JP6572523B2 - Electrochromic light control device - Google Patents

Description

  The present invention relates to an electrochromic light control device.

  A phenomenon in which a redox reaction occurs reversibly and a color changes reversibly by applying a voltage is called electrochromism. An electrochromic material exhibiting such electrochromism is generally formed between two opposing electrodes, and undergoes an oxidation-reduction reaction in a configuration in which an ion conductive electrolyte layer is filled between the electrodes. When a reduction reaction occurs in the vicinity of one of the two opposed electrodes, an oxidation reaction that is an inverse reaction occurs in the vicinity of the second electrode.

  As an application of the electrochromic material, there is an electrochromic dimming element capable of adjusting the transmitted light intensity to an arbitrary intensity. The electrochromic dimming element is a dimming window that adjusts the intensity of light taken into the room by using it in a building window, a dimming lens that can reduce glare according to each individual's sense by using it in a spectacle lens, Widely used as an anti-glare mirror that weakens low-angle sunlight and reflected light from the headlights of the following cars. In such an electrochromic light control device, when it is intended to obtain a high contrast ratio, it is important that the electrochromic light control device is made of a material having a state where the extinction coefficient is as small as possible in a desired wavelength region.

Examples of the material that can solve the above-described problems include viologen compounds that exhibit an electrochromic phenomenon in which a neutral state is a transparent state in a visible range and a color is generated in a reduced state. It has been reported that the viologen compound can maintain a high optical density and a high contrast ratio when combined with titanium oxide fine particles having a small extinction coefficient in the visible region. In particular, it is suitably used in a reflective display element using an electrochromic material.
In addition, as an electrochromic material that is neutral in a transparent state and develops color in an oxidized state, a triarylamine compound or the like has been reported (see Non-Patent Document 1 and Non-Patent Document 2).

  However, Non-Patent Document 1 discloses an electrochromic device in which a copolymer material with a triarylamine compound and poly (choline methylacrylate) (PCM) are laminated in ten or more layers. In addition, it is difficult to say that the manufacturing process is complicated and is a practical disclosure, and the repetition of about 500 times in the best configuration has been evaluated, but no light transmission is disclosed.

  Further, Non-Patent Document 2 shows that titanium oxide is used as the support particle for the triarylamine compound and has a good repeatability. However, the titanium oxide is known as a high refractive index material having a refractive index of about 2.5. This is remarkably high refractive index among the members constituting the electrochromic light control device, and light scattering is likely to occur at the interface with other members, resulting in a decrease in light transmittance.

  Therefore, the present invention aims to solve the above-described problems and achieve the following object. That is, an object of the present invention is to provide an electrochromic light control device using a triarylamine that is capable of stable operation and excellent in light transmittance.

The electrochromic dimming device of the present invention as a means for solving the above-described problems includes a first electrode, a second electrode, and an electrolyte between the first electrode and the second electrode. An electrochromic light control device comprising:
The first electrode has a polymer obtained by polymerizing an electrochromic composition containing a radical polymerizable compound having triarylamine,
The member which comprises the said electrochromic light control element has a light transmittance, It is characterized by the above-mentioned.

  According to the present invention, there is provided an electrochromic light control device using a triarylamine that can solve the above-described problems, can achieve the above-described object, can be stably operated, and has excellent light transmittance. Can do.

FIG. 1 is a schematic view showing an example of the electrochromic light control device of the present invention. FIG. 2 is a schematic view showing an example of the structure of glasses using the electrochromic light control device of the present invention.

(Electrochromic light control device)
The electrochromic light control device of the present invention includes a first electrode, a second electrode, an electrolyte between the first electrode and the second electrode, and a support. It is preferable to have other members as required.

As a result of extensive studies by the present inventors in order to solve the above-mentioned problems, attention was paid to a heat- or photo-curable triarylamine compound that is practically used for a photoreceptor of an electrophotographic copying machine.
The photoconductor containing the heat- or photo-curable triarylamine compound is an important member related to other than the fixing of the development process (charging, exposure, development, transfer, separation, fixing) of the copying machine.
During the development process of the copying machine, the photoreceptor is always exposed to the atmosphere containing moisture and oxygen. In addition, it is designed to be exposed to strong light in the process of exposure and charge removal and to repeat electrostatic charge and discharge at high speed.
The electrochromic device was studied by paying attention to the resistance to light durability and the repeated resistance to electrostatic charge and discharge similar to the oxidation-reduction process. In other words, select a skeleton of a heat- or photo-curable triarylamine compound that can be applied to the required physical properties for application to electrochromic devices (neutral, transparent, soluble, stackable, etc.) The inventors have found that by adapting the electrochromic device to the optimum configuration conditions and configuration position, the electrochromic device has superior effects, in particular, resistance to repetition and light durability.

In the present invention, the first electrode has a polymer obtained by polymerizing an electrochromic composition containing a radical polymerizable compound having a triarylamine.
The first electrode is a cross-linked cross-linked electrochromic composition containing a radical polymerizable compound having a triarylamine and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine. It is preferable from the viewpoint of solubility and durability of the polymer.

Here, “the first electrode has a polymer obtained by polymerizing an electrochromic composition containing a radical polymerizable compound having triarylamine” means an electrochromic containing a radical polymerizable compound having triarylamine. An aspect in which an electrochromic layer made of a polymer obtained by polymerizing a composition is laminated on the first electrode, an aspect in which two or more electrochromic layers are laminated on the first electrode, and the electrochromic layer in the first electrode The aspect laminated | stacked on one part on 1 electrode, etc. are mentioned.
Further, the above-mentioned “first electrode is a cross-linked cross-linked electrochromic composition containing a radical polymerizable compound having a triarylamine and another radical polymerizable compound different from the radical polymerizable compound having a triarylamine” "Having a product" is composed of a crosslinked product obtained by crosslinking an electrochromic composition containing a radical polymerizable compound having a triarylamine and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine. A mode in which an electrochromic layer is stacked on the first electrode, a mode in which two or more layers of the electrochromic layer are stacked on the first electrode, and a layer on which the electrochromic layer is stacked on the first electrode And the like.

In this invention, the member which comprises an electrochromic light control element has a light transmittance.
Here, “having light transmittance” means that the average value of light transmittance in the visible light region (400 nm to 700 nm) is 80% or more.
The average value of the light transmittance is obtained by arithmetically averaging the transmittance values in the visible light region (400 nm to 700 nm) obtained at 1 nm intervals.
The light transmittance can be measured, for example, using a spectrophotometer (manufactured by Hitachi, Ltd., U-33000 type spectrophotometer).
The haze value of the member constituting the electrochromic light control device is preferably 2% or less, and more preferably 0.5% or less.
The haze value can be measured using, for example, a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH-5000).
As a member which comprises the said electrochromic light control element, an electrode, an electrochromic layer, an electrolyte layer, a support body, an insulating porous layer, a deterioration prevention layer, a protective layer etc. are mentioned, for example.

