JP2010250132A - Electrochromic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrochromic device which is reduced in the necessity of strict sealing, is free from the risk of breakage of an electrode, and is fast in a response speed. <P>SOLUTION: The electrochromic device includes a first electrode 10, an electrochromic layer 30, and a second electrode 20 in this order. At least one of the first and second electrodes includes conductive layers 12 and 22 containing conductive fine particles and binders. The electrochormic layer contains a high polymer, an elasticizer, an electrochromic compound and an organic charge transport agent. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an electrochromic device, and more particularly to an electrochromic device capable of manufacturing an electrochromic device having a large area with a small number of manufacturing steps.

  An electrochromic (hereinafter abbreviated as “EC”) device, such as an EC display device, does not require a polarizing plate or the like, and therefore has no viewing angle dependency, is light-receiving and has excellent visibility, and is reversible by an electrochemical redox reaction. If it has at least an electrolyte containing an EC compound that develops or decolors and a pair of electrodes, the structure is simple and the size can be easily increased, and various color tones can be obtained by selecting the EC compound. In addition, since the display state can be stopped just by blocking the movement of electrons and maintaining the oxidation-reduction state, it has excellent memory characteristics and power consumption is low because it does not require power to maintain the display state. Since it has various advantages, it has been applied in various fields.

  Recently, for example, the EC material, the electrolyte, and the above are dissolved between a pair of electrodes composed of an electrode provided with a conductive layer such as indium-doped tin oxide (ITO) on the surface of a glass substrate. An EC apparatus in which a solvent to be sealed has been proposed has been proposed (Patent Document 1). Further, the EC compound is formed on the surface of one conductive layer of the pair of electrodes as described above, and a polymer solid electrolyte membrane is interposed between the electrodes to seal the outer peripheral edge of both electrodes. An EC apparatus has been proposed (Patent Document 2).

However, since the EC apparatus of Patent Document 1 uses a solvent, it is necessary to strictly seal so that this solvent does not leak, and even if strictly sealed, it is used as an electrode. There is a drawback that the encapsulated solvent leaks when the glass is broken.
In addition, in the EC device of Patent Document 2, due to the use of the solid polymer electrolyte membrane, there is still a difficulty that the response at the time of voltage application is slow, and the glass used as the electrode is easily damaged. There was a drawback.
These disadvantages have been a factor that leads to an increase in manufacturing cost, particularly in the case of an EC device having a large area.

Japanese Patent Laid-Open No. 9-120088 JP 7-152050 A

  The present invention aims to solve the above-described problems and to solve the following problems. That is, an object of the present invention is to provide an EC device that reduces the need for strict sealing, does not cause damage to electrodes, and has a high response speed.

Means for solving the above-mentioned problems are as follows.
<1> A first electrode, an electrochromic layer, and a second electrode are provided in this order, and at least one of the first and second electrodes has a conductive layer containing conductive fine particles and a binder. And the electrochromic layer contains a polymer, a plasticizer, an electrochromic compound and an organic charge transport agent.

<2> At least one of the first and second electrodes includes a conductive layer having a mesh pattern, the width X (μm) of the opening of the mesh pattern of the conductive layer, and the opening of the mesh pattern The electrochromic device according to <1>, wherein the surface resistance Y (Ω / □) of the portion satisfies the following formulas (a) and (b).
Formula (a) 50 ≦ X ≦ 7000
Formula (b) 10 ⁵ ≦ Y ≦ (5 × 10 ²³ ) × X ^−4.02

<3> The electrochromic device according to <1> or <2>, wherein the polymer is a thermoplastic polymer.
<4> The electrochromic device according to any one of <1> to <3>, wherein the polymer is polymethyl methacrylate, polyvinyl butyral, polycarbonate, polysulfone, or polyurethane.
<5> The electrochromic device according to any one of <1> to <4>, wherein the plasticizer has a boiling point of 150 ° C. or higher.

<6> The method according to any one of <1> to <5>, wherein the plasticizer is at least one compound selected from the group consisting of alkylene carbonate, polyalkylene glycol dialkyl ester, and dialkyl ester of dibasic carboxylic acid. Electrochromic device.
<7> The electrochromic device according to any one of <1> to <6>, wherein the electrochromic compound is a viologen compound.
<8> The electrochromic device according to any one of <1> to <7>, wherein the organic charge transfer agent is a compound selected from the group consisting of polyalkyne, polythiophene, and polyfuran.

<9> 30% by mass to 80% by mass of the polymer polymer, 10% by mass to 60% by mass of plasticizer, 1% by mass to 10% by mass of electrochromic compound, and 0.005% by mass to 20% The electrochromic device according to any one of <1> to <8>, wherein the electrochromic device contains a mass% organic charge transfer agent.
<10> The electrochromic layer according to any one of <1> to <7> and <9>, wherein the electrochromic layer contains 5% by mass to 20% by mass of an organic charge transfer agent, and the organic charge transfer agent is hydroquinone. Electrochromic device.

<11> The electrochromic device according to any one of <1> to <10>, wherein a mass ratio of the conductive fine particles and the binder contained in the conductive layer is in a range of 1:33 to 1.5: 1.
<12> The electrochromic device according to any one of the amount of the conductive fine particles contained in the conductive layer is said in the range of ^{0.05g / m 2 ~0.9g / m 2} <1> ~ <11> .
<13> The electrochromic device according to any one of <1> to <12>, wherein the conductive layer has a surface resistance of 0.01Ω / □ or more.

<14> Each of the first and second electrodes has a conductive layer containing conductive fine particles and a binder on one surface of the plastic film support, and at least one layer on the surface of the support. The electrochromic device according to any one of <1> to <13>, in which each of the conductive layers of the first and second electrodes is opposed to the electrochromic layer.
<15> The electrochromic device according to <14>, wherein the barrier layer is made of an inorganic oxide.

  According to the present invention, the need for strict sealing is reduced, and an EC device with no risk of electrode breakage and high response speed can be obtained. That is, in the present invention, an electrode having high conductivity can be manufactured at a low cost, and since the leakage of the liquid component from the electrochromic layer is small, the need for strict sealing is reduced. As a result, a large-area EC device can be manufactured at low cost. Therefore, the EC device of the present invention is used to obtain a window having a dimming function for reducing the illuminance of incident light or blocking the incident light, such as application fields that could not be conventionally used from the viewpoint of cost. For example, it can be applied to application fields that require a large area.

It is sectional drawing of EC apparatus of one embodiment of this invention. It is the elements on larger scale of one electrode of the electrode in the EC apparatus of FIG. It is a top view of a mesh.

Hereinafter, the EC apparatus of the present invention will be described in detail.
FIG. 1 is a cross-sectional view of an EC apparatus 1 according to an embodiment of the present invention, in which a first electrode 10 having a conductive layer 12 on one surface of a support 11 and a conductive layer on one surface of a support 21 are also shown. The second electrode 20 having 22 and the electrochromic layer 30 are included. The electrochromic layer 30 is disposed so as to be sandwiched between the conductive layer 12 and the conductive layer 22. At least one of the supports 11 and 21 is transparent. In the EC device having such a configuration, when a voltage is applied between the conductive layer 12 and the conductive layer 22, the electrochromic layer changes color or changes color.

[electrode]
In the EC apparatus of the present invention, at least one of the pair of electrodes, that is, the first electrode and the second electrode, more preferably both the first electrode and the second electrode are conductive fine particles. And a conductive layer containing a binder. The electrode is usually based on a structure having a support and a conductive layer on one surface thereof. Of the first electrode and the second electrode, at least one of the electrodes is preferably transparent. Here, “transparent” means that the total visible light transmittance is 70 to 100%. The transparent support used in the present invention preferably has a total visible light transmittance of 85 to 100%, particularly preferably 90 to 100%.
The support may be colored so long as transparency is ensured.

