JPH10206904A - Electrochromic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrochromic element having resistance against UV rays and durability for outdoor use by forming a UV-absorbing layer between a transparent substrate and a transparent electrode and by forming the UV- absorbing layer by applying and hardening a component prepared by the reaction of an aminosilane compd. and a UV-absorbent having carboxyl groups in the molecule to produce amides bond on the transparent substrate. SOLUTION: A transparent conductive substrate (A) comprising a transparent substrate 1a, a transparent electrode 2a located inside the substrate 1a, and a UV-absorbing layer 3 formed between them, and a transparent substrate (B) comprising a transparent substrate 1b and a transparent electrode 2b located inside the substrate 1b are disposed to face each other. Further, an electrochromic layer 4 is formed on the inner surface of the transparent electrode 2b of the transparent conductive substrate (B). An ionic conductive material 6 is held between the transparent substrate (A) and the transparent conductive substrate (B) with the electrochromic layer 4, and the layer of the ion conductive material 6 is sealed with a sealing agent. Thus, the electrochromic element can be produced at a low cost.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an electrochromic device.

[0002]

2. Description of the Related Art Devices using electrochromic materials are widely expected to be used, but conventional electrochromic devices have a drawback that they are liable to deteriorate in an environment where ultraviolet rays are irradiated such as outdoors. In order to prevent this, for example, it has been proposed to provide an ultraviolet shielding layer outside the substrate constituting the electrochromic element.
It is not satisfactory in terms of wear resistance and durability. In addition, the electrochromic dimmer generally has a pair of transparent electrodes disposed between a pair of transparent substrates, an electrochromic layer and an electrolyte layer are disposed therebetween, and an ultraviolet blocking layer is provided inside the transparent electrode. It has been proposed to prevent deterioration due to ultraviolet rays (Japanese Patent Application Laid-Open No. 62-148339).
JP-A-63-236016). According to this method, there is no effect on the scratch resistance and the like of the transparent substrate constituting the device. However, when the ultraviolet shielding layer is made of a metal oxide (Japanese Patent Application Laid-Open No. 62-148339), the near-ultraviolet region cannot be sufficiently cut, so that deterioration of ultraviolet radiation cannot be sufficiently suppressed. There is a point. Further, when a dichroic layer is employed as the ultraviolet shielding layer (Japanese Patent Application Laid-Open No. 63-236016), there is a problem that the film formation process is required many times, which is disadvantageous in cost.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrochromic device which has ultraviolet resistance enough to be used outdoors and can be manufactured at low cost.

[0004]

According to the present invention, an ion conductive material sandwiched between a pair of opposing conductive substrates having electrodes on at least inner surfaces thereof and an inner surface of the inner surface of the conductive substrate are provided. A layer containing an electrochromic substance provided on at least one of an electrode and an ion-conductive substance, wherein at least one of the counter electrodes is a transparent substrate and a transparent substrate disposed inside the transparent substrate. A transparent conductive substrate provided with electrodes,
An ultraviolet absorbing layer is provided between at least one of the transparent conductive substrates and the transparent electrode, and the ultraviolet absorbing layer is formed of at least (a) an aminosilane compound represented by the general formula (1) or a derivative thereof (hereinafter, referred to as an aminosilane compound). , Referred to as “Component A”)
And (b) an ultraviolet absorber having a carboxyl group in the molecule (hereinafter referred to as “component B”), and a component that forms an amide bond derived from the aminosilane or a derivative thereof is placed on a transparent substrate. The present invention provides an electrochromic device characterized by being produced by coating and curing the same. Further, according to the present invention, there is provided an electrochromic device, wherein an overcoat layer is provided between the ultraviolet absorbing layer and the transparent conductive film.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The electrochromic device of the present invention is basically composed of a pair of opposing conductive substrates having electrodes on at least inner surfaces, an ionic conductive material, a layer containing the electrochromic material, and an ultraviolet absorbing layer. Is configured. The opposing conductive substrate constituting the electrochromic element of the present invention may be a substrate having an electrode function on at least the inner side surface.Specifically, the entire conductive substrate is formed of a material having an electrode function, Any of those including an electrode disposed inside the substrate may be used. In the case where the entire conductive substrate is formed of a material having an electrode function, as the material having an electrode function, iron, copper, silver, aluminum, tin, lead, gold, a simple substance of a metal such as zinc, or a material thereof. Various alloys are listed. When a conductive substrate including the substrate and the electrodes is adopted, the substrate is not particularly limited as long as it has a smooth surface, but at least one of the pair of opposed conductive substrates is a transparent substrate. Required. Specific examples of the substrate include various plastics, resins, glass, wood, and stone materials. The transparent substrate is not particularly limited, for example, colorless or colored glass,
In addition to using tempered glass or the like, a colorless or colored resin having transparency may be used. Specifically, polyethylene terephthalate, polyamide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylenesulfide, polycarbonate, polyimide,
Examples include polymethyl methacrylate and polystyrene. The term “transparent” in the present invention means that the substrate has a transmittance of 10 to 100%, and the substrate in the present invention has a smooth surface at room temperature, and the surface may be flat or curved. Alternatively, it may be deformed by stress. The electrode in the case of employing a conductive substrate including the substrate and the electrode is not particularly limited as long as the object of the present invention is achieved, but it is preferable that the electrode satisfy transparency, and that at least one of the pair of opposed conductive substrates be used. The electrode on the transparent substrate side needs to be a transparent electrode. The form of the electrode is desirably a film or a layer. Examples of the electrode include a metal thin film such as gold, silver, chromium, copper, and tungsten, and a conductive film made of a metal oxide. Examples of the metal oxide include ITO (In ₂ O ₃ -SnO ₂ ), tin oxide,
Silver oxide, zinc oxide, vanadium oxide, and the like can be given. The thickness of the electrode is usually 100 to 5000 angstroms,
Preferably, it is 500 to 3000 angstroms. Further, the surface resistance (resistivity) can be appropriately selected depending on the use of the substrate of the present invention, but is usually 0.5 to 500 Ω / cm.
² , preferably 1 to 50 Ω / cm ² . The method for forming the electrode is not particularly limited, and a known method can be appropriately selected depending on the types of the metal, metal oxide, and the like constituting the electrode. Usually, it can be formed by a vacuum deposition method, an ion plating method, a sputtering method, a sol-gel method, or the like. In either case, the substrate temperature is usually 100
It is desirable to form within the range of -350 ° C. Also,
The electrode may be provided with a partially opaque electrode active material for the purpose of imparting oxidation-reduction ability, imparting conductivity, and imparting electric double layer capacitance. In this case, when a transparent electrode is used as the electrode, it is necessary to provide the electrode within a range that satisfies the transparency of the entire electrode surface. As an opaque electrode active material,
For example, metals such as copper, silver, gold, platinum, iron, tungsten, titanium, and lithium, organic substances having redox ability such as polyaniline, polythiophene, polypyrrole, and phthalocyanine; carbon materials such as activated carbon and graphite;
Metal oxides such as ₂ O ₅ , WO ₃ , MnO ₂ , NiO, and Ir ₂ O ₃ or a mixture thereof can be used. Further, in order to bind them to the electrodes, various resins may be used. In order to apply the opaque electrode active material or the like to the electrode, for example, a composition comprising activated carbon fiber, graphite, acrylic resin, or the like is formed on the ITO transparent electrode in a fine pattern such as a stripe, or gold (A).
u) On the thin film, a composition comprising V ₂ O ₅ , acetylene black, butyl rubber and the like can be formed in a mesh shape.

The ion conductive material used in the electrochromic device of the present invention is provided between the opposed conductive substrates. The method of sandwiching and providing is not particularly limited, and a vacuum injection method, an air injection method, a method of injecting into a gap provided between opposing conductive substrates by a meniscus method, or the like, a sputtering method, an evaporation method, a sol-gel method, or the like. After a layer of an ion conductive substance is formed on an electrode of a conductive substrate, a method of combining an opposing conductive substrate, a method of glass-forming using a film-shaped ion conductive substance, or the like can be used. This ion conductive substance is
The material is not particularly limited as long as it can color, decolor, and change the color of the electrochromic material described below, but is a material that generally exhibits an ionic conductivity of 1 × 10 ⁻⁷ S / cm or more at room temperature. Is preferred. The ion conductive substance is not particularly limited, and a liquid ion conductive substance, a gelled liquid ion conductive substance, a solid ion conductive substance, or the like can be used. In the present invention, a solid ion conductive substance is particularly desirable. As the liquid-based ionic conductive substance, a substance obtained by dissolving a supporting electrolyte such as salts, acids, and alkalis in a solvent can be used. The solvent is not particularly limited as long as it can dissolve the supporting electrolyte, but a polar solvent is particularly preferable. Specifically, water, methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile,
Organic polar solvents such as γ-butyrolactone, sulfolane, 1,3-dioxane, N, N-dimethylformamide, 1,2-dimethoxyethane, tetrahydrofuran, and the like, preferably propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, Organic polar solvents such as acetonitrile, γ-butyrolactone, sulfolane, 1,3-dioxane, N, N-dimethylformamide, 1,2-dimethoxyethane, and tetrahydrofuran are preferred. These can be used alone or as a mixture when used. Salts as a supporting electrolyte are not particularly limited, various alkali metal salts,
Examples thereof include inorganic ion salts such as alkaline earth metal salts, quaternary ammonium salts, and cyclic quaternary ammonium salts. Specific examples include LiClO ₄ , LiSCN, LiBF ₄ , and LiA.
sF ₆ , LiCF ₃ SO ₃ , LiPF ₆ , LiI, Na
I, NaSCN, NaClO ₄ , NaBF ₄ , NaAs
F _6, KSCN, Li of KCl and the like, Na, alkali metal salts of K such _{or, (CH 3) 4 NBF 4} , (C 2 H 5) 4 N
BF ₄ , (n-C ₄ H ₉ ) ₄ NBF ₄ , (C ₂ H ₅ ) ₄
NBr, (C ₂ H ₅ ) ₄ NClO ₄ , (n-C ₄ H ₉ )
Suitable examples include quaternary ammonium salts such as ₄ NCLO ₄ and cyclic quaternary ammonium salts, and the like, and mixtures thereof. The acids as the supporting electrolyte are not particularly limited, and include inorganic acids and organic acids. Specific examples include sulfuric acid, hydrochloric acid, phosphoric acids, sulfonic acids, and carboxylic acids. The alkali as a supporting electrolyte is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, and lithium hydroxide. As the gelled liquid ion-conductive substance, it is possible to use a viscous or gel-like substance obtained by further adding a polymer or a gelling agent to the liquid ion-conductive substance. it can. The polymer is not particularly limited, for example, polyacrylonitrile, carboxymethyl cellulose,
Polyvinyl chloride, polyethylene oxide, polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, cellulose, polyester,
Examples include polypropylene oxide and Nafion. The gelling agent is not particularly limited, oxyethylene methacrylate, oxyethylene acrylate,
Urethane acrylate, acrylamide, agar, and the like. The solid ion conductive material is not particularly limited as long as it is a solid at room temperature and has ionic conductivity, and includes polyethylene oxide, a polymer of oxyethylene methacrylate, Nafion, polystyrene sulfonic acid, Li ₃ N, Na-β-Al ₂ O ₃ ,
Sn (HPO ₄ ) ₂ .H ₂ O and the like.
In particular, a polymer solid electrolyte using a polymer compound obtained by polymerizing an oxyalkylene methacrylate compound, an oxyalkylene acrylate compound, or a urethane acrylate compound is preferable.