In the electrochromic light control device, it is desired to realize a high contrast ratio. That is, it is required that the color density is high in the colored state and the transmittance is high in the decolored state. In order to increase the color density, it is preferable to increase the thickness of the electrochromic material layer used for the electrode surface layer. However, when the absorbance of the electrochromic material itself is large, there is a problem that the light transmittance in a decolored state is lowered. As a material that can solve this problem, a viologen compound that exhibits an electrochromic phenomenon in which a neutral state is a transparent state in a visible range and color develops in a reduced state can be given. It has been reported that the viologen compound can obtain a high optical density and a good response speed (coloring and decoloring speed) when combined with titanium oxide particles having a small extinction coefficient in the visible region. In particular, it is suitably used in a reflective display element using an electrochromic material. However, problems still remain in this method. Titanium oxide is known as a high refractive index material having a refractive index of about 2.5, which is compared with members constituting an electrochromic light control device (for example, electrodes, electrochromic layers, electrolyte layers, etc.). Remarkably high value. For this reason, reflection and light scattering at the interface are likely to occur, resulting in a decrease in light transmittance.
Further, for example, in Japanese Patent Application Laid-Open No. 2012-98628, a plurality of titanium oxide particle layers having different densities are used adjacent to each other, thereby reducing reflected light generated at an interface with an electrode or an electrolyte layer. However, with this proposed method, the manufacturing process becomes complicated and it is difficult to say that it is practical.
In the present invention, an electrochromic layer formed by polymerizing a composition containing a radical polymerizable compound having triarylamine on the first electrode without using a high refractive index material such as titanium oxide described above. It has been found that the provision of an electrochromic light control device excellent in contrast ratio, repetition durability, and response speed can be provided.

<Electrochromic composition>
The electrochromic composition preferably contains a radical polymerizable compound having a triarylamine, and contains a radical polymerizable compound other than the radical polymerizable compound having a triarylamine and a filler, and a polymerization initiator. More preferably, it contains other components as necessary.

<< Radically polymerizable compound having triarylamine >>
The radically polymerizable compound having the triarylamine 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 include compounds represented by the following general formula 1.
[General Formula 1]
_An −B _m
However, when n = 2, m is 0, and when n = 1, m is 0 or 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 of R ₁ to R ₁₅ . The B is a structure represented by the following general formula 3, and is bonded to the A at any position from R ₁₆ to R ₂₁ .
[General formula 2]
[General formula 3]
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 alkoxy 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 aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl 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.
However, in the general formula (i), X ₁ represents an arylene group which may have a substituent, an alkenylene group which may have a substituent, a —CO— group, a —COO— group, a —CON (R ₁₀₀₎ - group _{[R 100} is represents hydrogen, an alkyl group, an aralkyl group, 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 acryloyloxy group, an acryloylamide group, And vinyl thioether group.

(2) Examples of the 1,1-substituted ethylene functional group include functional groups represented by the following general formula (ii).
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 which may have a substituent, an aralkyl group which 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, single bond, and alkylene group as X _{1 in the} general formula (i). Provided that at least one oxycarbonyl group in Y and X _2, a cyano group, an alkenylene group, 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-acryloyloxy chloride group, a methacryloyloxy group, an α-cyanoethylene group, an α-cyanoacryloyloxy group, and an α-cyanophenylene group. And a methacryloylamino group.

In addition, examples of the substituent further substituted with the substituent 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 radical polymerizable compound having the triarylamine include compounds represented by the following general formulas (1-1) to (1-3).

[General Formula 1-1]

[General Formula 1-2]

[General Formula 1-3]

In the general formulas (1-1) to (1-3), R ₂₇ to R ₈₈ are all monovalent organic groups, which may be the same or different, and the monovalent organic group. 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 general formulas (1-1) to (1-3) include those shown below. The radical polymerizable compound having the triarylamine is not limited thereto.

<Exemplary Compound 1>

<Exemplary Compound 2>

<Exemplary Compound 3>

<Exemplary Compound 4>

<Exemplary Compound 5>

<Exemplary Compound 6>

<Exemplary Compound 7>

<Exemplary Compound 8>

<Exemplary Compound 9>

<Exemplary Compound 10>

<Exemplary Compound 11>

<Exemplary Compound 12>

<Exemplary Compound 13>

<Exemplary Compound 14>

<Exemplary Compound 15>

<Exemplary Compound 16>

<Exemplary Compound 17>

<Exemplary Compound 18>

<Exemplary Compound 19>

<Exemplary Compound 20>

<Exemplary Compound 21>

<Exemplary Compound 22>

<Exemplary Compound 23>

<Exemplary Compound 24>

<Exemplary Compound 25>

<Exemplary Compound 26>

<Exemplary Compound 27>

<Exemplary Compound 28>

<Exemplary Compound 29>

<Exemplary Compound 30>

<Exemplary Compound 31>

<Exemplary Compound 32>

<Exemplary Compound 33>

<Exemplary Compound 34>

<Exemplary Compound 35>

<Exemplary Compound 36>

<Exemplary Compound 37>

<Exemplary Compound 38>

<Exemplary Compound 39>

<Exemplary Compound 40>

<< Other radical polymerizable compound >>
Unlike the radical polymerizable compound having a triarylamine, 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, and among these, an acryloyloxy group and a methacryloyloxy group are particularly preferable. preferable.

  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 and the other radical polymerizable compound different from the radical polymerizable compound having the triarylamine has two or more radical polymerizable functional groups. Is preferable from the viewpoint of forming a crosslinked product.
10 mass% or more and 100 mass% or less are preferable with respect to the electrochromic composition whole quantity, and, as for content of the radically polymerizable compound which has the said triarylamine, 30 mass% or more and 90 mass% or less are more preferable.
When the content is 10% by mass or more, the electrochromic function of the 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 electrochromic composition is necessary for efficiently proceeding with a crosslinking reaction between the radical polymerizable compound having the triarylamine and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine. Depending on the case, it is preferable to contain a polymerization initiator.
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 intended purpose. For example, 2,5-dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, benzoyl peroxide, t-Butylcumyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoyl) hexyne-3, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide Peroxide initiators such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, azobisisobutylamidine hydrochloride, azo initiators such as 4,4′-azobis-4-cyanovaleric acid, Etc. 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. Examples thereof include 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- ( acetophenone-based or ketal-based photopolymerization initiators such as o-ethoxycarbonyl) oxime; benzoin, benzoin methyl ester Benzoin ether photopolymerization initiators such as tereline, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether; benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 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). Phenylphosphine oxide, bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10-phenanthrene, acridine compound, triazine compound, imidazole compound, etc. Is 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.