[Support]
Examples of the support include a plastic film, a plastic plate, and a glass plate. More specifically, polyethylene terephthalate (PET) (melting point: 258 ° C.), polyethylene naphthalate (PEN) (melting point: 269 ° C.), polyethylene (PE) (melting point: 135 ° C.), polypropylene (PP) (melting point: 163 ), Polystyrene (melting point: 230 ° C.), polyvinyl chloride (melting point: 180 ° C.), polyvinylidene chloride (melting point: 212 ° C.), triacetyl cellulose (TAC) (melting point: 290 ° C.), etc. The following plastic film or plastic plate is preferable, and PET is particularly preferable from the viewpoints of light transmittance and workability.

[Conductive layer]
The electrode used in the present invention has a conductive layer containing conductive fine particles and a binder.
[Conductive fine particles]
The conductive fine particles further include metal oxides such as SnO ₂ , ZnO, TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, and MoO ₃ , and composite oxides thereof, and these metal oxides. Mention may be made of metal oxide particles containing different atoms. As the metal _{oxide, SnO 2, ZnO, TiO 2} , Al 2 O 3, In 2 O 3, MgO is preferred, SnO ₂ is particularly preferable. The SnO _2, SnO ₂ are preferred doped with antimony, SnO ₂ is preferred which is particularly doped antimony 0.2-2.0 mol%.

  There is no restriction | limiting in particular about the shape of the electroconductive fine particles used for this invention, A granular form, needle shape, etc. are mentioned. The particle diameter of the conductive fine particles is preferably 0.005 to 0.12 μm. The lower limit of the particle diameter is more preferably 0.008 μm and even more preferably 0.01 μm. The upper limit of the particle diameter is more preferably 0.08 μm and even more preferably 0.05 μm. By satisfy | filling the said particle diameter conditions, it is excellent in transparency and can form a uniform conductive layer in the electroconductive in-plane direction.

The lower limit value of the powder resistance (9.8 MPa green compact) of the conductive fine particles is preferably 0.8 Ωcm, more preferably 1 Ωcm, and even more preferably 4 Ωcm. The upper limit value of the powder resistance (9.8 MPa compact) of the conductive fine particles is preferably 35 Ωcm, more preferably 20 Ωcm, and even more preferably 10 Ωcm. By satisfying the above powder resistance condition, it is possible to form a conductive layer that is uniform in the conductive in-plane direction.
The specific surface area (Simple BET method) is preferably from ^{60~120m 2 / g, 70~100m 2 /} g is more preferable. Among these, those satisfying all of the above preferred conditions are particularly preferable.

When the conductive fine particles are spherical particles, the average primary particle size is preferably 0.005 to 0.12 μm, more preferably 0.008 to 0.05 μm, and 0.01 to 0.03 μm. More preferred. The powder resistance is preferably 0.8-7 Ωcm, more preferably 1-5 Ωcm.
In the case of needles, the average axial length is preferably 0.2-20 μm in the long axis and 0.01-0.02 μm in the short axis. The powder resistance is preferably 3 to 35 Ωcm, and more preferably 5 to 30 Ωcm.
As the conductive fine particles having the above-mentioned characteristics, the SN series manufactured by Ishihara Sangyo Co., Ltd. or the conductive material manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd. can be used.

[Binder of conductive layer]
The binder of the conductive layer has a function of uniformly dispersing the conductive fine particles in the conductive layer and fixing the conductive layer to the support surface. As such a binder, both a water-insoluble polymer and a water-soluble polymer can be used as a binder, but a water-soluble polymer is preferably used.

  Specific examples of the water-soluble polymer include, for example, gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polysaccharides such as starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, Examples include polyacrylic acid, polyalginic acid, polyhyaluronic acid, carboxycellulose, and the like. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group. Gelatin may be chemically modified gelatin such as acetylation, deamination, benzoylation, dinitrophenylation, trinitrophenylation, carbamylation, phenylcarbamylation, succinylation, succination, phthalation. There are gelatin and the like. Among these, the case where phthalated gelatin is used is preferable. When phthalated gelatin is used, it is possible to achieve both improved conductivity and improved coated surface. In the present invention, it is particularly preferable to use gelatin.

The mass ratio of the conductive fine particles to the binder is preferably 1:33 to 5: 1 in the former: latter ratio. The lower limit is more preferably 1: 3. The upper limit is more preferably 1.5: 1.
The conductive layer preferably content of the conductive fine particles are provided to be in the range of ^{0.05g / m 2 ~0.9g / m 2} . The lower limit is more preferably ^{0.1g / m 2, 0.2g / m} 2 is more preferred. The above upper limit is more preferably ^{0.5g / m 2, 0.45g / m} 2 is particularly preferred.
Furthermore, the content of the binder in the conductive layer ^is suitably be provided within an amount of ^{0.05g / m 2 ~0.5g / m 2} , a 0.05g / ^{m 2} ~0.3g / m 2 it is more preferable to provide a range, it is most preferable to provide the extent that further a ^{0.05g / m 2 ~0.2g / m 2} .
By setting the amount of the conductive fine particles and the amount of the binder in such a range, the conductive fine particles are uniformly dispersed and the desired conductivity as the electrode can be secured, so that an electrode having excellent transparency can be obtained. it can.

  It is preferable that the electrode used for this invention contains the mesh in which the line | wire is formed with the electroconductive metal in the said conductive layer or adjacent to the said conductive layer. By using a conductive layer including such a mesh, an electrode excellent in transparency and conductivity can be obtained more easily.

  FIG. 2 is a partially enlarged cross-sectional view showing an embodiment of a transparent electrode having a conductive layer including a mesh as described above. The transparent electrode 10 includes a second conductive layer 131 including a mesh 132 formed of a lattice-shaped metal on one surface of the transparent support 11 and a conductive fine particle powder 122 provided thereon. The conductive layer 12 is composed of one conductive layer 121.

As shown in FIG. 3, when the width of the opening 133 (one side of the square) is X (unit: μm) and the surface resistance of the opening 133 is Y (unit: Ω / □), as shown in FIG. In addition, it is preferably formed so as to satisfy the following formulas (a) and (b).
Formula (a) 50 ≦ X ≦ 7000
Formula (b) 10 ⁵ ≦ Y ≦ (5 × 10 ²³ ) × X ^−4.02

Y is more preferably formed to satisfy the following formula (b1), and more preferably the following formula (b2).
Formula (b1) 10 ⁵ ≦ Y ≦ 1 × 10 ²³ × (X) ^−4.02
Formula (b2) 10 ⁵ ≦ Y ≦ 3 × 10 ²² × (X) ^−4.25

  It is advantageous to produce the mesh using a photosensitive silver halide emulsion since a large-area electrode can be produced at low cost. Specifically, a light-sensitive silver halide emulsion layer is provided on a transparent support, which is exposed to a desired mesh pattern, developed and, if necessary, fixed, to form a line composed of developed silver. A mesh having a desired mesh pattern composed of (strings) can be produced. Hereinafter, this manufacturing method will be described.

  In the present invention, the mesh composed of the lines formed of developed silver is not intersected with the first line group composed of a number of lines extending in a certain direction without intersecting each other. It is composed of at least two line groups of the second line group composed of many lines extending in a certain direction, and the first line group and the second line group are arranged so as to cross each other. Those having a mesh pattern are included. In this case, a linear lattice in which a large number of each of the first line group and the second line group is constituted by a straight line, and the first line group and the second line group intersect at an angle substantially orthogonal to each other. The pattern includes a wavy grating pattern having a curved shape formed by first and second line groups each including a group of lines meandering with many lines. Furthermore, a mesh having a honeycomb-shaped mesh pattern in which one shape surrounded by each line is a hexagon is also included.