[0007] As a first example of the solid polymer electrolyte, a composite material containing a urethane acrylate represented by the following general formula (2), the organic polar solvent, and the supporting electrolyte (hereinafter abbreviated as composition A): Solid polymer electrolyte obtained by solidifying the polymer.

Embedded image (Wherein R ¹ and R ² are the same or different groups,
It represents a group selected from general formulas (3) to (5). R ³ and R ⁴ are the same or different groups and each have 1 to 2 carbon atoms.
0, preferably 2 to 12 divalent hydrocarbon residues. Y
Represents a polyether unit, a polyester unit, a polycarbonate unit or a mixed unit thereof. N is 1 to
100, preferably 1 to 50, more preferably 1 to 2
Indicates an integer in the range of 0. )

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Embedded image In the general formulas (3) to (5), R ^{5 to} R ⁷ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁸ represents a divalent to tetravalent organic residue having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms. Specific examples of the organic residue include a hydrocarbon residue such as an alkyltolyl group, an alkyltetralyl group, and an alkylene group represented by the following general formula (6).

Embedded image In the general formula (6), R ⁹ represents an alkyl group having 1 to 3 carbon atoms or hydrogen, and p represents an integer of 0 to 6. p is 2
In the above case, R ⁹ may be the same or different. In the above-mentioned hydrocarbon residue, a part of hydrogen atoms is substituted by an oxygen-containing hydrocarbon group such as an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms. Group. As R ^{8 in the} general formulas (3) to (5), specifically, And the like. General formula (3)-
The divalent hydrocarbon residue represented by R ³ and R ⁴ in (5) includes a chain divalent hydrocarbon group, an aromatic hydrocarbon group,
Examples thereof include an alicyclic hydrocarbon group, and examples of the chain divalent hydrocarbon group include an alkylene group represented by the general formula (6). The aromatic hydrocarbon group and the alicyclic hydrocarbon group include the following general formula (7)
To (9).

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Embedded image In the general formulas (7) to (9), R ¹⁰ and R ¹¹ are the same or different groups and include a phenylene group, a substituted phenylene group (such as an alkyl-substituted phenylene group), a cycloalkylene group, and a substituted cycloalkylene group ( Alkyl-substituted cycloalkylene group). R ^{12 to} R ¹⁵ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Q represents an integer of 1 to 5. General formula (2)
Specific examples of R ³ and R ⁴ in the following general formula (1)
0) to (16).

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Embedded image In the general formula (2), Y represents a polyether unit, a polyester unit, a polycarbonate unit or a mixed unit thereof, and the polyether unit, the polyester unit, the polycarbonate unit and the mixed unit thereof are represented by the following general formulas, respectively. Examples include units represented by formulas (a) to (d).

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Embedded image In the general formulas (a) to (d), R ^{16 to} R ²¹ are the same or different groups and have 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms.
Shows 12 divalent hydrocarbon residues. In particular, R ¹⁹ has 2 carbon atoms.
About 6 is preferable. As R ^{16 to} R ²¹ , a linear or branched alkylene group or the like is preferable, and specifically,
R ¹⁸ is preferably a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a propylene group, or the like. Also, R ^{16 to} R ¹⁷
And R ^{19 to} R ²¹ are preferably an ethylene group, a propylene group or the like. Also, m is 2 to 300, preferably 10
Shows an integer of ~ 200. Further, r is an integer of 1 to 300, preferably 2 to 200, and s is 1 to 200, preferably 2
An integer of -100, t is 1-200, preferably 2-10
U represents an integer of 0 to 300, preferably 10 to 200. In the general formulas (a) to (d), each unit may be the same or a copolymer of different units. That is,
When a plurality of R ^{16 to} R ²¹ are present, R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ^20, and R ²¹ may be the same or different. Particularly preferred examples of the copolymer include a copolymerized unit of ethylene oxide and propylene oxide. The general formula (2)
The molecular weight of the urethane acrylate represented by
0 to 30,000, preferably 3,000 to 20,000
0 is desirable. The number of polymerizable functional groups in one molecule of the urethane acrylate is preferably 2 to 6, more preferably 2
~ 4 is desirable. The urethane acrylate represented by the general formula (2) can be easily produced by a known method, and the production method is not particularly limited. The organic polar solvent contained in the composition A is not limited as long as it has polarity and can dissolve the supporting electrolyte. Specifically, propylene carbonate, ethylene carbonate, butylene carbonate, γ-butyrolactone, sulfolane, 1 , 3-dioxane, N, N-dimethylformamide, 1,2-dimethoxyethane, acetonitrile,
A single compound or a mixture of two or more compounds such as tetrahydrofuran is mentioned as a preferable compound. The amount of the organic polar solvent (organic non-aqueous solvent) is usually 100 to 1200 parts by weight, preferably 20 to 100 parts by weight of urethane acrylate.
0 to 900 parts by weight. If the added amount of the organic non-aqueous solvent is too small, the ionic conductivity is not sufficient, and if the added amount of the organic non-aqueous solvent is too large, the mechanical strength may be reduced.

[0008] The supporting electrolyte is appropriately selected depending on its purpose such as the use of the polymer solid electrolyte of the present invention, and is not particularly limited as long as the object of the present invention is not impaired. Can be The amount added is 0.1 to 30% by weight, preferably 1 to 20% by weight, based on the organic non-aqueous solvent. The composition A is basically obtained by solidifying a basic component consisting of the urethane acrylate, an organic non-aqueous solvent (organic polar solvent), and a supporting electrolyte. Further components that do not impair the purpose can be added as needed. Examples of such optional components include a crosslinking agent and a polymerization initiator (light or heat). The polymer solid electrolyte of the first example can be sandwiched between opposing conductive substrates by solidifying after injecting the composition A into a desired place by a known method as appropriate. The term “solidification” as used herein means that a polymerizable or crosslinkable component or the like hardens as polymerization (polycondensation) or crosslinking progresses, and the composition as a whole does not substantially flow at room temperature. In this case, it has a network-like basic structure.

Further, as a second example of the solid polymer electrolyte, monofunctional acryloyl-modified polyalkylene oxide, polyfunctional acryloyl-modified polyalkylene oxide represented by the following general formula (17), an organic polar solvent, A solid polymer electrolyte obtained by solidifying a composite material containing a supporting electrolyte (hereinafter, abbreviated as composition B) is exemplified.

Embedded image (Wherein, R ²² , R ²³ , R ²⁴ and R ²⁵ are each hydrogen or an alkyl group having 1 to 5 carbon atoms;
In the general formula (17), R ²² , R ²³ , R ²⁴ and R ²⁵
Is hydrogen or an alkyl group having 1 to 5 carbon atoms, each of which is a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n-butyl group, a t-butyl group. , N-pentyl group and the like, which may be the same or different, and in particular, R ²² is hydrogen, methyl, R ²³ is hydrogen, methyl, R ²⁴ is hydrogen, methyl, R ²⁵ is hydrogen, methyl And an ethyl group. Further, n in the general formula (17) is an integer of 1 or more, usually 1 ≦ n ≦ 100,
Preferably 2 ≦ n ≦ 50, more preferably 2 ≦ n ≦ 3
Indicates an integer in the range of 0. As the compound represented by the general formula (17), specifically, an oxyalkylene unit has 1 to 100, preferably 2 to 50, and more preferably 1 to 100.
Methoxy polyethylene glycol methacrylate, methoxy polypropylene glycol methacrylate, ethoxy polyethylene glycol methacrylate, ethoxy polypropylene glycol methacrylate, methoxy polyethylene glycol acrylate having
Examples thereof include methoxy polypropylene glycol acrylate, ethoxy polyethylene glycol acrylate, ethoxy polypropylene glycol acrylate, and mixtures thereof. When n is 2 or more, oxyalkylene units may have different so-called copolymerized oxyalkylene units,
For example, methoxypoly (ethylene / propylene) glycol methacrylate having oxyethylene units in the range of 1 to 50, preferably 1 to 20, and oxypropylene units in the range of 1 to 50, preferably 1 to 20, Ethoxy poly (ethylene / propylene) glycol methacrylate, methoxy poly (ethylene / propylene) glycol acrylate, ethoxy poly (ethylene / propylene) glycol acrylate,
Or a mixture thereof. The polyfunctional acryloyl-modified polyalkylene oxide usable in the present invention includes a so-called bifunctional acryloyl-modified polyalkylene oxide represented by the general formula (18) and a so-called trifunctional or higher polyalkylene oxide represented by the general formula (19). And functional acryloyl-modified polyalkylene oxide.