The electrochromic layer can be formed by a method for manufacturing an electrochromic light control device described later.
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.

<Support>
As the support, a known organic material or inorganic material can be used as it is as long as it is a transparent material capable of supporting each layer.
As the support, for example, a glass substrate such as alkali-free glass, borosilicate glass, float glass, or soda lime glass can be used. Further, as the support, a resin substrate such as polycarbonate resin, acrylic resin, polyethylene, polyvinyl chloride, polyester, epoxy resin, melamine resin, phenol resin, polyurethane resin, or polyimide resin may be used.
Further, the surface of 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.
The shape of the support may be rectangular or round, and is not particularly limited.
The support may be a plurality of stacked layers. For example, by providing a structure in which an electrochromic light control element is sandwiched between two glass substrates, it is possible to improve water vapor barrier properties and gas barrier properties.

A lens is suitable as the support.
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. Further, it is preferable that the expansion due to the thermal history is as small as possible, and a material having a high glass transition point Tg and a material having 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 (simple glass plate or the like).

  In this invention, it is preferable that the said electrochromic light control element is formed in the said support body, and what has a curved surface as said support body is more preferable. Thereby, there is little disorder of the image seen through the electrochromic light control element, 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.

<First electrode and second electrode>
The material of the first electrode and the second electrode is not particularly limited as long as it is a transparent material having conductivity, and can be appropriately selected according to the purpose. For example, indium oxide doped with tin (hereinafter referred to as “tin oxide”) , "ITO"), fluorine-doped tin oxide (hereinafter referred to as "FTO"), antimony-doped tin oxide (hereinafter referred to as "ATO"), and inorganic materials such as zinc oxide. . Among these, InSnO, GaZnO, SnO, In ₂ O ₃ and ZnO are preferable.
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. An electrode may be used.
The thickness of each of the first electrode and the second electrode is adjusted so as to obtain an electric resistance value necessary for the redox reaction of the electrochromic layer.
When ITO is used as a material for the first electrode and the second electrode, the thickness of each of the first electrode and the second electrode is preferably, for example, 50 nm or more and 500 nm or less.

As a manufacturing method of each of the first electrode and the second electrode, a vacuum deposition method, a sputtering method, an ion plating method, or the like can be used.
There is no particular limitation as long as the material of each 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 printing Various printing methods such as a method can be used.

<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 alkali supporting salts. Specifically, LiClO ₄ and 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, examples of the cationic component include imidazole derivatives such as N, N-dimethylimidazole salt, N, N-methylethylimidazole salt, and N, N-methylpropylimidazole salt; N, N-dimethylpyridinium salt, Examples thereof include pyridinium derivatives such as 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 light control device 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 10 micrometers or less are preferable.

  In the present invention, the electrolyte preferably contains a radical polymerizable compound, and has a crosslinked product obtained by curing the radical polymerizable compound. Thereby, as a method for producing an electrochromic light control device, it is not necessary to bond two supports together. For example, after forming a first electrode on a support and an electrochromic layer on the first electrode After forming the electrolyte in layers and curing to form the electrolyte layer, an electrochromic light control device can be produced by forming the second electrode.

  In the present invention, the electrolyte contains a radical polymerizable compound, and the radical polymerizable compound is the same as the other radical polymerizable compound in the electrochromic composition. The refractive index difference is reduced, and light reflection and light scattering at the material interface can be suppressed.

<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 deterioration prevention layer, a protective layer, etc. are mentioned.

-Insulating porous layer-
The insulating porous layer, the first electrode and the second electrode are isolated so as to be electrically insulated, and have a function of holding an electrolyte.
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.

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 specific method for forming the insulating porous layer, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like can be used. If the material of the insulating porous layer can be applied and formed, 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 Various printing methods such as 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 can be used. .
The average thickness of the insulating porous layer is preferably 0.5 μm or more and 3 μm or less.

  In the present invention, having an intermediate layer composed of the insulating porous layer and the electrolyte between the first electrode and the second electrode improves the mechanical strength of the electrochromic light control device and This is preferable from the viewpoint of reducing leakage current in the device.

-Deterioration prevention layer-
The role of the deterioration preventing layer is to perform a chemical reaction opposite to that of the electrochromic layer and balance the electric charge to suppress corrosion and deterioration of the first electrode and the second electrode due to an irreversible oxidation-reduction reaction. That is. In addition, the reverse reaction includes acting as a capacitor in addition to the case where the degradation preventing layer is oxidized and reduced.
The material for the deterioration preventing layer is not particularly limited as long as it is a material that plays a role of preventing corrosion due to the irreversible oxidation-reduction reaction of the first electrode and the second electrode, and is appropriately selected according to the purpose. For example, antimony tin oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, or a conductive or semiconductive metal oxide containing a plurality of them can be used.
The deterioration preventing layer can be composed of a porous thin film that does not hinder electrolyte injection. For example, conductive or semiconductive metal oxide fine particles such as antimony tin oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, etc., for example, acrylic, alkyd, isocyanate, urethane, epoxy, phenol, etc. By fixing to the second electrode with this binder, a suitable porous thin film satisfying the electrolyte permeability and the function as a deterioration preventing layer can be obtained.

-Protective layer-
The role of the protective layer is to protect the device from external stress and chemicals in the cleaning process, to prevent electrolyte leakage, and to prevent the electrochromic device such as moisture and oxygen in the atmosphere from operating stably. For example, to prevent intrusion.
There is no restriction | limiting in particular as thickness of the said protective layer, Although it can select suitably according to the objective, 1 micrometer or more and 200 micrometers or less are preferable.
As the material for the protective layer, for example, an ultraviolet curable resin or a thermosetting resin can be used, and specific examples include acrylic, urethane, and epoxy resins.

<Method for producing electrochromic light control device>
The method for manufacturing an electrochromic dimming element used in the present invention includes an electrochromic dimming having a first electrode, a second electrode, and an electrolyte between the first electrode and the second electrode. A method for manufacturing an element, comprising:
It includes an application step, preferably a cross-linking step, and further includes other steps as necessary.

<Application process>
The coating step includes an electrochromic composition comprising a radical polymerizable compound having triarylamine and another radical polymerizable compound different from the radical polymerizable compound having triarylamine on the first electrode. It is the process of apply | coating.

  The radical polymerizable compound having the triarylamine and the other radical polymerizable compound different from the radical polymerizable compound having the triarylamine should be the same as those described in the electrochromic light control device. Can do.

A coating solution containing a radical polymerizable compound having the triarylamine, another radical polymerizable compound different from the radical polymerizable compound having the triarylamine, and the filler 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.
In addition, the dilution rate with the said solvent changes with the solubility of a composition, the coating method, the thickness of the target electrochromic layer, etc., and can be selected suitably.
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 process>
The crosslinking step is a step of crosslinking by applying heating or light energy to the applied electrochromic composition.