FIG. 3 is a plan view of a square linear lattice pattern mesh. The line width D should be as narrow as possible if the mesh exhibits desired conductivity. Generally, it is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less. The line width is preferably 1 μm or more, and more preferably 3 μm or more. For example, in the linear lattice pattern, the ratio of the line width D / the width X of the opening, that is, the line / space is preferably 5/995 to 10/595.
In the present invention, the width X of the opening of the mesh of the conductive layer is 50 μm to 7,000 μm, more preferably 100 μm to 5,000 μm, and further preferably 200 to 2,000 μm. In the present invention, a transparent conductive layer having a higher resistance may be formed by further applying a conductive polymer or the like on the conductive layer within a range in which conductivity is ensured.

As the photosensitive silver halide emulsion, those used in silver salt photographic film, photographic paper, film for printing plate making, emulsion mask for photomask, and the like can be used. Light sensitive silver halide emulsion layer in the range of 0.1 to 40 g / m ² in terms of silver, more preferably from 0.5~25g / m ^2, more preferably of 0.5 to 10 g / m ² It is provided on the support so as to be in the range, most preferably in the range of 4 to 8.5 g / m ² .

The photosensitive silver halide emulsion may contain a metal compound belonging to Group VIII or Group VIIB. In particular, in order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, an iron compound, an osmium compound, or the like. These compounds may be compounds having various ligands.
In order to increase the sensitivity, doping with a metal hexacyanide complex such as K ₄ [Fe (CN) ₆ ], K ₄ [Ru (CN) ₆ ] or K ₃ [Cr (CN) ₆ ] is advantageous. To be done.
A water-soluble rhodium compound can be used as the rhodium compound. Examples of the water-soluble rhodium compound include a rhodium halide (III) compound, a hexachlororhodium (III) complex salt, a pentachloroacorodium complex salt, a tetrachlorodiacolodium complex salt, a hexabromorhodium (III) complex salt, and a hexaamine rhodium (III). ) Complex salt, trizalatodium (III) complex salt, K ₃ [Rh ₂ Br ₉ ] and the like.
Examples of the iridium compound include hexachloroiridium complex salts such as K ₂ [IrCl ₆ ] and K ₃ [IrCl ₆ ], hexabromoiridium complex salts, hexaammineiridium complex salts, and pentachloronitrosyliridium complex salts.

  When the photosensitive silver halide emulsion is produced, it is preferable that the washing and desalting be performed without using an anionic precipitating agent in the production process. In order to carry out water washing and desalting by precipitating the emulsion only by pH operation without the presence of an anionic precipitant and removing the supernatant, it is preferable to use chemically modified gelatin as a dispersion medium. When gelatin with amino group positive charge changed to uncharged or negative charge is used as dispersion medium, it is possible to precipitate the emulsion only by lowering the pH of the emulsion, and no anionic precipitation agent is required. . Examples of such gelatin include gelatin subjected to acetylation, deamination, benzoylation, dinitrophenylation, trinitrophenylation, carbamylation, phenylcarbamylation, succinylation, succination, phthalation, etc. . Among these, the case where phthalated gelatin is used is preferable. When phthalated gelatin is used, it is possible to achieve both improved conductivity and improved coated surface.

[Binder of photosensitive silver halide emulsion]
A light-sensitive silver halide emulsion (hereinafter also simply referred to as “emulsion”) helps to disperse silver halide grains uniformly and to allow the emulsion provided on the support to adhere well to the support. A binder is used for the purpose. As such a binder, both a water-insoluble polymer and a water-soluble polymer can be used as a binder, but a water-soluble polymer is preferably used.
Examples of the binder include polysaccharides such as gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, polyacrylic acid, polyacrylic acid, and the like. Examples include alginic acid, polyhyaluronic acid, and carboxycellulose. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group. As the gelatin, the above-mentioned chemically modified gelatin may be used. In the present invention, it is particularly preferable to use gelatin.

  The content of the binder contained in the emulsion is not particularly limited, and can be appropriately determined as long as dispersibility and adhesion can be exhibited. The binder content in the emulsion is preferably 1/10 or more in terms of Ag / binder volume ratio, more preferably 1/4 or more, still more preferably 1/2 or more, and particularly preferably 1/1 or more. The Ag / binder volume ratio is preferably 10/1 or less, more preferably 5/1. Note that the Ag / binder volume ratio is obtained by converting the amount of silver halide / binder amount (weight ratio) of the raw material into the amount of silver / binder amount (weight ratio), and further converting the amount of silver / binder amount (weight ratio) to the amount of silver / It can obtain | require by converting into binder amount (volume ratio).

[Emulsion solvent]
The solvent used in the emulsion is not particularly limited. For example, water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, sulfoxides such as dimethyl sulfoxide, And esters such as ethyl acetate, ethers, etc.), ionic liquids, and mixed solvents thereof.
The content of the solvent used in the emulsion is in the range of 30 to 90% by mass and in the range of 50 to 80% by mass with respect to the total mass of the photosensitive silver halide and binder contained in the emulsion. preferable.

[Other additives]
There are no particular restrictions on the various additives used in the emulsion, and any can be preferably used. For example, thickeners, antioxidants, matting agents, lubricants, antistatic agents, nucleation accelerators, spectroscopic agents. Examples include sensitizing dyes, surfactants, antifoggants, hardeners, and anti-black spot agents. Further, a substance having a high dielectric constant may be added, or a hydrophobic group introduction / hydrophobic compound may be added as an additive to the binder to make the surface hydrophobic.

The above-mentioned conductive fine particles can be contained in the emulsion. As a result, a conductive layer containing conductive fine particles and a binder (the binder used in the photosensitive silver halide emulsion can be used as it is) can be formed simultaneously with the formation of the mesh. Cost can be further reduced. The amount of the conductive fine particles in this case, is preferably selected from the range of 0.05g ^{/ m 2} ~0.9g ^/ m 2 as coated amount provided on the support, 0.1g ^/ m 2 ~0. is more preferably selected from the range of 6 g / ^{m 2,} it is most preferably selected from the range of ^{0.2g / m 2 ~0.4g / m 2} .

  The electrode used in the present invention may include a mesh in a conductive layer containing conductive fine particles and a binder as described above, and a conductive layer containing conductive fine particles and a binder (hereinafter referred to as a first conductive layer). A layer having a mesh (hereinafter also referred to as a second conductive layer) is formed as a layer adjacent to the first conductive layer and the second conductive layer as a conductive layer necessary as an electrode. It may have a function. In the case of an electrode having such a first conductive layer and a second conductive layer, an embodiment in which the second conductive layer and the first conductive layer are provided in this order on the support is preferable.

For in order on the support and a second conductive layer electrode having a first conductive layer, that the coating amount of the conductive fine particles in the first conductive layer is 0.1g ^/ m ² ~0.6g / m 2 ^preferably, more preferably ^{0.1g / m 2 ~0.5g / m 2} , further preferably ^{0.2g / m 2 ~0.4g / m 2} . Also, if having a first conductive layer and the second conductive layer are sequentially on a support, that the coating amount of the conductive fine particles contained in the first conductive layer is 0.1g ^/ m ² ~0.6g / m 2 are ^preferred, more preferably from ^{0.1g / m 2 ~0.5g / m 2} , it is more preferably from ^{0.16g / m 2 ~0.4g / m 2} . In these cases, the amount of the binder in the first conductive layer containing conductive fine particles is preferably from ^{0.05g / m 2 ~0.5g / m 2} , more preferably 0.05g ^/ m 2 ~0.3g / ^{m 2,} most preferably a ^{0.05g / m 2 ~0.2g / m 2} . By setting it as the quantity of a binder, electroconductive fine particles are contained uniformly and desired electroconductivity can be hold | maintained.