Embedded image Wherein R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are each hydrogen or an alkyl group having 1 to 5 carbon atoms, and m is 1
The following integers are shown. )

Embedded image (Wherein R ³⁰ , R ³¹ and R ³² are each hydrogen or 1 to
Is an alkyl group having 5 carbon atoms, p is an integer of 1 or more, q is an integer of 2 to 4, and L is a q-valent linking group. In the general formula (18), R ²⁶ , R ²⁷ , R ²⁸
And R ²⁹ are each hydrogen or an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n-butyl group, a t-butyl group; -Butyl group, n-pentyl group and the like. In particular, it is preferable that R ²⁶ is hydrogen, methyl, R ²⁷ is hydrogen, methyl, R ²⁸ is hydrogen, methyl, and R ²⁹ is hydrogen, methyl. In addition, m in the general formula (18) represents an integer of 1 or more, usually 1 ≦ m ≦ 100, preferably 2 ≦ m ≦ 50, more preferably 2 ≦ m ≦ 30. Is an oxyalkylene unit of 1 to 100, preferably 2 to 50, more preferably 1
Polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate having a range of
Examples thereof include polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, and mixtures thereof. When m is 2 or more, the oxyalkylene unit may have a so-called copolymerized oxyalkylene unit different from each other. For example, 1 to 50, preferably 1
Having an oxypropylene unit in the range of 1 to 50, preferably 1 to 20,
Examples thereof include poly (ethylene / propylene) glycol dimethacrylate, poly (ethylene / propylene) glycol diacrylate, and mixtures thereof. R ³⁰ , R ³¹ and R ³² in the general formula (19) are each hydrogen or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group and an i-
Propyl group, n-propyl group, n-butyl group, t-butyl group,
and an n-pentyl group. In particular, R ³⁰ , R ³¹ and R
³² is preferably hydrogen or a methyl group. Also, p in the equation is 1
Integer or more, usually 1 ≦ p ≦ 100, preferably 2 ≦ p ≦
50, more preferably an integer in the range of 2 ≦ p ≦ 30. q is the number of links of the linking group L, and 2 ≦ q ≦ 4
Indicates an integer. The linking group L usually has 1 to 3 carbon atoms.
0, preferably 1-20 divalent, trivalent or tetravalent hydrocarbon groups. Examples of the divalent hydrocarbon group include an alkylene group, an arylene group, an arylalkylene group, an alkylarylene group, and a hydrocarbon group having these as a basic skeleton.Specifically, And the like. Further, as a trivalent hydrocarbon group,
Examples thereof include an alkyltolyl group, an aryltolyl group, an arylalkyltolyl group, an alkylaryltolyl group, and a hydrocarbon group having these as a basic skeleton. And the like. Further, as a tetravalent hydrocarbon group,
Examples thereof include an alkyltetralyl group, an aryltetralyl group, an arylalkyltetralyl group, an alkylaryltetralyl group, and a hydrocarbon group having these as a basic skeleton. And the like. Specific examples of such a compound include an oxyalkylene unit of 1 to 100, preferably 2 to 100.
Trimethylolpropane tri (polyethylene glycol acrylate), trimethylol propane tri (polyethylene glycol methacrylate), trimethylol propane tri (polypropylene glycol acrylate), trimethylol propane tri (polypropylene glycol methacrylate) having a range of 50, more preferably 1 to 20 ), Tetramethylol methane tetra (polyethylene glycol acrylate), tetramethylol methane tetra (polyethylene glycol methacrylate), tetramethylol methane tetra (polypropylene glycol acrylate), tetramethylol methane tetra (polypropylene glycol methacrylate),
2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane, 2,2-bis [4
-(Acryloxypolyisopropoxy) phenyl] propane, 2,2-bis [4- (methacryloxypolyisopropoxy) phenyl] propane, and mixtures thereof. When p is 2 or more, the oxyalkylene units may have so-called copolymerized oxyalkylene units different from each other. For example, 1 to 50, preferably 1
Having an oxypropylene unit in the range of 1 to 50, preferably 1 to 20,
Trimethylolpropane tri (poly (ethylene / propylene) glycol acrylate), trimethylolpropane tri (poly (ethylene / propylene) glycol methacrylate), tetramethylolmethanetetra (poly (ethylene / propylene) glycol acrylate),
Tetramethylolmethanetetra (poly (ethylene propylene) glycol methacrylate), or a mixture thereof, and the like. Of course, the general formula (1)
The bifunctional acryloyl-modified polyalkylene oxide represented by 8) may be used in combination with the trifunctional or higher polyfunctional acryloyl-modified polyalkylene oxide represented by the general formula (19). When the compound represented by the general formula (18) and the compound represented by the general formula (19) are used in combination, the weight ratio is usually 0.01 / 99.9 to 99.9 / 0.01, preferably 1/99. ~ 99/1, more preferably 20/8
The range of 0 to 80/20 is desirable. The weight ratio of the compound represented by the general formula (1) to the polyfunctional acryloyl-modified polyalkylene oxide used in the present invention is usually 1 / 0.00.
The range is 1 to 1/1, preferably 1 / 0.05 to 1 / 0.5. The mixing ratio of the polar organic solvent is usually 50 to 50% by weight of the compound represented by the general formula (2) and the polyfunctional acryloyl-modified polyalkylene oxide.
800% by weight, preferably in the range of 100 to 500% by weight. The mixing ratio of the supporting electrolyte is usually 1 to 30% by weight, preferably 3 to 20% by weight based on the weight of the compound represented by the general formula (2), the polyfunctional acryloyl-modified polyalkylene oxide and the polar organic solvent. % Range. The composition B contains, in addition to these components,
As an optional component, another component can be added as needed, as long as the present invention is not impaired. Examples of the optional component include, but are not particularly limited to, a photopolymerization initiator for photopolymerization and a thermal polymerization initiator for thermal polymerization. The amount of the polymerization initiator used in the present invention is usually 0.1 to the weight sum of the compound represented by the general formula (1) and the polyfunctional acryloyl-modified polyalkylene oxide.
005 to 5% by weight, preferably 0.01 to 3% by weight.

The solid polymer electrolyte of the second example can be sandwiched between opposing conductive substrates by solidifying the composition B after injecting the composition B into a desired place by a known method. The solidification here means that a polymerizable or crosslinkable component, such as a monofunctional or polyfunctional acryloyl-modified polyalkylene oxide, is cured as polymerization (polycondensation) or crosslinking proceeds, and the composition as a whole is substantially cured at room temperature. Means that the fluid does not flow. In this case, the monofunctional or polyfunctional acryloyl-modified polyalkylene oxide usually has a network-like basic structure. Of course, the ion conductive substance of the present invention is not limited to these.

In the electrochromic device of the present invention, a layer containing an electrochromic substance is provided on at least one of the electrode on the inner surface of the conductive substrate and the ion conductive substance. The electrochromic material, electrochemical oxidation, or colored by the reduction reaction and the like, a decoloring substance exhibiting such color change is not particularly limited as far as it is to achieve the purpose of the present invention, Mo ₂ O ₃ , Ir ₂ O ₃ , NiO, V ₂ O ₅ , WO
₃ , viologen, polythiophene, polyaniline, polypyrrole, metal phthalocyanine and the like are preferred. The layer containing the electrochromic substance may be a layer (film) composed of only the electrochromic substance or a layer (film) obtained by dispersing the electrochromic substance and a matrix component. A layer (film) composed of only a chromic substance is more preferable. The thickness of the layer containing the electrochromic substance is generally 10 nm to 1 μm, and preferably 50 to 800 nm. The method for forming the layer containing the electrochromic substance is not particularly limited, and is not particularly limited. Various known methods such as an ion plating method, a sputtering method, an electrolytic polymerization method, a dip coating method, and a spin coating method can be used. In the electrochromic device of the present invention, it is necessary that at least one of the opposing conductive substrates is a transparent conductive substrate including a transparent substrate and a transparent electrode disposed inside the transparent substrate. An ultraviolet absorbing layer is provided between at least one of the transparent conductive substrates and the transparent electrode. As a specific embodiment, in the case of an electrochromic device in which the substrate and the electrodes of the pair of opposing conductive substrates are all transparent, the ultraviolet absorbing layer is provided on at least one or both of the transparent substrate and the transparent electrode . Further, when a transparent conductive substrate having a transparent substrate and a transparent electrode and a non-transparent conductive substrate having an opaque substrate and / or electrode are provided, the ultraviolet absorbing layer is always provided between the transparent substrate and the transparent electrode. In this case, the ultraviolet absorbing layer may be provided between the electrode of the non-transparent conductive substrate and the electrode. As described above, the ultraviolet absorbing layer includes at least (a) an aminosilane compound represented by the general formula (1) or a derivative thereof (hereinafter, referred to as “component A”) and (b) a carboxyl group in the molecule. By producing an amide bond derived from the aminosilane or a derivative thereof by reacting with an ultraviolet absorbent (hereinafter, referred to as “component B”) having the amide bond, and applying and curing the component on a transparent substrate. It is characterized by. The aminosilane compound used as the component A in the present invention is represented by the following general formula (1).

Embedded image In the general formula (1), R ¹ is an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or a general formula-(CH ₂ )
_m- NH- [m is a divalent group represented by 1 ≦ m ≦ 4]. Specific examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group. Each R ² is the same or different, and includes a hydrogen atom, a hydroxyl group, a halogen atom such as chlorine and bromine,
An alkyl or alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or 6 to 10 carbon atoms, preferably 6 carbon atoms
To 8 aryl groups. However, at least one of all R ² is an alkoxy group or a hydroxyl group. Examples of the alkyl group for R ² include a methyl group and an ethyl group. A propyl group, an i-propyl group and the like can be exemplified. As the aryl group, a phenyl group and a tolyl group can be exemplified. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and an i-propoxy group. n is n ≧ 0, preferably 0
≤n≤3. Preferred examples of the aminosilane compound represented by the general formula (1) include 3-aminopropyltriethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrichlorosilane, -
Examples include aminopropyl polydimethylsiloxane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, and the like. Further, as the derivative of the aminosilane compound, a hydrolyzate of the above-mentioned suitable compound is preferably exemplified. The component A which is an aminosilane compound or a derivative thereof can be produced by a known method. In the present invention, a derivative of the aminosilane compound represented by the general formula (1) can also be used. As such a derivative, a hydrolyzate of the above-mentioned compound is preferably mentioned.

