferable to use a complex.
The insulating porous layer is preferably provided between the first electrochromic layer and the second electrochromic layer.

  As the method for forming the insulating porous layer, a sintering method (using fine pores or inorganic particles that are partially fused by adding a binder or the like and utilizing pores formed between the particles), an extraction method ( After forming a constituent layer with an organic or inorganic substance soluble in a solvent and a binder that does not dissolve in the solvent, the organic or inorganic substance is dissolved with a solvent to obtain pores).

As the method for forming the insulating porous layer, a foaming method in which a polymer is foamed by heating or degassing, etc., a phase change in which a mixture of polymers is phase-separated by operating a good solvent and a poor solvent. Alternatively, a forming method such as a radiation irradiation method in which pores are formed by radiating various types of radiation may be used. Specific examples include polymer mixed particle films containing metal oxide fine particles (such as SiO ₂ particles and Al ₂ O ₃ particles) and a polymer binder, porous organic films (such as polyurethane resins and polyethylene resins), and porous film shapes. An inorganic insulating material film formed in the above. Among these, SiO ₂ particles can be suitably used from the viewpoint of excellent insulating properties, relatively low refractive index, and low cost.

As a method for forming the insulating porous layer, for example, a vacuum deposition method, a sputtering method, an ion rating method, or the like can be used. In addition, as long as the insulating porous layer material can be formed by coating, spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating Various printing methods such as a method, a slit coating method, a capillary coating method, a spray coating method, a nozzle coating method, a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an inkjet printing method. it can.
There is no restriction | limiting in particular in the average thickness of the said insulating porous layer, Although it can select suitably according to the objective, 0.5 to 3 micrometer is preferable.

(Encapsulant)
In the electrochromic module, it is preferable to provide a sealing material that seals the side surfaces of the bonded layers. By providing the sealing material, there are an effect of preventing leakage of the electrolyte and an effect of preventing the entry of unnecessary things for the stable operation of the electrochromic module such as moisture and oxygen in the atmosphere. The sealing material is not particularly limited, and for example, an ultraviolet curable resin or a thermosetting resin can be used, and specific examples include acrylic, urethane, and epoxy resins.

By using the first support and the second support as transparent resin films, a light control film can be obtained.
Moreover, it can be set as a light control lens by using the said 1st support body and / or 2nd support body as an optical lens.
Then, by incorporating the light control film or light control lens into a spectacle frame on which a power source and a switch are mounted, light control glasses can be obtained.
In dimming glasses with a dimming lens, power supply, optical sensor, switch, wiring, etc. mounted on the spectacles, the user controls the lens transmittance with an electrical signal, or reduces the lens transmittance in bright places and in dark places It is possible to control the transmittance to an optimum state by sensing the brightness of the environment, such as increasing the transmittance of the lens. In the past, photochromic light control lenses that change color with ultraviolet rays have been used, but there have been problems such as inability to be controlled by the user and slow response. With the light control glasses of the present invention, it becomes possible to control, and the problem that the reaction is slow can be solved.
The light control glasses include light control goggles.

  The preferred embodiment of the present invention has been described in detail above, but the present invention is not limited to the specific embodiment, and within the scope of the gist of the embodiment of the present invention described in the claims, Various modifications and changes are possible

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to a following example. Note that “parts” used in the examples all represent parts by mass.

Example 1
(Formation of first electrochromic layer)
First, an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) in which ITO as a first electrode was formed on a glass substrate as a first support was prepared. And mass ratio (57: 3: 140: 800) of polyethylene glycol diacrylate (Nippon Kayaku, PEG400DA), photoinitiator (BASF, IRGACURE184), a compound represented by the following structural formula A, and 2-butanone The solution mixed in was prepared. Thereafter, the prepared solution is applied onto an ITO glass substrate by a spin coating method, UV-cured in a nitrogen atmosphere, and the first electrode having a thickness of 1.1 μm containing the compound represented by the structural formula A is formed on the first electrode. An electrochromic layer was formed.

(Formation of insulating porous layer)
Next, a SiO ₂ fine particle dispersion liquid (silica solid content concentration 24.8 mass%, polyvinyl alcohol 1.2 mass%, and water 74 mass%) having an average primary particle diameter of 20 nm is spin-coated on the first electrochromic layer. The insulating porous layer was formed by coating by the method. The thickness of the formed insulating porous layer was about 2 μm.