When the electrode used for this invention has a 1st conductive layer and a 2nd conductive layer, it is preferable that a 1st conductive layer and a 2nd conductive layer satisfy | fill the following relationships. By satisfying such a relationship, the electrical characteristics of the electrode as the conductive layer become more uniform, and the performance as the electrode can be made sufficient.
(1) In the first conductive layer and the second conductive layer, the surface resistance of the second conductive layer is small.
(2) The surface resistance of the first conductive layer is 1 × 10 ³ Ω / sq or more (1 × 10 ¹⁴ Ω / sq or less), and the surface resistance of the second conductive layer is 1000Ω / sq or less (0.01Ω / sq). sq or more).
The upper limit value of the surface resistance of the first conductive layer (conductive fine particle-containing layer) is more preferably 1 × 10 ¹³ Ω / sq, and the lower limit value of the surface resistance of the first conductive layer is 1 × More preferably, it is 10 ⁸ Ω / sq, and particularly preferably 1 × 10 ⁹ Ω / sq.
The upper limit value of the surface resistance of the second conductive layer is more preferably 150Ω / sq. The lower limit value of the surface resistance of the second conductive layer is more preferably 0.1Ω / sq, and particularly preferably 1Ω / sq.

It is preferred for the first conductive layer to be made to contain in the range silica of ^{0.05g / m 2 ~0.3g / m 2} . The content of silica is, 0.16 g / ^{m 2} or more preferably, 0.24 g / ^{m 2} or more is more preferable. The content of silica is more preferably not more than ^{0.5g / m 2, 0.4g / m} 2 or less is more preferred.
As silica, colloidal silica (colloidal silica) is preferably used.
Colloidal silica refers to a colloid of silicic acid fine particles having an average particle diameter of 1 nm or more and 1 μm or less, and is described in JP-A-53-112732, JP-B-57-009051, JP-A-57-51653, and the like. You can refer to what is being done. These colloidal silicas can be prepared and used by a sol-gel method, or commercially available products can be used.
For preparing colloidal silica by the sol-gel method, see Werner Stober et al., J. MoI. Colloid and Interface Sci., 26, 62-69 (1968), Ricky D. It can be synthesized with reference to the description of Badley et al., Langmuir 6, 792-801 (1990), Journal of Color Material Association, 61 [9] 488-493 (1988).
In addition, when using commercially available products, SNOWTEX-XL (average particle size 40-60 nm), SNOWTEX-YL (average particle size 50-80 nm), SNOWTEX-ZL (average particle) manufactured by Nissan Chemical Co., Ltd. 70 to 100 nm in diameter), PST-2 (average particle diameter 210 nm), MP-3020 (average particle diameter 328 nm), Snowtex 20 (average particle diameter 10 to 20 nm, SiO ₂ / Na ₂ O> 57), Snowtex 30 (Average particle size 10-20 nm, SiO ₂ / Na ₂ O> 50), SNOWTEX C (average particle size 10-20 nm, SiO ₂ / Na ₂ O> 100), SNOWTEX O (average particle size 10-20 nm, SiO ₂ / Na ₂ O> 500) or the like can be preferably used (both are trade names. Here, SiO ₂ / Na ₂ O is the content mass ratio of silicon dioxide and sodium hydroxide to sodium hydroxide) conversion to the Na ₂ O And which is expressed upon, it is described in the catalog.). When using a commercial item, SNOWTEX-YL, SNOWTEX-ZL, PST-2, MP-3020, and SNOWTEX C are particularly preferable.

The main component of colloidal silica is silicon dioxide, but it may contain alumina or sodium aluminate as a minor component, and further, an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonia as a stabilizer. Or an organic base such as tetramethylammonium.
Examples of colloidal silica include colloidal silica having an elongated shape with a thickness of 1 to 50 nm and a length of 10 to 1000 nm described in JP-A-10-268464, JP-A-9-218488, or JP-A-10-111544. Also, composite particles of colloidal silica and organic polymer described in the above publication can be preferably used.

Next, a method for forming a mesh using the above emulsion will be described.
For an electrode comprising a light-sensitive silver halide emulsion layer prepared as described above and a first conductive layer containing conductive fine particles and a binder provided adjacent to the emulsion layer in some cases. The emulsion layer of the light-sensitive material is subjected to mesh-like exposure and then subjected to development and fixing processes to form a mesh composed of developed silver.
[exposure]
The method of exposing the emulsion layer in a pattern may be performed by surface exposure using a photomask or by scanning exposure using a laser beam. At this time, refractive exposure using a lens or reflection exposure using a reflecting mirror may be used, and exposure methods such as contact exposure, proximity exposure, reduced projection exposure, and reflection projection exposure can be used.

[Development processing]
After the emulsion layer is exposed, it is further developed. The development processing can be performed by a general development processing technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask, and the like.
In the present invention, by performing the above-described pattern exposure and development processing, a mesh-like conductive portion (metal silver portion) is formed in the exposed portion. After the development process, it is preferable to perform a fixing process for the purpose of removing and stabilizing the photosensitive silver halide in the unexposed area. For the fixing process, a technique of fixing process used for silver salt photographic film, photographic paper, film for printing plate making, emulsion mask for photomask, and the like can be used.
In the layer containing the mesh thus obtained, when the conductive layer is contained in the emulsion layer, the conductive fine particle is dispersed in the light transmitting portion from which the silver halide has been removed, and the layer containing the mesh is more than the metallic silver portion. A high resistance conductive layer is formed. When the first conductive layer containing conductive fine particles is provided in a layer other than the emulsion layer, a conductive layer in which conductive fine particles are dispersed is similarly formed in the light transmitting portion.

  The electrode formed by forming the first conductive layer or the first conductive layer and the second conductive layer on one surface of the support as described above can be used as an electrode of the EC device of the present invention as it is. It is preferable to provide a barrier layer on the other surface of the support (the surface of the support opposite to the surface on which the conductive layer is provided).

[Barrier layer]
The barrier layer is provided for the purpose of reducing moisture, gas, and the like contained in the air from entering the electrochromic layer through the electrode and suppressing deterioration of the electrochromic layer over time.
As the barrier layer, a layer containing polyvinylidene chloride may be used.
The barrier layer may include at least one organic region and at least one inorganic region, or may include at least one organic layer and at least one inorganic layer, at least two organic layers, and at least two layers. The inorganic layer of the layer may be laminated alternately.
In addition, the barrier layer may include a so-called gradient material layer in which the organic layer and the inorganic region continuously change in the film thickness direction in the composition constituting the barrier layer. Examples of the gradient material include a paper by Kim et al. “Journal of Vacuum Science and Technology A Vol. 23 p971-977 (2005 American Vacuum Society) Journal of Vacuum Science and Technology A Vol. 23, pages 971-977 (published in 2005). And a continuous layer in which the organic region and the inorganic region do not have an interface as disclosed in US Patent Publication No. 2004-46497. Hereinafter, for simplification, the organic layer and the organic region are described as “organic layers”, and the inorganic layer and the inorganic region are described as inorganic layers.
The number of layers constituting the barrier layer is not particularly limited, but typically 2 to 30 layers are preferable, and 3 to 20 layers are more preferable. Moreover, you may include other structural layers other than an organic layer and an inorganic layer.

  The organic layer in the barrier layer is preferably an organic layer containing an organic polymer as a main component. Here, the main component means that the first component of the component constituting the organic layer is an organic polymer, and usually 80% by weight or more of the component constituting the organic layer is an organic polymer. Examples of the organic polymer include polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, and polyurethane. , Polyether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound and other thermoplastic resins, or polysiloxane, etc. Examples thereof include organosilicon polymers. The organic layer may be made of a single material or a mixture, or may be a laminated structure of sublayers. In this case, each sublayer may have the same composition or a different composition. Further, as described above, as disclosed in US 2004-46497, the interface with the inorganic layer is not clear and the layer may be a layer whose composition changes continuously in the film thickness direction.