As the ultraviolet absorber having a carboxyl group in the molecule used as the component B, a compound having one or more carboxyl groups in the side chain of the molecule, for example, a compound having a benzotriazole skeleton or a benzophenone skeleton And the like. The compound having a benzotriazole skeleton is represented by the following general formula (20)
Compounds represented by the following formulas are preferred.

Embedded image R ³ in the general formula (20) represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10, preferably 1 to 6 carbon atoms. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group. The substitution position of R ³ is the 4- or 5-position of the benzotriazole skeleton, and the halogen atom and the alkyl group are usually located at the 4-position. R ⁴ in the formula represents a hydrogen atom or an alkyl group having 1 to 10, preferably 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group,
Examples thereof include a butyl group, a t-butyl group, and a cyclohexyl group. R ⁵ in the formula has 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms.
Represents an alkylene group or an alkylidene group. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group, and examples of the alkylidene group include an ethylidene group and a propylidene group. General formula (2
Examples of the compound represented by 0) include 3- (5-chloro-2).
H-benzotriazol-2-yl) -5- (1,1-
Dimethylethyl) -4-hydroxy-benzenepropanoic acid, 3- (2H-benzotriazol-2-yl) -4
-Hydroxybenzene ethane acid, 3- (5-methyl-2
H-benzotriazol-2-yl) -5- (1-methylethyl) -4-hydroxybenzenepropanoic acid.

Preferred examples of the compound having a benzophenone skeleton include benzophenone-based compounds represented by the following general formulas (21) to (24).

Embedded image

Embedded image

Embedded image

Embedded image In the general formulas (21) to (24), R ⁷ and R ⁸ are
The same or different groups represent a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 10, preferably 1 to 6 carbon atoms. n and m are integers in the range of 0 ≦ m ≦ 3 and 0 ≦ n ≦ 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, a cyclohexyl group, and the like.
Specific examples include a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, and a butoxy group. Wherein R ⁶ is
And represents an alkylene group having 1 to 10, preferably 1 to 3 carbon atoms or an alkylidene group. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group, and examples of the alkylidene group include an ethylidene group and a propylidene group. Specific examples of such a compound having a benzophenone skeleton include 2-hydroxy-4
-Methoxybenzophenone-5-carboxylic acid, 2,2 '
-Dihydroxy-4-methoxybenzophenone-5-carboxylic acid, 4- (2-hydroxybenzoyl) -3-hydroxybenzenepropanoic acid and the like are preferred. The ultraviolet absorbent having a benzotriazole skeleton or a benzophenone skeleton can be produced by a known method.

In the method for producing a coating component used in the present invention, the reaction for causing at least the component A and the component B to react to form an amide bond derived from the component A is usually mainly a dehydration reaction. At this time, the amount of the amide bond generated by the reaction is not particularly limited, but usually the component A
10 mol% or more, preferably 50 mol% of all aminosilanes
The upper limit is usually 100 mol%, but the upper limit may be less than 100 mol%.

In the method for producing a coating component used in the present invention, at least the component A and the component B may be reacted as described above, but at the time of the reaction or after the reaction, a range that does not impair the object of the present invention. The optional components may be further coexisted and added. Next, these optional components will be described. An example of the optional component is a silicone resin (hereinafter, referred to as “component C”). As the component C, a reactive silicone resin, that is, a silicone resin having a functional group capable of reacting with the alkoxysilyl group portion of the component A (usually a dehydration reaction and / or a dealcoholization reaction) is preferable. As the functional group, an alkoxysilyl group, a silanol group or the like is preferable. Generally, such a reactive silicone resin can be easily synthesized by a partial hydrolysis reaction of alkoxysilane or chlorosilanes and a subsequent condensation reaction. Commercially available products include pure silicone varnish (for example, trade name “XO7931-Clear”: manufactured by Okitsumo Co., Ltd.) and silicone resin (for example, trade name “S
R2410 ": Dow Corning Toray Silicone Co., Ltd.
Acryl-modified silicone resin (for example, trade name “Silacoat 1000”: manufactured by Chisso Corporation) and the like. Further, the silicone resin can be used in the form of a solution using various solvents as long as the object of the present invention is not impaired. The solvent is not particularly limited, but various hydrocarbon solvents, ketones, ethers, esters,
Ethers and esters. Further, various modifications of a silicone resin may be used. Component C
Can coexist during the reaction of component A and component B or after the reaction.
It is particularly preferred to coexist at the time of the reaction.

Other examples of the optional component include various epoxysilanes (hereinafter referred to as "component D").
Preferably, epoxysilanes represented by the following general formulas (25) to (26) are used.

Embedded image

Embedded image In the general formulas (25) to (26), R ⁹ and R ¹¹ are the same or different groups, and have an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or a group represented by the formula —R—O—R '−
Wherein R and R ′ each represent an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and each R ¹⁰ is the same or different, Hydrogen atom, hydroxyl group, halogen atom, carbon number 1-1
It represents 0, preferably 1 to 5 alkyl groups or alkoxy groups, or 6 to 10 carbon atoms, preferably 6 to 8 aryl groups. However, at least one of all R ¹⁰ is an alkoxy group or a hydroxyl group. n represents an integer of n ≧ 0, preferably 0 ≦ n ≦ 3. Preferable examples of the alkylene group include a methylene group, a trimethylene group, and a tetramethylene group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group,
t-butyl group, pentyl group, hexyl group, heptyl group,
An octyl group or the like is preferably exemplified.Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a t-butoxy group, a pentyloxy group, and a hexyloxy group. Examples include a phenyl group and a tolyl group.

Component D includes 3-glycidoxypropyltrimethoxysilane, dimethoxy-3-glycidoxypropylmethylsilane, 2- (3,4-epoxycyclohexylethyl) trimethoxysilane, dimethylethoxy-3-glycol Sidoxypropylsilane, 1,3-bis (3-glycidoxypropyl) -1,3-dimethyl-
Suitable examples include 1,3-dimethoxydisiloxane and mixtures thereof. Component D may be used after being hydrolyzed in advance. Further, the epoxy group can be used by ring-opening polymerization with an appropriate polymerization catalyst in advance. As the polymerization catalyst, a Lewis acid catalyst such as boron trifluoride diethyl ether complex, aluminum chloride, and diethyl zinc is preferable. The polymerization conditions for the ring-opening polymerization of the epoxy group are not particularly limited, but are usually about -80 ° C to 130 ° C, preferably about -20 ° C to 80 ° C. 10 minutes to 10 minutes
Time, preferably about 1 to 6 hours. The solvent used at this time is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, and various ketones and esters. Component D is allowed to coexist during or after the reaction of components A and B, but is preferably added after the reaction of components A and B. However, in the case of using a component D in which the epoxy group of the component D has been subjected to ring-opening polymerization in advance, it is preferably added during the reaction of the components A and B.

Other optional components include polyether-modified polysiloxanes (hereinafter, referred to as "component E"), and preferred are polyether-modified polysiloxanes represented by the following general formula (27). You.

Embedded image In the general formula (27), R ¹² , R ¹³ and R ¹⁴ are the same or different groups and represent an alkylene group having 1 to 10, preferably 1 to 5 carbon atoms, and each R ¹⁵ is the same or different. A different group is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group or an alkoxy group having 1 to 10, preferably 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. At least one of R ¹⁵ is an alkoxy group. m, n, and p are each m ≧
0, preferably 0 ≦ m ≦ 100, n ≧ 0, preferably 0
≦ n ≦ 10, p ≧ 0, preferably 0 ≦ p ≦ 10. Preferable examples of the alkylene group include a methylene group, a trimethylene group, and a tetramethylene group.
Preferred examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. As the alkoxy group, a methoxy group,
Examples include an ethoxy group, a propoxy group, a butoxy group, a t-butoxy group, a pentyloxy group, and a hexyloxy group. Examples of the aryl group include a phenyl group and a tolyl group. Such a component E represented by the general formula
Specific examples thereof include tetraethylene glycol-bis (triethoxysilylethyl) ether, polyethylene glycol-bis (triethoxysilylethyl) ether, polypropylene glycol-bis (triethoxysilylethyl) ether and mixtures thereof. Can be As the component E, those hydrolyzed in advance may be used. Component E is allowed to coexist during the reaction of component A and component B or after the reaction.
And it is preferably added during the reaction of component B. As the optional components, particularly, the epoxysilanes of the component D and the component E
By using the polyether-modified polysiloxanes, the UV-absorbing coating on the substrate has improved adhesion to the substrate without impairing the heat resistance, and is even more excellent, such as being less likely to break even in a thick film. It works.

As another optional component, an inorganic fine particle dispersion (hereinafter, referred to as “component F”) can be mentioned. The component F is not particularly limited, and examples thereof include a dispersion of fine particles of silica, alumina, titanium oxide, antimony oxide, and the like. The particle diameter of the fine particles is about 1 to 100 nm, and examples of the dispersion medium include water, methanol, xylene, and methyl ethyl ketone. As commercially available products, LUDOX L S (manufactured by DuPont), XBA-ST (manufactured by Nissan Chemical Industries, Ltd.) and the like are preferably exemplified. Component F is allowed to coexist during or after the reaction of components A and B, but is preferably added after the reaction of components A and B. By adding the component F, the surface hardness can be improved, and the wear resistance, chemical resistance, and the like can be improved. Incidentally, any of the optional components can be produced by a known method.