After applying the electrochromic composition onto the first electrode, energy is applied from the outside and cured to form an 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 a gas such as air, 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.

<Other processes>
Examples of the other steps include a first electrode forming step, a second electrode forming step, an insulating porous layer forming step, a deterioration preventing layer forming step, a protective layer forming step, and a bonding step. .

  Here, FIG. 1 is a cross-sectional view showing an example of the electrochromic light control device of the present invention. Referring to FIG. 1, the electrochromic dimming element 110 includes a lens 120 as a support and a thin film dimming function unit 130 stacked on the lens 120. The planar shape of the electrochromic light control element 110 can be, for example, a round shape.

  The thin-film light control function unit 130 has a structure in which a first electrode 131, an electrochromic layer 132, an insulating porous layer 133, a second electrode 134, a deterioration preventing layer 135, and a protective layer 136 are sequentially stacked. In addition, the electrochromic layer 132 is a part that performs color development / dimming (dimming). The protective layer 136 may be formed on the upper surface (the surface opposite to the lens 120) of the deterioration preventing layer 135, and is not necessarily limited to the first electrode 131, the electrochromic layer 132, and the insulating porous layer. 133, the second electrode 134, and the deterioration prevention layer 135 may not be formed on each side surface.

In the electrochromic light control element 110, a first electrode 131 is provided on the lens 120, and an electrochromic layer 132 is provided in contact with the first electrode 131.
A second electrode 134 is provided on the electrochromic layer 132 so as to face the first electrode 131 with an insulating porous layer 133 interposed therebetween.
The insulating porous layer 133 is provided to insulate the first electrode 131 and the second electrode 134, and the insulating porous layer 133 contains insulating metal oxide particles. The insulating porous layer 133 sandwiched between the first electrode 131 and the second electrode 134 is filled with an electrolyte (not shown).
The second electrode 134 is a porous electrode in which a large number of through holes penetrating in the thickness direction are formed. A deterioration preventing layer 135 is provided outside the second electrode 134. The deterioration preventing layer 135 is also porous in which a large number of through holes penetrating in the thickness direction are formed, and is filled with an electrolyte (not shown).
In the electrochromic dimming element 110, by applying a voltage between the first electrode 131 and the second electrode 134, the electrochromic layer 132 undergoes an oxidation-reduction reaction and exchanges color by charge transfer.

The manufacturing process of the electrochromic dimming element 110 includes a process of sequentially laminating the first electrode 131 and the electrochromic layer 132 on the lens 120, and a first process through the insulating porous layer 133 on the electrochromic layer 132. A step of laminating a second electrode 134 which is a porous electrode in which a through hole is formed so as to face the other electrode 131, and a porous deterioration preventing layer in which a through hole is formed on the second electrode 134 135, and the insulating porous layer 133 sandwiched between the first electrode 131 and the second electrode 134, the deterioration preventing layer 135 and the second electrode 134 via the deterioration preventing layer 135 and the second electrode 134. And a step of filling the electrolyte from the through-hole formed in the second electrode 134 and a step of forming the protective layer 136 on the deterioration preventing layer 135.
That is, the respective through holes formed in the deterioration preventing layer 135 and the second electrode 134 are injection holes when the insulating porous layer 133 and the like are filled with the electrolyte in the manufacturing process of the electrochromic light control device 110. It is.

As described above, in the electrochromic light control device 110 of the present invention, the deterioration prevention layer 135 and the second electrode 134 are formed on the insulating porous layer 133 sandwiched between the first electrode 131 and the second electrode 134. It is possible to fill the electrolyte from the formed through hole. Therefore, it is possible to form the low-resistance second electrode 134 before filling the electrolyte, and the performance of the electrochromic dimming element 110 can be improved.
In addition, since the deterioration preventing layer 135 is provided on the second electrode 134, an electrochromic light control element that operates repeatedly and stably can be realized.
In the present embodiment, since a through hole is formed in the second electrode, a deterioration preventing layer is formed on the outside of the second electrode (outside of the two opposing electrodes) in contact with the second electrode. it can. This is because ions can move between the front and back of the second electrode through the through-hole formed in the second electrode. As a result, since it is not necessary to form a deterioration preventing layer below the second electrode, it is possible to avoid the possibility that the deterioration preventing layer is damaged by sputtering or the like when forming the second electrode.
In addition, when forming the deterioration preventing layer, a process capable of forming a homogeneous deterioration preventing layer can be appropriately selected depending on whether it is formed on the permeable insulating porous layer or on the second electrode. it can. Alternatively, the deterioration preventing layer may be formed both above and below the second electrode as necessary.

  Since the electrochromic light control device of the present invention can operate stably and is excellent in light transmittance, it can be suitably used for, for example, an antiglare mirror, light control glass, and a spectacle lens.

In FIG. 1, the electrochromic layer 132 is formed in contact with the first electrode 131 and the deterioration preventing layer 135 is formed in contact with the second electrode 134. When one of these undergoes an oxidation reaction, the other is reduced. The reaction is such that when one undergoes a reduction reaction, the other undergoes an oxidation reaction. Therefore, the position to be formed may be reversed. That is, the deterioration preventing layer 135 may be formed in contact with the first electrode 131 and the electrochromic layer 132 may be formed in contact with the second electrode 134.
The electrochromic layer 132 may be formed in contact with the first electrode 131, and the deterioration preventing layer may be formed on both the upper side and the lower side of the second electrode 134 in contact with the second electrode 134. Alternatively, the deterioration preventing layer 135 may be formed in contact with the first electrode 131, and the electrochromic layer 132 may be formed on both the upper side and the lower side of the second electrode 134 in contact with the second electrode 134.

In the present invention, the deterioration preventing layer and the electrochromic layer may be referred to as an electroactive layer. That is, in the electrochromic dimming element 110, the thin film dimming function unit 130 includes a first electrode 131 stacked on the lens 120, a first electroactive layer stacked on the first electrode 131, and The insulating porous layer 133 laminated on the first electroactive layer, the porous second electrode 134 laminated on the insulating porous layer 133, and the second electrode 134 A porous second electroactive layer formed on at least one of the upper side and the lower side of the second electrode 134, and one of the first electroactive layer and the second electroactive layer is electro It is the chromic layer 132 and the other is the deterioration preventing layer 135.
In the electrochromic light control device 110, since the protective layer 136 is formed in the coating process after the electrolyte is injected, the thickness can be reduced with respect to the configuration in which two lenses are bonded, and the weight can be reduced. Can be made at low cost.