(Formation of second electrochromic layer)
First, an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) in which ITO as a second electrode was formed on a glass substrate as a second support was prepared. Then, a titanium oxide nanoparticle dispersion (trade name: SP210, manufactured by Showa Titanium Co., Ltd., average particle size: about 20 nm) was applied on the second electrode by a spin coating method. And the nanostructure semiconductor material which consists of a titanium oxide particle film of about 1.0 micrometer was formed by performing an annealing process for 15 minutes at 120 degreeC.

Next, 2,2,3,3-tetrafluoropropanol (hereinafter abbreviated as “TFP”) containing 1% by mass of an electrochromic compound represented by the following structural formula C on the obtained titanium oxide particle film. The solution was applied by spin coating. And the annealing process for 10 minutes was performed at 120 degreeC. Thus, the second electrochromic layer made of the titanium oxide particle film and the electrochromic compound was formed.
The first substrate and the second substrate thus fabricated were bonded so that the electrochromic layers face each other, and the following materials as the electrolyte were filled between the substrates.
Electrolytic solution: 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (manufactured by Sigma-Aldrich)
Thus, an electrochromic cell was produced.

  Two prepared electrochromic cells were prepared, and each was bonded using an optical adhesive so that the first electrochromic layer was on the outside as shown in FIG. An electrochromic module was produced as described above.

(Evaluation of operating characteristics)
The optical characteristics of the produced electrochromic module were measured with a USB 4000 manufactured by Ocean Optics for the transmittance at the absorption maximum wavelength λmax in the visible region (400 nm to 800 nm).
Moreover, based on JISK7373, YI value was computed using standard illuminant D65 and XYZ color system.
The transmittance was 68% and the YI value was 2.1.
In addition, a voltage of -2.0 V was applied to the first electrode for 5 seconds with respect to the second electrode. At that time, the transmittance changed from 68% to 2% or less.
Further, a voltage of +0.5 V was applied to the first electrode for 3 seconds with respect to the second electrode. At that time, the transmittance changed from 2% or less to 68%.

(Light resistance test)
The produced electrochromic module was irradiated with SUNTEST CP + at a light amount of 750 W / m ^{2 for} 50 hours as a pseudo solar light source in a colored state with a transmittance of about 2%. As a result, the transmittance was 57% and the YI value was 28.

Comparative Example 1
Two electrochromic cells prepared in the same manner as in Example 1 were prepared, and each was bonded using an optical adhesive layer such that the second electrochromic layer was on the outside. Except for this point, an electrochromic module was fabricated in the same manner as in Example 1.
(Evaluation of operating characteristics)
The optical characteristics of the produced electrochromic module were measured with a USB 4000 manufactured by Ocean Optics for the transmittance at the absorption maximum wavelength λmax in the visible region (400 nm to 800 nm).
Moreover, based on JISK7373, YI value was computed using standard illuminant D65 and XYZ color system.
The transmittance was 69% and the YI value was 2.0, which was almost the same value as in Example 1.
In addition, a voltage of -2.0 V was applied to the first electrode for 5 seconds with respect to the second electrode. At that time, the transmittance changed from 69% to 2% or less.
Further, a voltage of +0.5 V was applied to the first electrode for 3 seconds with respect to the second electrode. At that time, the transmittance changed from 2% or less to 69%.
(Light resistance test)
The produced electrochromic module was irradiated with light of 750 W / m ^{2 for} 50 hours as a simulated solar light source in a colored state with a transmittance of about 2% with SUNTEST CP +. As a result, the transmittance was 45% and the YI value was 35.
When the results of Example 1 and Comparative Example 1 were compared, it was confirmed in the present invention that the transmittance decrease and yellowing after the light resistance test were reduced, and the durability was improved.

Example 2
In the first electrochromic layer, an electrochromic module similar to that of Example 1 was produced except that a material represented by the following structural formula B was used instead of the compound represented by the structural formula A.

(Evaluation of operating characteristics)
The optical characteristics of the produced electrochromic module were measured with a USB 4000 manufactured by Ocean Optics for the transmittance at the absorption maximum wavelength λmax in the visible region (400 nm to 800 nm).
Moreover, based on JISK7373, YI value was computed using standard illuminant D65 and XYZ color system.
The transmittance was 67% and the YI value was 2.2.
In addition, a voltage of -2.0 V was applied to the first electrode for 5 seconds with respect to the second electrode. At that time, the transmittance changed from 67% to 8% or less.
Further, a voltage of +0.5 V was applied to the first electrode for 3 seconds with respect to the second electrode. At that time, the transmittance changed from 8% or less to 67%.