In the method for producing a coating component used in the present invention, at least the components A and B are used as described above.
And, if necessary, by reacting in the coexistence of the above-mentioned optional components. The reaction conditions are not particularly limited as long as the amide bond derived from the component A is generated, and the conditions are appropriately selected. Usually, the components A and B, and if desired, the optional components are dissolved in a solvent. After mixing, the reaction can be suitably performed in the presence of a solvent at room temperature to 350 ° C., preferably 60 to 250 ° C., usually for 5 minutes to 50 hours, preferably 10 minutes to 15 hours. These reaction operations can be performed repeatedly. The solvent used in this reaction is not particularly limited as long as the object of the present invention is not impaired, and examples thereof include aromatic solvents such as toluene and xylene, ketone solvents such as cyclohexanone, and mixtures thereof. The solvent may be removed after the reaction, or may be in a solution state without being removed.
In the above-mentioned reaction, the use ratio of the component A and the component B is not particularly limited.
5 to 90% by mass, preferably 10% by mass,
It can be arbitrarily selected in the range of 80% by mass. The coating component (reaction mixture) may be applied as it is immediately after completion of the reaction, or after completion of the above reaction, that is, after obtaining the coating component, coating with various components. It can also be used as a liquid. The various components are not particularly limited as long as the object of the present invention is not impaired. For example, an antioxidant, a quencher or a radical scavenger, or an inorganic or organic acid such as hydrochloric acid, sulfuric acid, or acetic acid, and boron trifluoride Diethyl ether complex, Lewis acid such as sodium hexafluoroantimonate, potassium hydroxide, sodium hydroxide, triethylamine, bases such as aniline, dibutyltin dilaurate, as exemplified by organic metals such as titanium tetraisopropoxide, A catalyst having a curing promoting action (usually preferably 0.1 to 5.0% by mass based on the ultraviolet absorbing material), toluene, xylene, ethanol, isopropanol, dimethylformamide, cyclohexanone, 1-
Solvents such as methoxy-2-acetoxypropane and various kinds of thinners can be added, and those containing these components can be used as a coating solution. The amount of the silicone resin as an optional component is not particularly limited, but is preferably 5 to 300 parts by mass, and more preferably 20 to 150 parts by mass with respect to 100 parts by mass of the total of components A and B. The amount of the epoxysilane used is not particularly limited, but the total amount of the component A and the component B is 100%.
10 to 500 parts by mass, preferably 10 parts by mass,
0 to 400 parts by mass is desirable. The amount of the polyether-modified polysiloxane is not particularly limited, but is preferably 10 parts by mass based on 100 parts by mass of the components A and B.
-500 parts by mass, preferably 100-400 parts by mass. The use amount of the inorganic fine particle dispersion is not particularly limited, but is 5 to 400 parts by mass, preferably 10 to 200 parts by mass with respect to 100 parts by mass of the total of components A and B.
Parts by weight are preferred.

The specific ultraviolet absorbing layer of the present invention can be obtained by applying the coating composition thus obtained on a transparent substrate and curing. The coating component is usually in a liquid state, and the coating method is not particularly limited, and a known method is appropriately selected. For example, spin coating, spray coating, dip coating, cast coating, blade coating, flow coating and the like are appropriately used according to the purpose. The curing reaction is usually performed at room temperature to 250 ° C, preferably 40 ° C to
It can be cured at about 200 ° C. Even without using the catalyst, the temperature is usually from room temperature to 350 ° C, preferably from 60 ° C to
It can be cured by heating at 250 ° C. The time required for curing is appropriately selected, but is usually about 10 minutes to 5 hours. The thickness of the ultraviolet absorbing layer formed on the transparent substrate is not particularly limited and may be appropriately selected, but is usually in the range of about 0.5 to 50 μm. If it is less than 0.5 μm, it may be difficult to achieve a sufficient ultraviolet blocking ability, and if it is more than 50 μm, it may be difficult to apply it without causing cracks. Further, for the purpose of protecting the organic ultraviolet absorber during the formation of the transparent electrode, an overcoat layer may be provided between the ultraviolet absorbing layer and the transparent electrode. Therefore, it is desirable that the polymer used in the overcoat layer is stable and smooth at the time of forming the transparent electrode. Although there is no particular limitation on the overcoat layer, a resin excellent in heat resistance is usually used. Specific examples include polyimide, polyamide, polycarbonate, polyarylate, polyethersulfone, melamine resin, phenolic resin, epoxy resin, silicone resin such as silicone varnish, urea resin, etc. The agent is optimal. These may be used in combination. It is also commonly used with glass filler and inorganic powder. As the inorganic powder, ZnO, TiO ₂ , C
Fine particles such as eO ₂ and silica are used. Examples of the silicone resin overcoating agent include silicone resin-based materials in which inorganic fine particles such as colloidal silica are dispersed, and partial hydrolysis products and partial polycondensation products of silanes such as alkoxysilane and chlorosilane. Specifically, Tosgard 510 (made by Toshiba Silicone) is a commercially available product
And APZ7703, APZ7705 (manufactured by Nippon Unicar), N-L11
And polysilazane (manufactured by Tonen) such as O.N-L710. It is also known that a partial hydrolysis product of epoxysilane is excellent in abrasion resistance and the like as an overcoat agent. The method for forming the overcoat layer is not particularly limited and a known method may be appropriately selected, but is usually obtained by applying a solution of a resin constituting the overcoat layer or a solution of a precursor. . After application, necessary processing is performed depending on the properties of each resin, and an overcoat layer is obtained. A method of attaching a film made of the above resin is also performed. Specifically, for example, when a silicone varnish is used, a catalyst such as dibutyltin dilaurate is added, and after coating, 100
By heating and curing at about 200 ° C. for about 5 minutes to 2 hours, an overcoat layer of 1 to 20 μm can be obtained. Further, for example, when an acryl-melamine resin precursor is used, an overcoat layer having a thickness of 10 to 100 μm can be obtained by heating and curing at 130 to 190 ° C. for about 5 minutes to 2 hours after application. When a photocurable acrylic resin precursor or the like is used, it is usually within 5 minutes by applying and then placing it under high pressure mercury lamp irradiation.
An overcoat layer of 10 μm can be obtained. As a coating method, a known method is used. For example, spin coating, spray coating, cast coating, blade coating, dip coating and the like can be mentioned. Further, by applying a light surface modification or a primer treatment before producing the overcoat, the coatability of the overcoat material can be improved, and the adhesion of the overcoat layer to the ultraviolet absorbing layer can also be improved.

The electrochromic device of the present invention comprises a pair of opposing conductive substrates, at least one of which is a transparent conductive substrate, an ion conductive material, a layer containing an electrochromic material, and an ultraviolet absorbing layer. The specific form will be described in more detail with reference to the drawings. As an example of the simplest form of the electrochromic device of the present invention, as shown in FIG.
And a transparent conductive substrate A including a transparent electrode 2a located inside thereof and an ultraviolet absorbing layer 3 formed therebetween, and a transparent conductive substrate B including a transparent substrate 1b and a transparent electrode 2b located therein. The electrochromic layer 4 is formed inside the transparent electrode 2b of the transparent conductive substrate B, and between the transparent substrate A and the transparent conductive substrate B on which the electrochromic layer 4 is formed. An electrochromic element in which the ion conductive material 6 is sandwiched and the layer of the ion conductive material 6 is sealed with the sealant 5 can be given. Further, as shown in FIG. 2, one or more intermediate layers 7 can be provided between the transparent substrate 1a and the ultraviolet absorbing layer 3. The function of the intermediate layer 7 is not particularly limited,
For example, since some organic ultraviolet absorber types sometimes deteriorated organic ultraviolet absorber by far ultraviolet, for the purpose of suppressing the degradation, ZnO, an ultraviolet absorbing layer containing inorganic oxides such as CeO _2, TiO ₂ provided Or
For the purpose of improving the adhesion between the ultraviolet absorbing layer 3 and the transparent substrate 1a, an intermediate layer 7 containing a silane coupling agent, a surfactant or the like can be provided. In FIG. 2, members denoted by the same reference numerals as those in FIG. Further, as shown in FIG. 3, an overcoat layer 8 can be provided between the ultraviolet absorbing layer 3 and the transparent electrode 2a. The function of the overcoat layer 8 is not particularly limited.
For protecting the transparent electrode 2a and the ultraviolet absorbing layer 3 after the assembly of the electrochromic element. In FIG. 3, members denoted by the same reference numerals as those in FIG. Further, as shown in FIG. 4, an intermediate layer 7 can be provided between the transparent electrode 1a and the ultraviolet absorbing layer 3, and an overcoat layer 8 can be provided between the ultraviolet absorbing layer 3 and the transparent electrode 2a. In FIG. 4, the members denoted by the same reference numerals as those in FIGS. As shown in FIG. 5, instead of the transparent conductive substrate A shown in FIGS. 1 to 4, a conductive substrate C including a non-transparent opaque substrate 9 and a non-transparent opaque electrode can be provided. FIG.
In FIG. 7, members denoted by the same reference numerals as those in FIG. The method for forming each film and layer constituting the electrochromic device of the present invention is not particularly limited, and each film and layer can be sequentially formed according to the above-described manufacturing method. For example, in the case of the electrochromic device having the configuration shown in FIG. 1, the ultraviolet absorbing layer 3 and the transparent electrode 2a are sequentially formed on the transparent substrate 1a by the above-described method, to obtain the transparent conductive substrate A. Next, the transparent electrode 2b and the electrochromic layer 4 are formed on the other transparent conductive substrate 1b by the above-described method.
Get. These transparent conductive substrates (1a, 1b) are
They are opposed at intervals of about 00 μm, and the periphery except for the injection port is sealed with a sealant 5. The electrochromic device can be obtained by injecting the ion conductive substance 6 by the above-described method. When the transparent conductive substrates (1a, 1b) are opposed to each other, a spacer can be used to secure a constant interval. The spacer is not particularly limited, but beads or sheets made of glass, polymer, or the like can be used. The spacer can be provided by a method of inserting the spacer into a gap between the opposing conductive substrates, a method of forming a projection made of an insulating material such as a resin on an electrode of the conductive substrate, or the like. The method of forming the ion conductive material 6 can be formed by, for example, injecting a precursor or the like of the solid ion conductive material into a gap between the opposing conductive substrates and then curing the same. The curing method is not particularly limited, but a method using light, a method using heat, after mixing a reaction solution that cures with time immediately before injection,
Immediately injecting and hardening may be used. In the case of the electrochromic device having the configuration shown in FIG. 2, an intermediate layer 7 is formed on the transparent substrate 1a, and thereafter, the electrochromic device can be obtained by the same procedure as in the configuration shown in FIG. In the case of the electrochromic device having the configuration shown in FIG. 3, the ultraviolet absorbing layer 3 is formed on the transparent substrate 1a, and then the overcoat layer 7 is formed. Can be obtained. In the case of the electrochromic device having the configuration shown in FIG. 4, the intermediate layer 7 is provided on the transparent substrate 1a.
The ultraviolet absorbing layer 3 and the overcoat layer 8 are sequentially formed, and thereafter, an electrochromic device can be obtained by the same procedure as in the configuration shown in FIG.