The organic layer is preferably formed by curing a polymerizable composition containing a polymerizable compound.
(Polymerizable compound)
The polymerizable compound is preferably a radical polymerizable compound and / or a cationic polymerizable compound having an ether group as a functional group, more preferably a compound having an ethylenically unsaturated bond at the terminal or side chain, and / or A compound having an epoxy or oxetane at the terminal or side chain. Of these, compounds having an ethylenically unsaturated bond at the terminal or side chain are preferred. Examples of compounds having an ethylenically unsaturated bond at the terminal or side chain include (meth) acrylate compounds, acrylamide compounds, styrene compounds, maleic anhydride, etc., (meth) acrylate compounds and / or Styrenic compounds are preferred, and (meth) acrylate compounds are more preferred.
As the (meth) acrylate compound, (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and the like are preferable.
As the styrene compound, styrene, α-methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxystyrene, 4-carboxystyrene and the like are preferable.

  When the organic layer is formed by coating and curing a polymerizable composition containing a polymerizable compound, the polymerizable composition may contain a polymerization initiator. When using a photoinitiator, it is preferable that the content is 0.1 mol% or more of the total amount of the polymerizable compounds, and more preferably 0.5 to 2 mol%. By setting it as such a composition, the polymerization reaction via an active component production | generation reaction can be controlled appropriately. Examples of photopolymerization initiators are commercially available from Irgacure series, Darocure series, Quantacure PDO, and Lamberti, which are commercially available from Ciba Specialty Chemicals. Examples include Ezacure series and oligomer type Ezacure KIP series.

  A method for forming the organic layer is not particularly defined, but for example, it can be formed by a solution coating method or a vacuum film forming method. Examples of the solution coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a slide coating method, or a method described in US Pat. No. 2,681,294. It can apply | coat by the extrusion coat method which uses a hopper. Although there is no restriction | limiting in particular as a vacuum film-forming method, Film-forming methods, such as vapor deposition and plasma CVD, are preferable. Further, a polymer may be applied by solution, or a hybrid coating method containing an inorganic substance as disclosed in JP 2000-323273 A or JP 2004-25732 A may be used.

Usually, a composition containing a polymerizable compound is cured by light irradiation, and the light to be irradiated is usually ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp. The radiation energy is preferably 0.1 J / cm ² or more, 0.5 J / cm ² or more is more preferable. When a (meth) acrylate compound is employed as the polymerizable compound, the polymerization is inhibited by oxygen in the air, and therefore it is preferable to reduce the oxygen concentration or oxygen partial pressure during polymerization. When the oxygen concentration during polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less. When the oxygen partial pressure during polymerization is reduced by the decompression method, the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. Further, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of 0.5 J / cm ² or more under a reduced pressure condition of 100 Pa or less.

The film thickness of the organic layer is not particularly limited, but if it is too thin, it is difficult to obtain film thickness uniformity, and if it is too thick, cracks are generated due to external force and the barrier property is lowered. From this viewpoint, the thickness of the organic layer is preferably 50 nm to 2000 nm, and more preferably 200 nm to 1500 nm.
The organic layer is preferably smooth as described above. The smoothness of the organic layer is preferably less than 1 nm and more preferably less than 0.5 nm as an average roughness (Ra value) of 1 μm square. The surface of the organic layer is required to be free of foreign matters such as particles and protrusions. For this reason, it is preferable that the organic layer is formed in a clean room. The degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less.
It is preferable that the organic layer has a high hardness. It has been found that when the hardness of the organic layer is high, the inorganic layer is formed smoothly and as a result, the barrier ability is improved. The hardness of the organic layer can be expressed as a microhardness based on the nanoindentation method. The microhardness of the organic layer is preferably 100 N / mm or more, and more preferably 150 N / mm or more.

(Inorganic layer)
The inorganic layer is usually a thin film layer made of a metal compound. As a method for forming the inorganic layer, any method can be used as long as it can form a target thin film. For example, there are a physical vapor deposition method (PVD) such as a vapor deposition method, a sputtering method, and an ion plating method, various chemical vapor deposition methods (CVD), and a liquid phase growth method such as plating and a sol-gel method. The component contained in the inorganic layer is not particularly limited as long as it satisfies the above performance. For example, it is a metal oxide, metal nitride, metal carbide, metal oxynitride, or metal oxycarbide, and Si, Al, In An oxide, nitride, carbide, oxynitride or oxycarbide containing one or more metals selected from Sn, Zn, Ti, Cu, Ce and Ta can be preferably used. Among these, a metal oxide, nitride or oxynitride selected from Si, Al, In, Sn, Zn and Ti is preferable, and a metal oxide, nitride or oxynitride of Si or Al is particularly preferable. These may contain other elements as secondary components.
The smoothness of the inorganic layer is preferably less than 1 nm as an average roughness (Ra value) of 1 μm square, and more preferably 0.5 nm or less. The inorganic layer is preferably formed in a clean room. The degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less.

  Although it does not specifically limit regarding the thickness of an inorganic layer, It attaches to 1 layer, Usually, it exists in the range of 5-500 nm, Preferably it is 10-200 nm. The inorganic layer may have a laminated structure including a plurality of sublayers. In this case, each sublayer may have the same composition or a different composition. Further, as described above, as disclosed in US 2004-46497, the interface with the organic layer is not clear and the layer may be a layer whose composition changes continuously in the film thickness direction.

Lamination of an organic layer and an inorganic layer Lamination of an organic layer and an inorganic layer can be performed by successively and repeatedly forming an organic layer and an inorganic layer according to a desired layer configuration. When the inorganic layer is formed by a vacuum film forming method such as a sputtering method, a vacuum vapor deposition method, an ion plating method, or a plasma CVD method, the organic layer is also preferably formed by a vacuum film forming method such as the flash vapor deposition method. . During production of the barrier layer, it is particularly preferable to always laminate the organic layer and the inorganic layer in a vacuum of 1000 Pa or less without returning to atmospheric pressure in the middle. The pressure is more preferably 100 Pa or less, more preferably 50 Pa or less, and further preferably 20 Pa or less.
In particular, when at least two organic layers and at least two inorganic layers are alternately laminated, high barrier properties can be exhibited. Alternating lamination may be carried out in the order of organic layer / inorganic layer / organic layer / inorganic layer from the support side, or may be laminated in the order of inorganic layer / organic layer / inorganic layer / organic layer.
When the barrier layer as described above is provided, the plastic film as the support is preferably made of a heat resistant material. Specifically, it is preferable that the glass transition temperature (Tg) is 100 ° C. or higher and / or the linear thermal expansion coefficient is 40 ppm / ° C. or lower and is made of a transparent material having high heat resistance. Tg and a linear expansion coefficient can be adjusted with an additive. As such a thermoplastic resin, for example, polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, ZEONOR 1600: 160 ° C. manufactured by Nippon Zeon Co., Ltd.), polyarylate ( PAr: 210 ° C., polyethersulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: Japanese Patent Laid-Open No. 2001-150584 compound: 162 ° C.), polyimide (for example, Mitsubishi Gas Chemical) Neoprim: 260 ° C.), fluorene ring-modified polycarbonate (BCF-PC: compound of JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound of JP 2000-227603 A) : 205 ° C), acryloyl compound (Compound described in JP-A 2002-80616: 300 ° C. or more) (the parenthesized data are Tg). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

  An adhesive layer for ensuring a good adhesive force between the conductive layer and the electrochromic layer may be provided between the conductive layer and the electrochromic layer of the electrode used in the present invention. The thickness of such an adhesive layer is preferably as thin as possible within a range where a desired adhesive force can be secured. In that case, it is preferable that the conductive fine particles contained in the conductive layer penetrate through the adhesive layer and are in contact with the electrochromic layer.

[Electrochromic layer]
The electrochromic layer used in the EC device of the present invention contains a polymer, a plasticizer, an electrochromic compound and an organic charge transport agent.
[Polymer polymer]
The polymer used in the present invention is preferably selected from thermoplastic polymers. Specifically, polyacrylic esters such as polymethyl methacrylate, polyvinyl acetals such as polyvinyl butyral, and poly (bisphenol A) are used. Polycarbonates represented by carbonic acid esters (commonly called polycarbonate), polysulfones, and polyurethanes are included.