(Light resistance test)
The produced electrochromic module was irradiated with SUNTEST CP + at a light amount of 750 W / m ^{2 for} 50 hours as a pseudo solar light source in a colored state with a transmittance of about 8%. As a result, the transmittance was 59% and the YI value was 18.

Comparative Example 2
In the first electrochromic layer, an electrochromic module similar to that of Comparative Example 1 was produced, except that the material represented by the structural formula B was used instead of the compound represented by the structural formula A.
(Evaluation of operating characteristics)
The optical characteristics of the produced electrochromic module were measured with a USB 4000 manufactured by Ocean Optics for the transmittance at the absorption maximum wavelength λmax in the visible region (400 nm to 800 nm).
Moreover, based on JISK7373, YI value was computed using standard illuminant D65 and XYZ color system.
The transmittance was 67% and the YI value was 2.1.
In addition, a voltage of -2.0 V was applied to the first electrode for 5 seconds with respect to the second electrode. At that time, the transmittance changed from 67% to 7% or less.
Further, a voltage of +0.5 V was applied to the first electrode for 3 seconds with respect to the second electrode. At that time, the transmittance changed from 7% or less to 67%.

(Light resistance test)
The produced electrochromic module was irradiated with SUNTEST CP + at a light amount of 750 W / m ^{2 for} 50 hours as a pseudo solar light source in a colored state with a transmittance of about 7%. As a result, the transmittance was 52% and the YI value was 25.

Example 3
In the second electrochromic layer, an electrochromic module similar to that of Example 1 was produced except that a material represented by the following structural formula D was used instead of the compound represented by the structural formula C.

(Evaluation of operating characteristics)
The optical characteristics of the produced electrochromic module were measured with a USB 4000 manufactured by Ocean Optics for the transmittance at the absorption maximum wavelength λmax in the visible region (400 nm to 800 nm).
Moreover, based on JISK7373, YI value was computed using standard illuminant D65 and XYZ color system.
The transmittance was 69% and the YI value was 1.8.
In addition, a voltage of -2.0 V was applied to the first electrode for 5 seconds with respect to the second electrode. At that time, the transmittance changed from 69% to 4% or less.
Further, a voltage of +0.5 V was applied to the first electrode for 3 seconds with respect to the second electrode. At that time, the transmittance changed from 4% or less to 69%.

(Light resistance test)
The produced electrochromic module was irradiated with SUNTEST CP + at a light amount of 750 W / m ^{2 for} 50 hours as a pseudo solar light source in a colored state with a transmittance of about 4%. As a result, the transmittance was 56% and the YI value was 31.

Comparative Example 3
In the second electrochromic layer, an electrochromic module similar to that of Comparative Example 1 was produced except that the material represented by the structural formula D was used instead of the compound represented by the structural formula C.
(Evaluation of operating characteristics)
The optical characteristics of the produced electrochromic module were measured with a USB 4000 manufactured by Ocean Optics for the transmittance at the absorption maximum wavelength λmax in the visible region (400 nm to 800 nm).
Moreover, based on JISK7373, YI value was computed using standard illuminant D65 and XYZ color system.
The transmittance was 67% and the YI value was 1.7.
In addition, a voltage of -2.0 V was applied to the first electrode for 5 seconds with respect to the second electrode. At that time, the transmittance changed from 67% to 5% or less.
Further, a voltage of +0.5 V was applied to the first electrode for 3 seconds with respect to the second electrode. At that time, the transmittance changed from 5% or less to 67%.

(Light resistance test)
The produced electrochromic module was irradiated with SUNTEST CP + at a light amount of 750 W / m ^{2 for} 50 hours as a pseudo solar light source in a colored state with a transmittance of about 5%. As a result, the transmittance was 51% and the YI value was 39.

Example 4
In the second electrochromic layer, an electrochromic module element similar to that of Example 2 was produced except that the material represented by the structural formula D was used instead of the compound represented by the structural formula C.

(Evaluation of operating characteristics)
The optical characteristics of the produced electrochromic module were measured with a USB 4000 manufactured by Ocean Optics for the transmittance at the absorption maximum wavelength λmax in the visible region (400 nm to 800 nm).
Moreover, based on JISK7373, YI value was computed using standard illuminant D65 and XYZ color system.
The transmittance was 68% and the YI value was 2.0.
In addition, a voltage of -2.0 V was applied to the first electrode for 5 seconds with respect to the second electrode. At that time, the transmittance changed from 68% to 11% or less.
Further, a voltage of +0.5 V was applied to the first electrode for 3 seconds with respect to the second electrode. At that time, the transmittance changed from 11% or less to 68%.