  There is no restriction | limiting in particular in the thickness of the said thin film light control function part 130, Although it can select suitably according to the objective, 2 micrometers or more and 200 micrometers or less are preferable. If the thickness is less than 2 μm, a sufficient dimming function may not be obtained. If the thickness exceeds 200 μm, cracks and peeling occur during processing of the round lens, and the optical characteristics of the lens are affected. Sometimes.

<Electrochromic light control glasses>
FIG. 2 is a perspective view illustrating the electrochromic dimming glasses according to this embodiment. Referring to FIG. 2, the electrochromic dimming glasses 50 include an electrochromic dimming lens 51, a spectacle frame 52, a switch 53, and a power source 54. The electrochromic light control lens 51 is obtained by processing the electrochromic light control element 110 of the present invention into a desired shape.

The two electrochromic dimming lenses 51 are incorporated in the spectacle frame 52. The spectacle frame 52 is provided with a switch 53 and a power source 54. The power source 54 is electrically connected to the first electrode 131 and the second electrode 134 through a switch 53 by wiring (not shown).
By switching the switch 53, for example, one state is selected from a state in which a positive voltage is applied between the first electrode 131 and the second electrode 134, a state in which a negative voltage is applied, and a state in which no voltage is applied. Can be selected.
As the switch 53, for example, an arbitrary switch such as a slide switch or a push switch can be used. However, it is limited to a switch that can switch at least the three states described above.
As the power source 54, for example, an arbitrary DC power source such as a button battery or a solar battery can be used. The power source 54 can apply a voltage of about plus or minus several volts between the first electrode 131 and the second electrode 134.
For example, by applying a positive voltage between the first electrode 131 and the second electrode 134, the two electrochromic dimming lenses 51 are colored in a predetermined color. Further, by applying a negative voltage between the first electrode 131 and the second electrode 134, the two electrochromic dimming lenses 51 are decolored and become transparent.
However, depending on the characteristics of the material used for the electrochromic layer 132, color is developed by applying a negative voltage between the first electrode 131 and the second electrode 134, and the color is erased and transparent by applying a positive voltage. It may become. Note that once the color is developed, the color development continues even if no voltage is applied between the first electrode 131 and the second electrode 134.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
<Formation of electrochromic layer on first electrode>
In order to form an electrochromic layer on the first electrode, an electrochromic composition having the following composition was prepared.
[composition]
-Triarylamine compound 1 having monofunctional acrylate (Exemplary Compound 1): 50 parts by mass-IRGACURE184 (manufactured by BASF Japan): 5 parts by mass-PEG400DA having bifunctional acrylate (manufactured by Nippon Kayaku Co., Ltd.): 50 parts by mass-Methyl ethyl ketone: 900 parts by mass

  The obtained electrochromic composition was applied on an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a first electrode by spin coating, and the obtained coating film was applied. A crosslinked electrochromic layer having an average thickness of 0.4 μm was formed by irradiating with UV irradiation apparatus (USHIO Corporation, SPOT CURE) at 10 mW for 60 seconds and annealing at 60 ° C. for 10 minutes.

-Filling with electrolyte-
An electrolyte solution having the following composition was prepared.
IRGACURE184 (manufactured by BASF Japan KK): 5 parts by mass PEG400DA (manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass 1-ethyl-3-methylimidazolium tetracyanoborate (manufactured by Merck): 50 parts by mass

30 mg of the obtained electrolyte solution was measured with a micropipette and dropped onto an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) as a second electrode. On top of that, an ITO glass substrate having a cross-linked electrochromic layer was bonded so that there was an electrode lead-out portion, and a bonded element was produced.
The obtained bonded element was irradiated for 60 seconds at 10 mW with a UV (wavelength 250 nm) irradiation device (USHIO Inc., SPOT CURE). The electrochromic light control element was produced by the above.

<Color generation / erasing drive>
The color generation / decoloration of the produced electrochromic light control device was confirmed. Specifically, when a voltage of −3 V is applied for 5 seconds between the lead portion of the first electrode and the lead portion of the second electrode, the first electrode and the second electrode overlap. The blue-green color derived from the electrochromic of the triarylamine (Exemplary Compound 1) of the electrochromic cross-linked layer was confirmed in the part.
Next, when a voltage of +3 V is applied for 5 seconds between the lead portion of the first electrode and the lead portion of the second electrode, the portion where the first electrode and the second electrode overlap each other It was confirmed that the color disappeared and became transparent.

<Test 1: Repeat test>
About the produced electrochromic element, -3V5s and + 3V5s color development / erasing drive was repeated 500 times. The absorption maximum in the visible region (400 nm to 800 nm) at that time was defined as λmax. The change in absorbance at that time was measured with USB4000 manufactured by Ocean Optics, and evaluated according to the following criteria. The results are shown in Table 1. Note that λmax differs depending on the material, and is 680 nm in the case of Example 1.
[Evaluation criteria]
A: When the absorbance at λmax is 90% or more compared to the initial state. ○: When the absorbance at λmax is 80% or more and less than 90% compared to the initial state. Δ: The absorbance at λmax is 50% compared to the initial state. When it is less than 80% x: When the absorbance at λmax is less than 50% compared to the initial state

<Test 2: Light transmission test>
Measurement of light transmittance in a visible light region (400 nm to 700 nm) using a spectrophotometer (manufactured by Hitachi, Ltd., U-33000 spectrophotometer) with respect to the decolored state of the produced electrochromic light control device. Went. As a reference, a glass substrate (OA10, manufactured by Nippon Sheet Glass Co., Ltd., thickness 0.7 mm2) having the same thickness as the element was used.
Moreover, about the electrochromic light control element of the same state, the haze value (%) was measured with the haze meter (Nippon Denshoku Industries Co., Ltd. make, NDH-5000).
Based on these measurement results, light transmittance was evaluated according to the following criteria. The results are shown in Table 1.
[Evaluation criteria]
○: When the average value of light transmittance in the visible light region (400 nm to 700 nm) is 80% or more and the haze value is 2% or less Δ: Average light transmittance in the visible light region (400 nm to 700 nm) When the value is not less than 60% and less than 80% and the haze value is more than 2% and not more than 5% ×: The average value of light transmittance in the visible light region (400 nm to 700 nm) is less than 60% or the haze value is 5 If it is over%

(Examples 2 to 40)
Example 1 is the same as Example 1 except that the triarylamine compound 1 (the exemplified compound 1) is changed to the triarylamine compounds 2 to 40 (the exemplified compounds 2 to 40) shown in Table 1 below. Thus, an electrochromic light control device was produced.
About each produced electrochromic light control element, it carried out similarly to Example 1, and performed the said test 1 and the said test 2. FIG. The results are shown in Table 1.