[Plasticizer]
The plasticizer used in the present invention has a function of imparting flexibility, elasticity and desired optical properties to the electrochromic layer, and imparting adhesion to the electrode.
A preferred group of such plasticizers include alkylene carbonates such as propylene carbonate, aliphatic carboxylic acid esters of polyolene glycol such as triethylene glycol di (2-ethylhexanoate), dihexyl adipate. And dialkyl esters of aliphatic dibasic acids such as dibutyl sebacate. These plasticizers may be used alone or in combination of two or more.
[Electrochromic compounds]
The electrochromic compound used in the present invention is a compound that reversibly develops, discolors, or decolors by at least one of an electrochemical oxidation reaction and a reduction reaction. A compound selected from “EC dye” is also preferred.
One group of particularly preferred EC dyes includes (1) pyridine compounds, (2) conductive polymers, (3) styryl compounds, (4) donor / acceptor type compounds, (5) other organic dyes, (6) A metal complex dye or the like is included. These may be used individually by 1 type and may use 2 or more types together.

Examples of (1) pyridine compounds include viologen, heptyl viologen (such as diheptyl viologen dibromide), methylene bispyridinium, phenanthroline, azobipyridinium, 2,2-bipyridinium complex, and quinoline / isoquinoline.
Examples of the conductive polymer (2) include polypyrrole, polythiophene, polyaniline, polyphenylenediamine, polyaminophenol, polyvinylcarbazole, polymer viologen polyion complex, TTF, and derivatives thereof.
Examples of the (3) styryl compounds include 2- [2- [4- (dimethylamino) phenyl] ethenyl] -3,3-dimethylindolino [2,1-b] oxazolidine, 2- [4- [4- (Dimethylamino) phenyl] -1,3-butadienyl] -3,3-dimethylindolino [2,1-b] oxazolidine, 2- [2- [4- (dimethylamino) phenyl] ethenyl]- 3,3-dimethyl-5-methylsulfonylindolino [2,1-b] oxazolidine, 2- [4- [4- (dimethylamino) phenyl] -1,3-butadienyl] -3,3-dimethyl-5 -Sulfonylindolino [2,1-b] oxazolidine, 3,3-dimethyl-2- [2- (9-ethyl-3-carbazolyl) ethenyl] indolino [2,1-b] oxazolidine 2- [2- [4- (acetylamino) phenyl] ethenyl] -3,3-dimethyl-indolino [2,1-b] oxazolidine, and the like.

Examples of the (4) donor / acceptor type compounds include tetracyanoquinodimethane and tetrathiafulvalene.
Examples of (5) other organic dyes include carbazole, methoxybiphenyl, anthraquinone, quinone, diphenylamine, aminophenol, Tris-aminophenylamine, phenylacetylene, cyclopentyl compound, benzodithiolium compound, squalium salt, cyanine, rare earth Examples include phthalocyanine complexes, ruthenium diphthalocyanines, merocyanines, phenanthroline complexes, pyrazolines, redox indicators, pH indicators, and derivatives thereof.
Examples of the (6) metal complex dye include Prussian blue, metal-bipyridyl complex, metal phenanthroline complex, metal-phthalocyanine complex, metaferricyanide, and derivatives thereof.

  Among these, viologen dyes such as viologen and heptyl viologen (diheptyl viologen dibromide, etc.) are excellent in electrochromic characteristics, especially in response speed and repeated durability, and it is easy to obtain a desired hue. It is preferable from the point of being. Further, as the EC dye, a reduction coloring type that shows colorless or ultra-light color in the oxidation state and develops color in the reduction state, an oxidation coloring type that shows colorless or ultra-light color in the reduction state and develops color in the oxidation state, It may be any of the multicolor coloring types that exhibit color development in the reduced state or the oxidized state, and develop several kinds of colors depending on the degree of reduction or oxidation, and can be appropriately selected according to the purpose.

  The combination when two or more EC dyes are used in combination is not particularly limited and may be appropriately selected according to the purpose. For example, a combination of viologen and polyaniline, a combination of polypyrrole and polymethylthiophene, Examples include a combination of polyaniline and Prussian blue.

[Organic charge transfer agent]
The organic charge transfer agent used in the present invention is hydroquinone and hydroquinone having 1 to 2 lower alkyl groups having 1 to 4 carbon atoms, benzoic acid, 3,4-dihydroxybenzoic acid, urea, diphenyl ether, 4,4 ′. In addition to diaminodiphenyl ether, 1,10-phenanthroline, biphenol, benzophenone, diphenylthiocarbazone and the like, polythiophene or polyfuran represented by the following general formula (1), oligomers and polymers of acetylene, and conductive polymers such as polyvinylcarbazole Is done. Among these, hydroquinone and polythiophene represented by the following general formula (1) are preferable.

In the general formula (1), R ^{1 to} R ⁸ independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, an alkoxy group, or an aryloxy group, X represents S or O, and n represents 1 Integers of ~ 5 are shown.

In the general formula (1), R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. R ³ , R ⁴ , R ⁷ and R ⁸ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. R ⁵ and R ⁶ are preferably an alkyl group substituted with an alkoxycarbonyl group, more preferably a methoxycarbonylmethyl group or a methoxyethyl group, and n is more preferably an integer of 1 to 3.

  When a conductive polymer is used as the organic charge transfer agent, this electrolyte polymer is considered to act as an electrolyte for the electrochromic layer. In this case, when a voltage is applied between the first electrode and the second electrode, electrons injected from one electrode (cathode) travel along the conductive polymer and are carried to the other electrode (anode). Become. At this time, if an EC dye is present in the vicinity of the conductive polymer, it is presumed that electrons transmitted through the conductive polymer are hopped to the nearby EC dye and the EC dye is reduced to develop color. Therefore, the electrochromic layer using the conductive polymer does not need to contain a component corresponding to the conventional electrolytic solution (gel), and therefore the electrolytic solution may leak from the electrochromic layer. It will be resolved. Therefore, in the EC device according to the present invention, there is a great advantage that it is freed from the necessity of sealing in preparation for leakage of the electrolyte from the electrochromic layer.

[Other additives]
It is preferable to further contain an ultraviolet absorber in the electrochromic layer. Such an ultraviolet absorber can be appropriately selected from commercially available compounds.

  The electrochromic layer used in the present invention comprises 30% to 80% by weight polymer, 10% to 60% by weight plasticizer, 1% to 10% by weight electrochromic compound and 0.005% by weight. It is preferable to contain the organic charge transport agent of% -20 mass%. Furthermore, by selecting the amount of each component to be used from such a range, it is easy to create an EC device that has excellent electrochromic characteristics, that is, responsiveness when a voltage is applied, and that does not leak even without sealing the electrochromic layer. Is obtained. A more preferable use range of the organic charge transfer agent is selected from a range of 5% by mass to 20% by mass.

The electrochromic layer used in the present invention is obtained by uniformly mixing the above components. When mixing each component uniformly, it is preferable to mix these components and then to a uniform mixture by heating to a temperature sufficient to melt the polymer. Although the specific heating temperature varies depending on the type of the polymer, the general range is 200 ° C. or less.
As another method, it is also possible to employ a method in which each component is dissolved or emulsified and dispersed by additionally using an organic solvent to obtain a uniform solution, and then the low boiling point solvent is removed by heating.

  A specific method for forming the electrochromic layer between the first electrode and the second electrode is to place the spacer between the first electrode and the second electrode so that the respective conductive layers face each other. It is possible to employ a method in which the solution is disposed by being interposed, and a solution in which each component is heated and melted as described above is cast between the electrodes and then spread between the electrodes, and then cooled. As another method, the electrochromic layer is melt-cast to form a self-supporting film having a desired thickness, and then the first electrode and the second electrode are bonded to each of these electrodes through an adhesive layer. A method of assembling the EC device of the present invention by joining the conductive layers so as to sandwich each other may be used. Alternatively, after the electrochromic layer is melt-formed and before cooling and solidification, the EC device of the present invention may be assembled by being joined so as to be sandwiched between the first electrode and the second electrode without using an adhesive. In addition, when a low boiling point solvent is additionally used to dissolve or disperse each component of the electrochromic layer to form a uniform solution, this solution is used as either the first electrode or the second electrode. After coating most of the low boiling point solvent contained in the coating liquid layer and evaporating most of the low-boiling solvent contained in the coating liquid layer, the conductive layer of the other electrode is superposed so as to be in contact with the coating liquid layer. It is preferable to employ a method in which all or almost all of the remaining low-boiling solvent is removed by heating or the like.