(Light resistance test)
The produced electrochromic module was irradiated with SUNTEST CP + at a light amount of 750 W / m ^{2 for} 50 hours as a pseudo solar light source in a colored state with a transmittance of about 11%. As a result, the transmittance was 57% and the YI value was 25.

Comparative Example 4
In the second electrochromic layer, an electrochromic module similar to that of Comparative Example 2 was produced except that the material represented by the structural formula D was used instead of the compound represented by the structural formula C.
(Evaluation of operating characteristics)
The optical characteristics of the produced electrochromic module were measured with a USB 4000 manufactured by Ocean Optics for the transmittance at the absorption maximum wavelength λmax in the visible region (400 nm to 800 nm).
Moreover, based on JISK7373, YI value was computed using standard illuminant D65 and XYZ color system.
The transmittance was 67% and the YI value was 1.9.
In addition, a voltage of -2.0 V was applied to the first electrode for 5 seconds with respect to the second electrode. At that time, the transmittance changed from 67% to 10% or less.
Further, a voltage of +0.5 V was applied to the first electrode for 3 seconds with respect to the second electrode. At that time, the transmittance changed from 10% or less to 67%.

(Light resistance test)
The produced electrochromic module was irradiated with SUNTEST CP + at a light amount of 750 W / m ^{2 for} 50 hours as a pseudo solar light source in a colored state with a transmittance of about 10%. As a result, the transmittance was 52% and the YI value was 34.

Example 5
An electrochromic light control lens was produced in the same manner as in Example 1 except that a polycarbonate resin lens having a thickness of 2 mm was used as the first support and the second support.
The produced electrochromic dimming lens was incorporated in a spectacle frame to produce electrochromic dimming glasses as shown in FIG. In addition, a driving power supply, a signal control circuit, a switch, and wiring were mounted on the spectacle frame.
It was confirmed that when the color switch was input, the transmittance of the lens was lowered, and when the switch of decoloring was input, the transmittance of the lens was increased.
(Evaluation of operating characteristics)
The optical characteristics of the produced electrochromic light control glasses were measured with a USB 4000 manufactured by Ocean Optics for the transmittance at the absorption maximum wavelength λmax in the visible region (400 nm to 800 nm).
Moreover, based on JISK7373, YI value was computed using standard illuminant D65 and XYZ color system.
The transmittance was 67% and the YI value was 2.0.
In addition, a voltage of -2.0 V was applied to the first electrode for 5 seconds with respect to the second electrode. At that time, the transmittance changed from 67% to 2% or less.
Further, a voltage of +0.5 V was applied to the first electrode for 3 seconds with respect to the second electrode. At that time, the transmittance changed from 2% or less to 67%.

JP 2015-014743 A

Claims (6)

A first support and a second support provided opposite each other at an interval;
A first electrode and a second electrode provided so as to face the first support and the second support, respectively;
A first electrochromic layer containing an oxidized electrochromic compound provided on a surface of the first electrode on the second electrode side;
A second electrochromic layer containing a reduced electrochromic compound provided on the first electrode side surface of the second electrode;
An electrolyte provided between the first electrode and the second electrode;
Having an electrochromic cell having a structure in which at least two or more are stacked,
Supports that are the upper and lower surfaces are all first supports, and at least one of the first supports that are the upper and lower surfaces is transparent and supports other than the first support that is the upper and lower surfaces An electrochromic module in which the body is transparent and the electrodes provided on the transparent support are transparent. Crosslinking in which the oxidized electrochromic compound crosslinks a radical polymerizable compound having a triarylamine structure and an electrochromic composition containing another radical polymerizable compound different from the radical polymerizable compound having the triarylamine structure Including things,
The electrochromic module according to claim 1. The reduced electrochromic compound includes semiconductive metal oxide particles,
The electrochromic module according to claim 1 or 2.   It is a light control film using the electrochromic module in any one of Claims 1 thru | or 3, Comprising: The light control film in which a 1st support body and a 2nd support body consist of a transparent resin film.   It is a light control lens using the electrochromic module in any one of Claims 1 thru | or 3, Comprising: The light control lens which a 1st support body and / or a 2nd support body consist of an optical lens.   Light control glasses in which the light control film according to claim 4 or the light control lens according to claim 5 is incorporated in a spectacle frame on which a power source and a switch are mounted.