[0023]

The electrochromic device of the present invention has
An ultraviolet absorbing layer is provided between the transparent substrate and the transparent electrode, and has durability and ultraviolet resistance that can withstand outdoor use. Further, it can be manufactured at low cost. Further, since the organic ultraviolet absorber and the base material in the ultraviolet absorbing layer are chemically bonded, the stability of the ultraviolet absorbing layer at the time of forming the transparent electrode can be maintained. In particular, by appropriately selecting the ultraviolet absorbing layer, a wavelength of 400 nm or less can be very clearly cut off. Further, by adopting a configuration in which an overcoat layer is provided between the ultraviolet absorbing layer and the transparent electrode, the formation of the transparent electrode can be facilitated, and an electrochromic device manufactured using such an electrochromic element It can protect itself from UV rays. Therefore, the electrochromic device of the present invention is used not only for indoor windows, but also for windows facing the outdoors, skylights, window materials for solar houses, windows for vehicles, sunroofs, dimming devices such as partitions, and weather-resistant display devices. be able to. As described above, the present invention has been described in detail. As the preferred embodiments of the electrochromic device of the present invention, the following embodiments are mentioned. 1. When reacting at least (a) the aminosilane compound represented by the general formula (1) or a derivative thereof, and (b) the ultraviolet absorber having a carboxyl group in the molecule, the coating component for forming the ultraviolet absorption layer is: An electrochromic device obtained by performing this reaction in the presence of the silicone resin. 2. The coating component for forming the ultraviolet absorbing layer is reacted with at least (a) the aminosilane compound represented by the general formula (1) or a derivative thereof, and (b) the ultraviolet absorbing agent having a carboxyl group in the molecule. An electrochromic device obtained by forming an amide bond derived from aminosilane and further adding the epoxysilane. 3. The coating component for forming the ultraviolet absorbing layer is reacted with at least (a) the aminosilane compound represented by the general formula (1) or a derivative thereof, and (b) the ultraviolet absorbing agent having a carboxyl group in the molecule. After generating an amide bond derived from aminosilanes,
An electrochromic device obtained by further adding an inorganic fine particle dispersion.

[0024]

EXAMPLES The present invention will be described below with reference to examples of the present invention, but the present invention is not limited thereto.

Example 1 Synthesis of UV absorber having a carboxyl group 225 g (0.46 mol) of 3- (5-chloro-2H-)
Benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid octyl ester (TINUVIN 109, trade name, C)
iba-Geigy) was dissolved in 700 ml of acetone, 600 ml of a 2N aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 24 hours. After 650 ml of 2N hydrochloric acid was added to make the solution acidic, the insolubilized product was separated by filtration and washed with distilled water until the filtrate became neutral. The product is dried in vacuo and recrystallized from toluene to give 3- (5-chloro-2H-benzotriazol-2-yl) -5-.
(1,1-Dimethylethyl) -4-hydroxy-benzenepropanoic acid [Compound I] was obtained. Preparation of UV Absorbing Layer 3 g of 3-aminopropyltriethoxysilane was dissolved in 35 g of xylene, and 5 g of the compound I was gradually added while heating to 80 ° C. After the addition was completed, the temperature was raised to 130 ° C. and refluxed for 3 hours. After allowing to cool, 16 g of 3-glycidoxypropyltrimethoxysilane was added, and this was used as an ultraviolet absorbing coating solution. 13C-NMR of the obtained coating solution
As a result, a peak of a carbonyl derived from an amide bond (about 173 ppm) was observed, and it was confirmed that an amide bond derived from a starting material aminosilane was present. The ultraviolet absorbing coating solution was spray-coated on a glass substrate, left at room temperature for 20 minutes, and then heated at 200 ° C. for 20 minutes to produce an ultraviolet absorbing glass having an ultraviolet absorbing film having a thickness of about 17 μm. Preparation of a transparent conductive substrate having an ultraviolet absorbing layer On the ultraviolet absorbing layer thus obtained, a silicone resin coating solution (APZ-6615 manufactured by Nippon Unicar Co., Ltd.)
Was diluted 2-fold with ethanol and spray coated. When the solvent was dried and cured by heating at 100 ° C. for 20 minutes, a protective layer made of a silicone resin of about 6.5 μm was obtained on the ultraviolet absorbing layer. Thus, an ultraviolet absorbing layer containing an organic ultraviolet absorbing agent on the transparent glass substrate,
Further, a protective layer was formed thereon. Further, ITO was sputtered thereon at a substrate temperature of 200 ° C. to form a transparent electrode having a thickness of about 3900 angstroms and a resistance of 8.2 Ω / cm ² , thereby obtaining a transparent conductive substrate having a function of blocking ultraviolet rays. FIG. 6 shows the spectral transmittance of this transparent conductive substrate. On the ITO glass making 10 × 10 cm of the color forming material electrode, under the conditions of 20 to 30 A / sec, to be about 5000 Å thick, deposited WO _3, to prepare a color forming material electrode. Preparation of Counter Electrode On a transparent conductive substrate having the ultraviolet absorbing layer of 10 × 10 cm, activated carbon fiber (Gunei Chemical Co., Ltd.) having a surface area of 1500 m ² / g was coated with a conductive adhesive (trade name “Sylvest P”).
-255 ": manufactured by Tokuriki Chemical Laboratory). At this time, the shape of the lattice of the activated carbon fibers is 2 lattice intervals.
cm, the grid line width is 0.8 mm, and the amount of activated carbon fiber used is 0.
85 mg / cm. Next, a polyester film was adhered on the activated carbon fiber, and an insulating layer was provided to prepare a counter electrode. Preparation of light control body The color-forming material electrode and the counter electrode were opposed to each other, the periphery was sealed with an epoxy resin to a width of 5 mm, and a propylene carbonate solution of LiClO _{4 as} an electrolytic solution (1 M /
Liter) was vacuum injected and the inlet was sealed with epoxy resin. Next, a lead wire was connected to each of the coloring material and the counter electrode to form a dimmer. Next, the performance evaluation of the obtained light control body was evaluated based on the following tests. Coloring / Decoloring Test Next, when a voltage of 1 V was applied for 120 seconds so that the color material electrode side was a negative electrode and the counter electrode side was a positive electrode, the color was uniformly colored blue, and the optical density at the time of coloring was 1.08. . Subsequently, when a voltage of 1 V was applied for 60 seconds so that the color-forming material electrode side became a positive electrode and the counter electrode side became a negative electrode, the coloring disappeared immediately, and the optical density at this time was 0.20.
At this time, the difference in optical density between coloring and decoloring was 0.88. Cycling test under ultraviolet irradiation The coloring test and the decoloring test were performed 1200 times in a sun tester, but the coloring remained, disappearance of the response, decrease of the optical density difference, etc. were hardly observed, and extremely stable. It was cycle characteristics.

Example 2 Preparation of ultraviolet absorbing layer 3 g of 3-aminopropyltriethoxysilane was dissolved in 40 g of xylene and heated to 60 ° C. while 5 g of Example 1 was used.
Was slowly added. After the addition, 130
C., and refluxed for 3 hours to obtain a solution-type ultraviolet absorbing coating solution. When the obtained solution was analyzed by ¹³ C-NMR, a carbonyl peak (about 173 ppm) derived from an amide bond was observed, and it was confirmed that an amide bond derived from aminosilanes as a raw material was present.
Spray the coating solution on a glass substrate and apply at room temperature.
After standing for 0 minutes, the mixture was heated at 130 ° C. for 30 minutes to produce an ultraviolet absorbing glass having an ultraviolet absorbing coating having a thickness of about 10 μm. Preparation of Transparent Conductive Substrate Having Ultraviolet Absorbing Layer An overcoat was applied in the same manner as in Example 1 on the ultraviolet absorbing layer thus obtained, and then a transparent electrode was manufactured under the same conditions as in Example 1. When the spectral transmittance of this transparent conductive substrate was measured, it was possible to obtain a substrate which almost completely cuts light of 400 nm or less in the same manner as in Example 1. Preparation of Coloring Material Electrode WO ₃ was vapor-deposited on a 10 × 10 cm ITO glass in the same manner as in Example 1 to prepare a coloring material electrode. Preparation of Counter Electrode Activated carbon fibers were arranged on a transparent conductive substrate having the ultraviolet absorbing layer of 10 × 10 cm in the same manner as in Example 1 to prepare a counter electrode. Preparation of light control body The color-forming material electrode and the counter electrode were opposed to each other, the periphery was sealed with an epoxy resin to a width of 5 mm, and a propylene carbonate solution of LiClO _{4 as} an electrolytic solution (1 M /
Liter) was vacuum injected and the inlet was sealed with epoxy resin. Next, a lead wire was connected to each of the coloring material and the counter electrode to form a dimmer. Next, the performance evaluation of the obtained light control body was evaluated based on the following tests. Coloring / Decoloring Test Next, when a voltage of 1 V was applied for 120 seconds so that the color material electrode side was a negative electrode and the counter electrode side was a positive electrode, the color was uniformly colored blue, and the optical density at the time of coloring was 1.08. . Subsequently, when a voltage of 1 V was applied for 60 seconds so that the color-forming material electrode side became a positive electrode and the counter electrode side became a negative electrode, the coloring disappeared immediately, and the optical density at this time was 0.20.
At this time, the difference in optical density between coloring and decoloring was 0.88. Cycling test under ultraviolet irradiation The coloring test and the decoloring test were performed 1200 times in a sun tester, but the coloring remained, disappearance of the response, decrease of the optical density difference, etc. were hardly observed, and extremely stable. It was cycle characteristics.