  The thickness of the electrochromic layer in the EC device according to the present invention is selected so that the optical density during coloring (usually when voltage is applied) is in a desired range. The general range is selected from the range of 30 μm to 500 μm, and more preferably selected from the range of 50 μm to 300 μm.

  In the EC device of the present invention, the electrochromic layer is colored from colorless or light to dark hue by applying a voltage between the first electrode and the second electrode. What is necessary is just to select suitably the voltage applied at this time according to the electrochromic compound and organic charge transfer agent which were used. Generally, it is selected from the range of 0.5V to 10V.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.
In the following examples, “%” in the unit of concentration means “mass%”.

[Example 1]
(Preparation of emulsion A)
・ 1 liquid:
750 ml of water
Gelatin (phthalated gelatin) 8g
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
・ Two liquids 300ml
150 g silver nitrate
・ 3 liquid water 300ml
Sodium chloride 38g
Potassium bromide 32g
Hexachloroiridium (III) potassium salt
(0.005% KCl 20% aqueous solution) 5 ml
Ammonium hexachlororhodate
(0.001% NaCl 20% aqueous solution) 7 ml

Potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution) and ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) used in the three liquids were mixed with their respective complex powders, KCl 20% aqueous solution, NaCl. It was dissolved in a 20% aqueous solution and prepared by heating at 40 ° C. for 120 minutes.
To 1 liquid maintained at 38 ° C. and pH 4.5, 90% of the 2 and 3 liquids were simultaneously added over 20 minutes with stirring, and an average particle diameter (diameter. The same applies hereinafter) of 0.16 μm. ) Core particles were formed. Subsequently, the following 4th and 5th liquids are added over 8 minutes, and the remaining 10% of the 2nd and 3rd liquids are added over 2 minutes to grow the particle size of the above core particles to 0.21 μm. It was. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete the formation of silver halide grains.

・ 4 liquid water 100ml
Silver nitrate 50g
・ 5 liquid 100ml
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5mg

  Thereafter, desalting was performed by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., and the pH was lowered using sulfuric acid until the silver halide precipitated (the pH was in the range of 3.6 ± 0.2).

  Next, about 3 liters of the supernatant was removed (first water washing). Further, 3 liters of distilled water was added, and sulfuric acid was added again until silver halide precipitated. Again, 3 liters of the supernatant was removed (second water wash). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting process.

The emulsion after washing and desalting was adjusted to pH 6.4, pAg 7.5, and 10 mg sodium benzenethiosulfonate, 3 mg sodium benzenethiosulfinate, 15 mg sodium thiosulfate and 10 mg chloroauric acid were added, and the optimum sensitivity was obtained at 55 ° C. And 1,3,3a, 7-tetraazaindene (100 mg) as a stabilizer and 100 mg of proxel (trade name, manufactured by ICI Co., Ltd.) as a preservative were added. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain diameter of 0.22 μm and a coefficient of variation of 9% was obtained. Finally, pH = 6.4, pAg = 7.5, conductivity = 40 μS / m, density = 1.2 × 10 ³ kg / m ³ , and viscosity = 60 mPa · s.

(Preparation of emulsion layer coating solution A)
The emulsion A was subjected to spectral sensitization by adding sensitizing dye 5.7 × 10 ⁻⁴ mol / mol Ag having the following structural formula: SD-1. Add KBr 3.4 × 10 ⁻⁴ mol / mol Ag, 2-diethylamino-4,6-bis (hydroxyamino) -1,3,5-triazine 8.0 × 10 ⁻⁴ mol / mol Ag, and mix well. did.
Then, 1,3,3a, 7-tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻⁴ mol / mol Ag 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 90 mg / m ² , colloidal silica having a particle size of 10 μm and 15% of gelatin, aqueous latex having the following structural formula: aqL-6 50 mg / m ² , polyethyl acrylate latex 100 mg / m ² , latex copolymer of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoxyethyl methacrylate (mass ratio 88: 5: 7) 100 mg / m ² , core-shell type latex (core: styrene / butadiene mass ratio is 37/63 co-weight) Copolymer, shell: copolymer having a mass ratio of styrene / 2-acetoxyethyl acrylate of 84/16, core / shell mass ratio = 50/50) 100 mg / m ² , 4% of the following structural formula: Cpd- Emulsion layer coating solution A was prepared by adding the compound having No. 7 respectively. Further, the pH of the coating solution A was adjusted to 5.6 using citric acid.

(Preparation of electrode A)
The following silver halide emulsion layer, first conductive layer (layer containing conductive fine particles and binder), and adhesion-imparting layer are formed on one surface of a polyethylene terephthalate film support having a moisture-proof subbing layer containing vinylidene chloride on both sides. Were applied in this order to prepare electrode preparation sample A.
<Silver halide emulsion layer>
Emulsion layer coating solution A prepared as described above was coated on the undercoat layer so that the amount in terms of Ag was 8.0 g / m ² and gelatin was 0.94 g / m ² .
<First conductive layer>
On the silver halide emulsion layer, the following 6 solutions were applied at 20 ml / m ² to provide a conductive fine particle layer.
・ 6 liquids:
943 ml of water
Gelatin 33g
Sb-doped tin oxide (trade name: SN100P, manufactured by Ishihara Sangyo Co., Ltd.) 20g
Sb-doped tin oxide is a spherical conductive fine particle having an average particle diameter (primary particle diameter) in the range of 0.01 to 0.03 μm, a powder resistance in the range of 1 to 5 Ωcm, and a specific surface area. (Simple BET method) was in the range of 70 to 80 m ² / g. In addition, a surfactant, preservative, and pH adjuster were added as appropriate.
<Adhesion imparting layer>
The following 7 solutions were applied to the upper part of the silver halide emulsion layer and the conductive fine particle layer at 10 ml / m ² to provide an adhesion-imparting layer.
・ 7 liquids:
1000ml of water
15g gelatin
In addition, a surfactant, preservative, and pH adjuster were added as appropriate.

The coated product thus obtained was dried and used as sample A.
In sample A, the conductive particles are applied to the first conductive layer so that the conductive particles contain 0.4 g / m ² and the conductive particle / binder ratio is 0.6 / 1 (mass ratio). In Sample A, the total binder amount of the first conductive layer and the adhesion-imparting layer is applied at 0.3 g / m ² . In addition, in order to investigate the resistance (conductive film resistance) of the first conductive layer alone, this coated sample A was not exposed and developed, and only the fixing process was performed, and the surface resistance was measured by removing the silver halide. It was 10 ⁷ Ω / □. The surface resistance (Ω / □) was measured with a digital ultrahigh resistance / microammeter 8340A (trade name, manufactured by ADC Corporation).