(Comparative Example 1)
As Comparative Example 1, a triarylamine compound supported on titanium oxide was used.
-Formation of a titanium oxide particle film on the first electrode-
On the ITO glass substrate (40 mm × 40 mm, average thickness 0.7 mm, ITO film thickness: about 100 nm) as the first electrode, titanium oxide nanoparticle dispersion (trade name: SP210, manufactured by Showa Titanium Co., Ltd.) (Average particle diameter: about 20 nm) was applied by spin coating, and annealed at 120 ° C. for 15 minutes to form a titanium oxide particle film having a thickness of about 1.0 μm.

Next, in order to carry on titanium oxide, an electrochromic composition having the following composition was prepared.
-Triarylamine compound 101 represented by the following structural formula: 50 parts by mass <Triarylamine compound 101>
・ Methanol: 950 parts by mass

The obtained electrochromic composition was applied to the titanium oxide particle film by a spin coat method and annealed at 120 ° C. for 10 minutes to form a titanium oxide particle film.
Next, in the same manner as in Example 1, the deterioration preventing layer was formed on the second electrode and the electrolyte was filled to produce an electrochromic light control device.
About the produced electrochromic light control element, the said test 1 and the said test 2 were done like Example 1. FIG. The results are shown in Table 1.

(Comparative Example 2)
An electrochromic light control device was produced in the same manner as in Comparative Example 1 except that the triarylamine compound 101 was changed to the triarylamine compound 102 represented by the following structural formula in Comparative Example 1.
About the produced electrochromic light control element, the said test 1 and the said test 2 were done like Example 1. FIG. The results are shown in Table 1.
<Arylamine compound 102>

(Comparative Example 3)
An electrochromic composition having the following composition was prepared using a polymer in which triarylamines were linked by a main chain.
-Composition of electrochromic composition-
-Triarylamine polymer 103 represented by the following general formula: 50 parts by mass <Triarylamine polymer 103>
However, n represents 180-150 (estimated from polystyrene conversion).
-Toluene: 950 parts by mass

Next, the obtained electrochromic composition was applied to an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) by a spin coating method, and dried at 120 ° C. for 10 minutes. By doing so, an electrochromic layer was formed.
Next, in the same manner as in Example 1, formation of a deterioration preventing layer on the second electrode and filling of an electrolyte were performed to produce an electrochromic light control device.
About the produced electrochromic light control element, the said test 1 and the said test 2 were done like Example 1. FIG. The results are shown in Table 1.

* "-" In Test 2 of Comparative Example 3 indicates that measurement is impossible.

From the results shown in Table 1, the electrochromic light control devices using the triarylamine compounds of the exemplified compounds 1 to 40 all show good electrochromic properties, and are hardly deteriorated such as coloring after repeated driving of 500 times. I couldn't see it. Moreover, the light transmittance was also favorable. In particular, with regard to the repetition test, those in which the carbon at the 4-position of the phenyl group of triarylamine was substituted (not a hydrogen atom) had more preferable results.
On the other hand, although the electrochromic light control device using the triarylamine compound supported on the titanium oxide of Comparative Examples 1 and 2 can be repeated 500 times, the light transmittance is lowered.
Further, the electrochromic light control device using the triarylamine polymer of Comparative Example 3 was significantly deteriorated with respect to repetition.

(Example 41)
In the formation of the electrochromic layer on the first electrode, an electrochromic composition having the following composition was examined. That is, as shown in Table 2, by adjusting the mass ratio of the radically polymerizable compound 1 having triarylamine (Exemplary Compound 1) in the range of X = 100 to 0, radically polymerizable having triarylamine is obtained. The mass ratio of the compound and another radical polymerizable compound different from the radical polymerizable compound having triarylamine was examined.
The operations other than those described above were performed in the same manner as in Example 1 to produce an electrochromic light control device.

-Composition of electrochromic composition-
-Triarylamine compound 1 having monofunctional acrylate (Exemplary Compound 1): X parts by mass-IRGACURE 184 (BASF Japan Ltd.): 5 parts by mass-PEG400DA having bifunctional acrylate (Nippon Kayaku Co., Ltd.): (100-X) parts by mass Methyl ethyl ketone: 900 parts by mass

  About the obtained electrochromic element, in order to confirm the difference in composition, coloring property, decoloring property, pixel evaluation, and comprehensive evaluation were performed. The results are shown in Table 2.

<Color development and decolorization>
Regarding color developability, each element was colored at −3 V5 s, and the change in transmittance at that time was measured with a USB4000 manufactured by Ocean Optics. The case where the transmittance of λmax was 50% or more was judged as “◯”, the case where it was less than 50% but colored, Δ, and the case where it was not colored was judged “X”.
Regarding decoloring property, + 3V5s was applied to each colored element, and ◯ when the λmax returned to the initial state, △ when the transmittance was attenuated but did not completely return to the initial value. When there was no change at all, it was determined as x.

<Pixel evaluation>
The pixel after repeating -3V5s color development and + 3V5s decoloration 500 times was confirmed with a digital microscope (KH-7700, manufactured by Hilox Corporation). Pixel evaluation was performed by sensorially evaluating the degree of color development and the degree of decoloration after repetition.

<Comprehensive judgment>
As a comprehensive judgment, a comprehensive judgment was made based on the results of color development, decolorization, and pixel evaluation, and the evaluation was made according to the following criteria.
○: Color development, color erasing, and pixel evaluation are satisfied Δ: Color development, color erasing, and image evaluation are not satisfied ×: Color development and color erasing are functioning Absent

(Example 42)
In Example 41, an electrochromic light control device was produced in the same manner as in Example 41 except that the electrochromic composition having the following composition was used and the mass ratios shown in Table 3 were used.
Using the obtained electrochromic light control device, color erasability, pixel evaluation, and comprehensive evaluation were performed in the same manner as in Example 41. The results are shown in Table 3.

-Composition of electrochromic composition-
-Triarylamine compound 2 having bifunctional acrylate (Exemplified Compound 2): X parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 5 parts by mass-2- (2-Ethoxyethyl) ethyl Acrylate (Tokyo Chemical Industry Co., Ltd.) Manufactured): (100-X) parts by massMethyl ethyl ketone: 900 parts by mass

(Example 43)
In Example 41, an electrochromic light control device was produced in the same manner as in Example 41 except that an electrochromic composition having the following composition was used and the mass ratios shown in Table 4 were used.
Using the obtained electrochromic light control device, color erasability, pixel evaluation, and comprehensive evaluation were performed in the same manner as in Example 41. The results are shown in Table 4.

-Composition of electrochromic composition-
-Triarylamine compound 3 having monofunctional acrylate (Exemplary Compound 3): X parts by mass-IRGACURE184 (manufactured by BASF Japan Ltd.): 5 parts by mass-Acrylate monomer (DPCA-60, Nippon Kayaku Co., Ltd.): (100-X) parts by mass Methyl ethyl ketone: 900 parts by mass

  From the results of Examples 41 to 43, when the mass ratio X of the radical polymerizable compound having triarylamine is in the range of 100 parts by mass to 10 parts by mass, the behavior of deterioration of materials such as yellowing is repeated after 500 repetitions. I couldn't see it. In particular, it was found that good color development and decoloring behavior was exhibited when the mass ratio X was in the range of 90 to 30 parts by mass.