Example 3 Preparation of Ultraviolet Absorbing Coating Solution 17.7 g of silicone varnish (XO-7931-Clear, manufactured by Okitsumo) and 3 g of 3-aminopropyltriethoxysilane were dissolved in 35 g of xylene, and heated at 80 ° C. Compound I (5 g) was slowly added. After the addition, 13
The temperature was raised to 0 ° C., and the mixture was refluxed for 3 hours to obtain a solution-type ultraviolet absorbing coating solution. The ultraviolet absorbing coating solution is spray-coated on a glass substrate and left at room temperature for 20 minutes.
After heating for a minute, an ultraviolet absorbing glass having an ultraviolet absorbing coating having a thickness of about 17 μm was produced. When a cross-cut test was performed on this ultraviolet absorbing glass, 50% peeling was observed. Further, this ultraviolet absorbing transparent substrate was washed with boiling acetone for 2 hours.
Extraction for 4 hours showed no weight loss. From this, it was found that the ultraviolet absorber was bonded to the resin via the aminosilane. Preparation of a transparent conductive substrate having an ultraviolet absorbing layer On the ultraviolet absorbing layer thus obtained, a silicone resin coating solution (APZ-6615 manufactured by Nippon Unicar Co., Ltd.)
Was diluted 2-fold with ethanol and spray coated. When the solvent was dried and cured by heating at 100 ° C. for 20 minutes, a protective layer made of a silicone resin of about 6.5 μm was obtained on the ultraviolet absorbing layer. Thus, an ultraviolet absorbing layer containing an organic ultraviolet absorbing agent on the transparent glass substrate,
Further, a protective layer was formed thereon. Further, ITO was sputtered thereon at a substrate temperature of 200 ° C. to form a transparent electrode having a thickness of about 3900 angstroms and a resistance of 8.2 Ω / cm ² , thereby obtaining a transparent conductive substrate having a function of blocking ultraviolet rays. FIG. 7 shows the spectral transmittance of this transparent conductive substrate. Preparation of Coloring Material Electrode WO ₃ was vapor-deposited on a 10 × 10 cm ITO glass in the same manner as in Example 1 to prepare a coloring material electrode. Preparation of Counter Electrode Activated carbon fibers were arranged on a transparent conductive substrate having the ultraviolet absorbing layer of 10 × 10 cm in the same manner as in Example 1 to prepare a counter electrode. Preparation of light control body The color-forming material electrode and the counter electrode were opposed to each other, the periphery was sealed with an epoxy resin to a width of 5 mm, and a propylene carbonate solution of LiClO _{4 as} an electrolytic solution (1 M /
Liter) was vacuum injected and the inlet was sealed with epoxy resin. Next, a lead wire was connected to each of the coloring material and the counter electrode to form a dimmer. Next, the performance evaluation of the obtained light control body was evaluated based on the following tests. Coloring / Decoloring Test Next, when a voltage of 1 V was applied for 120 seconds so that the color material electrode side was a negative electrode and the counter electrode side was a positive electrode, it was uniformly colored blue, and the optical density at the time of coloring was 1.1. . Subsequently, when a voltage of 1 V was applied for 60 seconds so that the color-forming material electrode side became a positive electrode and the counter electrode side became a negative electrode, the coloring disappeared immediately, and the optical density at this time was 0.21. At this time, the difference in optical density between coloring and decoloring was 0.89. Cycling test under ultraviolet irradiation The coloring test and the decoloring test were performed 1200 times in a sun tester, but the coloring remained, disappearance of the response, decrease of the optical density difference, etc. were hardly observed, and extremely stable. It was cycle characteristics.

Example 4 Preparation of Ultraviolet Absorbing Coating Solution 17.7 g of silicone varnish (XO-7931-Clear, manufactured by Okitsumo) and 3 g of 3-aminopropyltriethoxysilane were dissolved in 35 g of xylene, and heated to 80 ° C. Compound I (5 g) was slowly added. After the addition, 13
The temperature was raised to 0 ° C and refluxed for 3 hours. After cooling, 16 g of 3-glycidoxypropyltrimethoxysilane was added to obtain an ultraviolet absorbing coating solution. The ultraviolet absorbing coating solution is spray-coated on a glass substrate and left at room temperature for 20 minutes.
Heating was performed at 0 ° C. for 20 minutes to produce an ultraviolet absorbing glass having an ultraviolet absorbing coating having a thickness of about 17 μm. FIG. 8 shows an ultraviolet-visible absorption spectrum of this glass substrate. Further, no peeling was observed in the grid test as in Example 3. Preparation of a transparent conductive substrate having an ultraviolet absorbing layer On the ultraviolet absorbing layer thus obtained, a silicone resin coating solution (APZ-6615 manufactured by Nippon Unicar Co., Ltd.)
Was diluted 2-fold with ethanol and spray coated. When the solvent was dried and cured by heating at 100 ° C. for 20 minutes, a protective layer made of a silicone resin of about 6.5 μm was obtained on the ultraviolet absorbing layer. Thus, an ultraviolet absorbing layer containing an organic ultraviolet absorbing agent on the transparent glass substrate,
Further, a protective layer was formed thereon. Further, ITO was sputtered thereon at a substrate temperature of 200 ° C. to form a transparent electrode having a thickness of about 3900 angstroms and a resistance of 8.2 Ω / cm ² , thereby obtaining a transparent conductive substrate having a function of blocking ultraviolet rays. FIG. 8 shows the spectral transmittance of this transparent conductive substrate. Preparation of Coloring Material Electrode WO ₃ was vapor-deposited on a 10 × 10 cm ITO glass in the same manner as in Example 1 to prepare a coloring material electrode. Preparation of Counter Electrode Activated carbon fibers were arranged on a transparent conductive substrate having the ultraviolet absorbing layer of 10 × 10 cm in the same manner as in Example 1 to prepare a counter electrode. Preparation of light control body The color-forming material electrode and the counter electrode were opposed to each other, the periphery was sealed with an epoxy resin to a width of 5 mm, and a propylene carbonate solution of LiClO _{4 as} an electrolytic solution (1 M /
Liter) was vacuum injected and the inlet was sealed with epoxy resin. Next, a lead wire was connected to each of the coloring material and the counter electrode to form a dimmer. Next, the performance evaluation of the obtained light control body was evaluated based on the following tests. Coloring / Decoloring Test Next, when a voltage of 1 V was applied for 120 seconds so that the color-forming material electrode side was a negative electrode and the counter electrode side was a positive electrode, it was uniformly colored blue, and the optical density at the time of coloring was 1.11. . Subsequently, when a voltage of 1 V was applied for 60 seconds so that the color-forming material electrode side was a positive electrode and the counter electrode side was a negative electrode, the coloring disappeared immediately, and the optical density at this time was 0.22.
At this time, the difference in optical density between coloring and decoloring was 0.89. Cycling test under ultraviolet irradiation The coloring test and the decoloring test were performed 1200 times in a sun tester, but the coloring remained, disappearance of the response, decrease of the optical density difference, etc. were hardly observed, and extremely stable. It was cycle characteristics.

Example 5 Preparation of UV Absorbing Coating Solution 17.7 g of silicone varnish (XO-7931-Clear, manufactured by Okitsumo) and 3 g of 3-aminopropyltriethoxysilane were dissolved in 35 g of xylene, and heated to 80 ° C. Compound I (5 g) was slowly added. After the addition, 13
The temperature was raised to 0 ° C and refluxed for 3 hours. After cooling, 16 g of 3-glycidoxypropyltrimethoxysilane and 8 g of a colloidal silica dispersion (manufactured by Nissan Chemical Industries, MIBK-ST) were added to obtain an ultraviolet absorbing coating solution. The above-mentioned ultraviolet absorbing coating solution is spray-coated on a glass substrate and left at room temperature for 20 minutes.
Heating was performed at 00 ° C. for 20 minutes to produce an ultraviolet absorbing glass having an ultraviolet absorbing coating having a thickness of about 17 μm. Pencil hardness is 4
H. FIG. 9 shows an ultraviolet-visible absorption spectrum of this glass substrate. Preparation of a transparent conductive substrate having an ultraviolet absorbing layer A substrate temperature of 200 ° C was placed on the ultraviolet absorbing layer thus obtained.
To form a transparent electrode having a thickness of about 3900 angstroms and a resistance of 8.2 Ω / cm ² , thereby obtaining a transparent conductive substrate having an ultraviolet blocking ability. FIG. 9 shows the spectral transmittance of this transparent conductive substrate. Preparation of Coloring Material Electrode WO ₃ was vapor-deposited on a 10 × 10 cm ITO glass in the same manner as in Example 1 to prepare a coloring material electrode. Preparation of Counter Electrode Activated carbon fibers were arranged on a transparent conductive substrate having the ultraviolet absorbing layer of 10 × 10 cm in the same manner as in Example 1 to prepare a counter electrode. Preparation of light control body The color-forming material electrode and the counter electrode were opposed to each other, the periphery was sealed with an epoxy resin to a width of 5 mm, and a propylene carbonate solution of LiClO _{4 as} an electrolytic solution (1 M /
Liter) was vacuum injected and the inlet was sealed with epoxy resin. Next, a lead wire was connected to each of the coloring material and the counter electrode to form a dimmer. Next, the performance evaluation of the obtained light control body was evaluated based on the following tests. Chakushoiro test Next, when coloring material electrode side negative electrode, the counter electrode side is applied for 120 seconds a voltage of 1V so that the positive electrode was uniformly colored in blue, with the optical density on coloration was 1.09 . Subsequently, when a voltage of 1 V was applied for 60 seconds so that the color-forming material electrode side became a positive electrode and the counter electrode side became a negative electrode, the coloring disappeared immediately, and the optical density at this time was 0.20.
At this time, the difference in optical density between coloring and decoloring was 0.87. Cycling test under ultraviolet irradiation The coloring test and the decoloring test were performed 1200 times in a sun tester, but the coloring remained, disappearance of the response, decrease of the optical density difference, etc. were hardly observed, and extremely stable. It was cycle characteristics.