<Exposure / Development / Fixing>
Next, a photomask line / space of the shape shown in FIG. 3 that can give a developed silver image of line / space = 5 μm / 595 μm to the sample A / photo with space of 595 μm / 5 μm (pitch 600 μm) in which the space is a lattice. Exposure using parallel light using a high-pressure mercury lamp as a light source through a mask, development with the following developer, and further fixing with a fixer (trade name: N3X-R for CN16X: manufactured by Fuji Film) The electrode A was obtained by thoroughly washing with pure water and then drying. By this treatment, a second conductive layer including a mesh formed of developed silver was formed.
Developer composition:
The following compounds are contained in 1 liter of developer.
Hydroquinone 0.037mol / L
N-methylaminophenol 0.016 mol / L
Sodium metaborate 0.140 mol / L
Sodium hydroxide 0.360 mol / L
Sodium bromide 0.031 mol / L
Potassium metabisulfite 0.187 mol / L

(Production of electrodes B to C)
In the production of the electrode A, the amount of conductive fine particles contained in the first conductive layer (g / m ² ) and the amount of conductive fine particles / binder were changed by changing the coating amount of the liquids 6 and 7, the amount of conductive fine particles and the amount of gelatin. Electrodes B to C were produced in the same manner as the electrode A except that the mass ratio was changed as shown in Table 1 below. In the electrode C, the first conductive layer is not provided on the silver halide emulsion layer, but the first conductive layer is provided on the moisture-proof subbing layer containing vinylidene chloride, and the halogenated layer is provided on the first conductive layer. It was produced in the same manner as the electrode A except that a silver emulsion layer was provided.

(Production of electrochromic device A)
The following components are heated to a temperature of 150 ° C. to 200 ° C. and uniformly melt-mixed to form a film having a thickness of 65 μm on an aluminum thin plate electrode, and then cooled and solidified as described above. The produced electrode A was bonded so that the adhesion providing layer faced the aluminum thin plate electrode, and a lead wire was joined to each electrode to produce an electrochromic device A.
Polyvinyl butyral (Sekisui Chemical's ESREC BL-1) 30%
Triethylene glycol di-2-ethylhexanoate 25%
Propylene carbonate 37%
Viologen compound 1 (having the following structural formula) 4%

Hydroquinone 4%
(Production of electrochromic devices B to C)
Electrochromic devices B to C were prepared in the same manner as the above electrochromic device A, except that electrodes B to C were used instead of electrode A, respectively.
When a voltage was applied to the electrochromic devices A to C produced as described above, the entire surface of the device was instantly changed from pale yellow to blue. Moreover, when the application of the voltage was stopped, the original light yellow color was restored within 1 second.
An electrode AX was prepared in the same manner as the electrode A except that the conductive fine particle layer was not provided, and an EC device AX was prepared in the same manner as the EC device A except that the electrode AX was used. When a voltage was applied to the EC apparatus AX, the position corresponding to the developed silver mesh of the apparatus changed from pale yellow to blue, but the entire surface did not change.
It was confirmed that the EC device according to the present invention instantaneously changes color by using the electrode having the conductive fine particle-containing layer as described above.

In the production of the electrode A, the conductive fine particle content (g / m ² ) and the conductive fine particle / The following electrodes were prepared in the same manner as the electrode A except that the binder mass ratio was changed as shown in Table 2 below. An EC device was produced in the same manner as EC device A except that these were used. In any of these EC devices, when a voltage was applied, the entire surface of the device was instantly changed from pale yellow to blue. However, when the electrode P was used, the discoloration at the mesh opening of the developed silver was slightly insufficient as compared with that using the electrode A.

(Example 2)
In the same manner as in the electrochromic device A of Example 1, except that an electrochromic layer having the following composition was heated and melted at 150 ° C. to 200 ° C. and then formed into a film having a thickness of 65 μm. Electrochromic G was prepared by pressing and adhering to each other. When a voltage was applied to the electrochromic device, the color changed from pale yellow to blue in 20 seconds. Moreover, even when the voltage application was stopped, the blue state was maintained, and the original light yellow color was restored in about 30 minutes.
Polyvinyl butyral (Sekisui Chemical's ESREC BL-1) 52%
Triethylene glycol di-2-ethylhexanoate 30%
Propylene carbonate 10%
Viologen compound 1 4%
4% polythiophene of the following structural formula

(Example 3)
In the production of the electrochromic device A of Example 1, the example was carried out in the same manner as the device A, except that the content of hydroquinone was changed to 5%, 6%, 7%, 8%, 9% and 10%, respectively. 3 EC devices were prepared. With respect to the electrochromic devices produced as described above, when a voltage was applied, the entire surface of the device changed from pale yellow to blue. When the application of voltage was stopped, the original light yellow color was restored within 1 second.

  According to the present invention, the electrochromic device reduces the need for strict sealing, and an electrochromic device with no risk of electrode breakage and high response speed can be obtained. Therefore, in the present invention, an electrode having high conductivity can be produced at a low cost, and since the leakage of the liquid component from the electrochromic layer is small, the need for strict sealing is reduced. As a result, a large-area EC device can be manufactured at low cost. Thus, the EC device of the present invention is used to obtain a window having a dimming function for reducing the illuminance of incident light or blocking the incident light, such as an application field that could not be conventionally used from the viewpoint of cost. In other words, application to application fields that require a large area becomes possible.

DESCRIPTION OF SYMBOLS 10 ... Electrode 11 ... Support 12 ... Conductive layer 30 ... Electrochromic layer 121 ... First conductive layer 122 ... Conductive fine particle powder 131 ... Second conductive layer 132- ··mesh

Claims (15)

Having a first electrode, an electrochromic layer and a second electrode in this order,
At least one of the first and second electrodes has a conductive layer containing conductive fine particles and a binder, and the electrochromic layer contains a polymer, a plasticizer, an electrochromic compound, and an organic charge transport agent. Contains electrochromic device. At least one of the first and second electrodes includes a conductive layer having a mesh pattern, the width X (μm) of the opening of the mesh pattern of the conductive layer, and the surface of the opening of the mesh pattern The electrochromic device according to claim 1, wherein the resistance Y (Ω / □) satisfies the following expressions (a) and (b).
Formula (a) 50 ≦ X ≦ 7000
Formula (b) 10 ⁵ ≦ Y ≦ (5 × 10 ²³ ) × X ^−4.02   The electrochromic device according to claim 1, wherein the high molecular polymer is a thermoplastic polymer.   The electrochromic device according to any one of claims 1 to 3, wherein the polymer is polymethyl methacrylate, polyvinyl butyral, polycarbonate, polysulfone, or polyurethane.   The electrochromic device according to any one of claims 1 to 4, wherein the plasticizer has a boiling point of 150 ° C or higher.   The electrochromic according to any one of claims 1 to 5, wherein the plasticizer is at least one compound selected from the group consisting of alkylene carbonate, polyalkylene glycol dialkyl ester and dialkyl ester of dibasic carboxylic acid. apparatus.   The electrochromic device according to any one of claims 1 to 6, wherein the electrochromic compound is a viologen compound.   The electrochromic device according to any one of claims 1 to 7, wherein the organic charge transfer agent is a compound selected from the group consisting of polyalkyne, polythiophene, and polyfuran.   30% to 80% by weight of the polymer polymer, 10% to 60% by weight plasticizer, 1% to 10% by weight electrochromic compound and 0.005% to 20% by weight of the electrochromic layer. The electrochromic device according to any one of claims 1 to 8, comprising an organic charge transfer agent.   The electrochromic layer according to any one of claims 1 to 7 and 9, wherein the electrochromic layer contains 5% by mass to 20% by mass of an organic charge transporting agent, and the organic charge transporting agent is hydroquinone. apparatus.   The electrochromic device according to any one of claims 1 to 10, wherein a mass ratio of the conductive fine particles and the binder contained in the conductive layer is in a range of 1:33 to 1.5: 1. The electrochromic device according to any one of claims 1 to 11, the amount of the conductive fine particles contained in the conductive layer is in the range of ^{0.05g / m 2 ~0.9g / m 2} .   The electrochromic device according to claim 1, wherein the conductive layer has a surface resistance of 0.01Ω / □ or more.   Each of the first and second electrodes has a conductive layer containing conductive fine particles and a binder on one surface of the plastic film support, and at least one barrier layer on the surface of the support The electrochromic device according to claim 1, wherein each of the conductive layers of the first and second electrodes is opposed to the electrochromic layer.   The electrochromic device according to claim 14, wherein the barrier layer is made of an inorganic oxide.

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