(Example 44)
<Preparation of electrochromic light control device having intermediate layer>
In the same manner as in Example 1, an electrochromic composition having the following composition was prepared.
-Preparation of electrochromic composition-
-Triarylamine compound 1 having monofunctional acrylate (Exemplary Compound 1): 50 parts by mass-IRGACURE184 (manufactured by BASF Japan): 5 parts by mass-PEG400DA having bifunctional acrylate (manufactured by Nippon Kayaku Co., Ltd.): 50 parts by mass-Methyl ethyl ketone: 900 parts by mass

The obtained electrochromic composition was applied to an ITO glass substrate (40 mm × 40 mm, thickness 0.7 mm, ITO film thickness: about 100 nm) by a spin coat method.
The obtained coating film was irradiated for 60 seconds at 10 mW with a UV irradiation apparatus (USHIO Inc., SPOT CURE), and annealed at 60 ° C. for 10 minutes, whereby a cross-linked electrochromic layer having an average thickness of 0.4 μm. Formed.

-Formation of insulating porous layer-
An insulating porous layer coating solution having the following composition was prepared.
MA-ST-UP (manufactured by Nissan Chemical Industries, Ltd., solid content concentration 20% by mass): 50 parts by mass A 3% by mass aqueous solution of polyvinyl alcohol (PVA) (manufactured by Tokyo Chemical Industry Co., Ltd., degree of polymerization 3,500): 10 parts by mass Pure water: 20 parts by mass

  The obtained insulating porous layer coating solution was applied to the produced electrochromic layer by a spin coating method, and the resulting film was dried and cured by heating at 120 ° C. for 60 seconds in an oven. An insulating porous layer was formed.

-Filling with electrolyte-
As an electrolyte, an electrolyte solution having the following composition was prepared.
IRGACURE184 (manufactured by BASF Japan KK): 5 parts by mass PEG400DA (manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass 1-ethyl-3-methylimidazolium tetracyanoborate (manufactured by Merck): 50 parts by mass

Next, 30 mg of the obtained electrolyte solution was measured with a micropipette and dropped onto an ITO glass substrate. On top of that, an ITO glass substrate having the electrochromic layer and the insulating porous layer was bonded so that there was an electrode lead-out portion.
The obtained bonded element was irradiated with a UV irradiation apparatus (USHIO Inc., SPOT CURE) at 10 mW for 60 seconds and cured to produce an electrochromic light control element having an intermediate layer.

(Example 45)
<Preparation of electrochromic light control device having intermediate layer>
In the same manner as in Example 44, an electrochromic layer and an insulating porous layer were formed on the first electrode, and an electrolyte solution was prepared.

-Formation of intermediate layer-
30 mg of the obtained electrolyte solution was measured with a micropipette and added dropwise to the insulating porous layer. On the electrolyte solution, a film having a gas barrier property (Tetron Co., Ltd., Tetoron film G2) was bonded so that there was an electrode lead portion.
The obtained bonded body was irradiated for 60 seconds at 10 mW with a UV irradiation apparatus (USHIO Inc., SPOT CURE) and cured, and then the film was peeled off to form an intermediate layer.

-Formation of second electrode-
A second electrode having a film thickness of 60 nm was formed on the obtained intermediate layer by a sputtering method using an ITO target. Thus, an electrochromic light control device having an intermediate layer was produced.

(Example 46)
<Preparation of electrochromic light control device formed on lens curved surface>
Using a lens made of thiourethane resin as a support, an electrochromic light control device was produced as follows.

-Formation of the first electrode-
First, a 60-nm-thick first electrode was formed on the convex surface of the thiourethane resin lens by a sputtering method using an ITO target.

-Formation of electrochromic layer, intermediate layer, second electrode-
Next, in the same manner as in Example 45, an electrochromic layer and an intermediate layer were sequentially formed on the first electrode.
Next, a second electrode having a film thickness of 60 nm was formed on the intermediate layer by a sputtering method using an ITO target. Thus, an electrochromic light control element formed on a resin lens curved surface as a support was produced.

(Comparative Example 4)
Using a PET film with an ITO film on one side as a support, an electrochromic dimming element produced in the same manner as in Example 1 was further attached to the convex surface of a resin lens similar to that in Example 46, and electrochromic dimming was performed. An element was produced.

<Test 5: Viewing angle and distortion evaluation>
Viewing angle and image distortion when Example 1, Example 46, and Comparative Example 4 fabricated on a flat plate are fixed in front of the eye at a distance equivalent to that of a spectacle lens and viewed through an electrochromic light control device. Was evaluated according to the following criteria. The results are shown in Table 5.
When the viewing angle is remarkably limited with respect to the state where there is nothing or distortion appears in the visible image, it was evaluated as x, and the others were evaluated as ◯.

From the results of Table 5, in Example 1, the viewing angle was narrowed, and in Comparative Example 4, distortion of the image derived from wrinkles of the film was observed in the peripheral portion. For Example 46, good results were obtained for both viewing angle and distortion.

As an aspect of this invention, it is as follows, for example.
<1> An electrochromic light control device having a first electrode, a second electrode, and an electrolyte between the first electrode and the second electrode,
The first electrode has a polymer obtained by polymerizing an electrochromic composition containing a radical polymerizable compound having triarylamine,
The member that constitutes the electrochromic light control device is light transmissive, and is an electrochromic light control device.
<2> The first electrode is a cross-linked electrochromic composition containing a radical polymerizable compound having a triarylamine and another radical polymerizable compound different from the radical polymerizable compound having the triarylamine. It is an electrochromic light control element as described in said <1> which has a crosslinked material.
<3> Either one of the radical polymerizable compound having triarylamine and the other radical polymerizable compound different from the radical polymerizable compound having triarylamine has two or more radical polymerizable functional groups. The electrochromic light control device according to <2>.
<4> The electrochromic light control device according to any one of <2> to <3>, wherein the radical polymerizable functional group of the other radical polymerizable compound is at least one of an acryloyloxy group and a methacryloyloxy group. It is.
<5> The electrochromic according to any one of <1> to <4>, wherein the radical polymerizable functional group of the radical polymerizable compound having a triarylamine is at least one of an acryloyloxy group and a methacryloyloxy group. It is a light control element.
<6> The electrochromic light control device according to any one of <1> to <5>, wherein the radical polymerizable compound having a triarylamine is represented by the following general formula 1.
<General formula 1>
_An −B _m
However, when n = 2, m is 0, and when n = 1, m is 0 or 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 of R ₁ to R ₁₅ . The B is a structure represented by the following general formula 3, and is bonded to the A at any position from R ₁₆ to R ₂₁ .
<General formula 2>
<General formula 3>
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. .
<7> The electrochromic light control device according to any one of <1> to <6>, wherein the electrolyte includes a radical polymerizable compound and the crosslinked product obtained by curing the radical polymerizable compound.
<8> The electrochromic light control according to any one of <1> to <7>, wherein an intermediate layer composed of an insulating porous layer and an electrolyte is provided between the first electrode and the second electrode. It is an element.
<9> The electrochromic light control device according to any one of <7> to <8>, wherein the radical polymerizable compound contained in the electrolyte is the same as another radical polymerizable compound in the electrochromic composition. .
<10> The substrate according to any one of <1> to <9>, including a support, wherein the support is a curved surface, and a member constituting an electrochromic light control element is formed on the curved surface of the support. It is an electrochromic light control element of description.
<11> The electrochromic light control device according to <10>, wherein the support is a lens.

110 Electrochromic light control device 120 Support (lens)
131 First electrode 132 Electrochromic layer 134 Second electrode

Chem. Mater. 2006, 18, 5823-58259. Org. Electron. 2014, 15, 428-434.

Claims (10)

An electrochromic dimming device having a first electrode, a second electrode, and an electrolyte between the first electrode and the second electrode,
The first electrode has a polymer obtained by polymerizing an electrochromic composition containing a radical polymerizable compound having a triarylamine represented by the following general formula 1,
The electrochromic light control device, wherein the member constituting the electrochromic light control device has optical transparency.
<General formula 1>
_An −B _m
However, when n = 2, m is 0, and when n = 1, m is 0 or 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 of R ₁ to R ₁₅ . The B is a structure represented by the following general formula 3, and is bonded to the A at any position from R ₁₆ to R ₂₁ .
<General formula 2>
<General formula 3>
However, R ₁ to R ₂₁ are a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, an optionally substituted alkoxycarbonyl group, or an optionally substituted aryl. An oxycarbonyl group, an optionally substituted alkylcarbonyl group, an optionally substituted arylcarbonyl group, an amide group, an optionally substituted monoalkylaminocarbonyl group, a substituent A dialkylaminocarbonyl group which may have a monoarylaminocarbonyl group which may have a substituent, a diarylaminocarbonyl group which may have a substituent, a sulfonic acid group and a substituent. An optionally substituted alkoxysulfonyl group, an optionally substituted aryloxysulfonyl group, and an optionally substituted a A killsulfonyl group, an arylsulfonyl group which may have a substituent, a sulfonamide group, a monoalkylaminosulfonyl group which may have a substituent, a dialkylaminosulfonyl group which may have a substituent, A monoarylaminosulfonyl group which may have a substituent, a diarylaminosulfonyl group which may have a substituent, an amino group, a monoalkylamino group which may have a substituent, and 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, an alkynyl group which may have a substituent, and a substituent Aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylthio which may have a substituent A group, an arylthio group optionally having substituent (s), or a heterocyclic group optionally having substituent (s) , each of which may be the same or different, and is selected from the above R ₁ to R ₂₁ At least one is a radically polymerizable functional group;
The radical polymerizable functional group is any one of the functional groups represented by the following general formula (i) and general formula (ii).
However, in said general formula (i), X < ₁ > is the arylene group which may have a substituent, the alkenylene group which may have a substituent, -CO- group, -COO- group, or -S-. Represents a group.
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, or -COOR ₁₀₁ group (R ₁₀₁ has 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). X ₂ represents an arylene group which may have a substituent, an alkenylene group which may have a substituent, a —CO— group, a —COO— group, a —S— group, a single bond, or an alkylene group. Represent. Provided that at least one oxycarbonyl group in Y and X _2, a cyano group, an alkenylene group, or an aromatic ring.   A cross-linked product obtained by cross-linking an electrochromic composition in which the first electrode includes a radical polymerizable compound having triarylamine and another radical polymerizable compound different from the radical polymerizable compound having triarylamine. The electrochromic light control device according to claim 1.   Either one of the radically polymerizable compound having the triarylamine and the other radically polymerizable compound different from the radically polymerizable compound having the triarylamine has two or more radically polymerizable functional groups. Item 3. The electrochromic light control device according to Item 2.   The electrochromic light control device according to any one of claims 2 to 3, wherein the radical polymerizable functional group of the other radical polymerizable compound is at least one of an acryloyloxy group and a methacryloyloxy group.   The electrochromic light control device according to any one of claims 1 to 4, wherein the radical polymerizable functional group in the general formulas (2) and (3) is at least one of an acryloyloxy group and a methacryloyloxy group. The electrochromic light control device according to claim 1, wherein the triarylamine represented by the general formula 1 is at least one selected from compounds represented by the following structural formulas.
<Exemplary Compound 1>
<Exemplary Compound 2>
<Exemplary Compound 3>
<Exemplary Compound 4>
<Exemplary Compound 5>
<Exemplary Compound 6>
<Exemplary Compound 7>
<Exemplary Compound 8>
<Exemplary Compound 9>
<Exemplary Compound 10>
<Exemplary Compound 11>
<Exemplary Compound 12>
<Exemplary Compound 13>
<Exemplary Compound 14>
<Exemplary Compound 15>
<Exemplary Compound 16>
<Exemplary Compound 17>
<Exemplary Compound 18>
<Exemplary Compound 19>
<Exemplary Compound 20>
<Exemplary Compound 21>
<Exemplary Compound 22>
<Exemplary Compound 23>
<Exemplary Compound 24>
<Exemplary Compound 25>
<Exemplary Compound 26>
<Exemplary Compound 27>
<Exemplary Compound 28>
<Exemplary Compound 29>
<Exemplary Compound 30>
<Exemplary Compound 31>
<Exemplary Compound 32>
<Exemplary Compound 33>
<Exemplary Compound 34>
<Exemplary Compound 35>
<Exemplary Compound 36>
<Exemplary Compound 37>
<Exemplary Compound 38>
<Exemplary Compound 39>
<Exemplary Compound 40>
  The electrochromic light control device according to any one of claims 1 to 6, wherein the electrolyte contains a radical polymerizable compound and has a crosslinked product obtained by curing the radical polymerizable compound.   The electrochromic light control device according to any one of claims 1 to 7, further comprising an intermediate layer made of an insulating porous layer and an electrolyte between the first electrode and the second electrode.   The electrochromic light control according to any one of claims 1 to 8, further comprising a support body, the support body being a curved surface, and a member constituting an electrochromic light control element formed on the curved surface of the support body. element.   The electrochromic light control device according to claim 9, wherein the support is a lens and electrochromic light control glasses.