EXAMPLE 6 Polymerization of Epoxysilane 200 g of 3-glycidoxypropyltrimethoxysilane
Was dissolved in 75 g of xylene, 4 ml of boron trifluoride / diethyl ether complex was gradually added at room temperature, and the mixture was stirred for 4 hours to carry out ring-opening polymerization of an epoxy group. The molecular weight of the obtained polymer was Mw = 3300 (in terms of polystyrene). Preparation of UV absorbing coating solution 17.7 g of silicone varnish (XO-7931-Clear, manufactured by Okitsumo) and 3 g of 3-aminopropyltriethoxysilane were dissolved in 29 g of xylene, and 5 g of compound I was gradually added while heating to 80 ° C. did. After the addition, 13
The temperature was raised to 0 ° C and refluxed for 3 hours. After cooling, 22 g of the above epoxysilane polymer solution was added to obtain an ultraviolet absorbing material. The solution-type UV absorbing material was used as a coating solution, and spray-coated on a glass substrate.
After standing for 150 minutes, the substrate was heated at 150 ° C. for 30 minutes to produce a glass substrate having an ultraviolet absorbing layer having a thickness of about 15 μm. The pencil hardness was 6H. Preparation of a transparent conductive substrate having an ultraviolet absorbing layer On the ultraviolet absorbing layer thus obtained, a silicone resin coating solution (APZ-661 manufactured by Nippon Unicar Co., Ltd.)
5) was diluted twice with ethanol and spray-coated. When the solvent was dried and cured by heating at 100 ° C. for 20 minutes, a protective layer made of a silicone resin of about 6.5 μm was obtained on the ultraviolet absorbing layer. Thus, an ultraviolet absorbing layer containing an organic ultraviolet absorbing agent was formed on the transparent glass substrate, and a protective layer was further formed thereon. Furthermore, ITO is sputtered on the substrate at a substrate temperature of 200 ° C.
Approximately 3900 angstrom film thickness, resistance 8.2 Ω / cm ²
Was formed to obtain a transparent conductive substrate having ultraviolet blocking ability. FIG. 10 shows the spectral transmittance of this transparent conductive substrate. Preparation of Coloring Material Electrode WO ₃ was vapor-deposited on a 10 × 10 cm ITO glass in the same manner as in Example 1 to prepare a coloring material electrode. Preparation of Counter Electrode Activated carbon fibers were arranged on a transparent conductive substrate having the ultraviolet absorbing layer of 10 × 10 cm in the same manner as in Example 1 to prepare a counter electrode. Preparation of light control body The color-forming material electrode and the counter electrode were opposed to each other, the periphery was sealed with an epoxy resin to a width of 5 mm, and a propylene carbonate solution of LiClO _{4 as} an electrolytic solution (1 M /
Liter) was vacuum injected and the inlet was sealed with epoxy resin. Next, a lead wire was connected to each of the coloring material and the counter electrode to form a dimmer. Next, the performance evaluation of the obtained light control body was evaluated based on the following tests. Chakushoiro test Next, when coloring material electrode side negative electrode, the counter electrode side is applied for 120 seconds a voltage of 1V so that the positive electrode was uniformly colored in blue, with the optical density on coloration was 1.09 . Subsequently, when a voltage of 1 V was applied for 60 seconds so that the color-forming material electrode side became a positive electrode and the counter electrode side became a negative electrode, the coloring disappeared immediately, and the optical density at this time was 0.20.
At this time, the difference in optical density between coloring and decoloring was 0.89. Cycling test under ultraviolet irradiation The coloring test and the decoloring test were performed 1200 times in a sun tester, but the coloring remained, disappearance of the response, decrease of the optical density difference, etc. were hardly observed, and extremely stable. It was cycle characteristics.

Example 7 Preparation of Ultraviolet Absorbing Coating Solution Example 3 with 3 g of 3-aminopropyltriethoxysilane
11 g of the epoxysilane polymer solution was dissolved in 32 g of xylene, and 5 g of Compound I was gradually added while heating to 80 ° C. After the addition was completed, the temperature was raised to 130 ° C. and refluxed for 3 hours to obtain an ultraviolet absorbing material. The solution-type ultraviolet absorbing material is used as a coating liquid, spray-coated on a glass substrate, left at room temperature for 20 minutes, and then heated at 150 ° C. for 30 minutes to obtain a glass substrate having an ultraviolet absorbing layer having a thickness of about 15 μm. Was prepared. The pencil hardness was 5H. Preparation of a transparent conductive substrate having an ultraviolet absorbing layer On the ultraviolet absorbing layer thus obtained, a silicone resin coating solution (APZ-6615 manufactured by Nippon Unicar Co., Ltd.)
Was diluted 2-fold with ethanol and spray coated. When the solvent was dried and cured by heating at 100 ° C. for 20 minutes, a protective layer made of a silicone resin of about 6.5 μm was obtained on the ultraviolet absorbing layer. Thus, an ultraviolet absorbing layer containing an organic ultraviolet absorbing agent on the transparent glass substrate,
Further, a protective layer was formed thereon. Further, ITO was sputtered thereon at a substrate temperature of 200 ° C. to form a transparent electrode having a thickness of about 3900 angstroms and a resistance of 8.2 Ω / cm ² , thereby obtaining a transparent conductive substrate having a function of blocking ultraviolet rays. FIG. 11 shows the spectral transmittance of this transparent conductive substrate. Preparation of Coloring Material Electrode WO ₃ was vapor-deposited on a 10 × 10 cm ITO glass in the same manner as in Example 1 to prepare a coloring material electrode. Preparation of Counter Electrode Activated carbon fibers were arranged on a transparent conductive substrate having the ultraviolet absorbing layer of 10 × 10 cm in the same manner as in Example 1 to prepare a counter electrode. Preparation of light control body The color-forming material electrode and the counter electrode were opposed to each other, the periphery was sealed with an epoxy resin to a width of 5 mm, and a propylene carbonate solution of LiClO _{4 as} an electrolytic solution (1 M /
Liter) was vacuum injected and the inlet was sealed with epoxy resin. Next, a lead wire was connected to each of the coloring material and the counter electrode to form a dimmer. Next, the performance evaluation of the obtained light control body was evaluated based on the following tests. Coloring / Decoloring Test Next, when a voltage of 1 V was applied for 120 seconds so that the color material electrode side was a negative electrode and the counter electrode side was a positive electrode, the color was uniformly colored blue, and the optical density at the time of coloring was 1.08. . Subsequently, when a voltage of 1 V was applied for 60 seconds so that the color-forming material electrode side became a positive electrode and the counter electrode side became a negative electrode, the coloring disappeared immediately, and the optical density at this time was 0.21.
At this time, the difference in optical density between coloring and decoloring was 0.87. Cycling test under ultraviolet irradiation The coloring test and the decoloring test were performed 1200 times in a sun tester, but the coloring remained, disappearance of the response, decrease of the optical density difference, etc. were hardly observed, and extremely stable. It was cycle characteristics.

Example 8 Preparation of Coloring Material Electrode WO ₃ was vapor-deposited on a 10 × 10 cm ITO glass in the same manner as in Example 1 to prepare a coloring material electrode. Preparation of Counter Electrode Activated carbon fibers were arranged on the transparent conductive substrate having the ultraviolet absorbing layer of 10 × 10 cm prepared in Example 7 in the same manner as in Example 1 to prepare a counter electrode. Preparation of Solid Ion Conductive Precursor 1 g of methoxypolyethylene glycol # 230 methacrylate (manufactured by Shin-Nakamura Chemical, M-40G) and polyethylene glycol # 400 dimethacrylate (manufactured by Shin-Nakamura Chemical, 9
G) 0.02 g of a photopolymerization initiator (Darocur 117)
3, Ciba-Geigy) 20 mg in 1M-LiClO ₄ /
It was dissolved in 4 g of a γ-butyrolactone solution to obtain a solid ion conductive material precursor. Preparation of light modulating body The color developing material electrode and the counter electrode were opposed to each other with glass beads having a particle size of 200 μm therebetween, and the periphery was sealed with an epoxy resin to a width of 5 mm. After vacuum injection and ultraviolet curing, the injection port was sealed with epoxy resin. Next, a lead wire was connected to each of the coloring material and the counter electrode to form a dimmer. Next, the performance evaluation of the obtained light control body was evaluated based on the following tests. When a color- discoloration test was performed under the same conditions as in Example 1, a color-discoloration test was performed.
It was uniformly colored blue, and the optical density at the time of coloring was 1.15. Subsequently, when a voltage of 1 V was applied for 60 seconds so that the color-forming material electrode side became a positive electrode and the counter electrode side became a negative electrode, the coloring disappeared immediately, and the optical density at this time was 0.25. At this time, the difference in optical density between coloring and decoloring was 0.9
It was 0. Cycling test under ultraviolet irradiation The coloring test and the decoloring test were performed 1200 times in a sun tester, but the coloring remained, disappearance of the response, decrease of the optical density difference, etc. were hardly observed, and extremely stable. It was cycle characteristics.

Example 9 Preparation of Intermediate Layer A ZnO ultrafine particle dispersion coating material (UV-S-400, manufactured by Resino Color Industrial Co., Ltd.) was applied on a glass substrate by dip coating, and cured by heating at 200 ° C. for 20 minutes. An ultraviolet absorbing layer having a thickness of about 2 μm was prepared. On top of this, polyether sulfone (VICTRE, manufactured by ICI)
X'PES 4100P) was spin-coated with a methylene chloride solution to prepare a polymer layer having a thickness of about 2 µm. Preparation of UV-absorbing layer Further, as in the case of Example 7, the thickness was about 15 μm.
m of an ultraviolet absorbing layer. Preparation of Overcoat Layer A polyimide varnish (RN-812, manufactured by Nissan Chemical Industries, Ltd.) was spin-coated on the ultraviolet absorbing layer thus obtained. After the solvent was dried on a hot plate at 60 ° C,
An overcoat layer having a thickness of about 2 μm was obtained by heating and curing in an oven at 200 ° C. for 30 minutes. Preparation of Transparent Conductive Film Further, ITO was sputtered on the transparent conductive film at a substrate temperature of 250 ° C. or less to obtain a transparent conductive substrate having a thickness of 2050 Å and a surface resistance of 9.5 Ω / cm ² , which has a function of blocking ultraviolet rays from transparent electrodes. Preparation of Coloring Material Electrode Transparent Conductive Substrate 1 Obtained in this Way Having Ultraviolet Ray Blocking Ability
Using 0 × 10 cm, 5 mol / l aniline hydrochloride, 0.
Electropolymerization was performed in a 5N perchloric acid solution at a current density of 500 μA / cm ² , and the polymerization area was 70 cm ² and the thickness was about 3
A polyaniline film of 000 Å was obtained. Preparation of Counter Electrode A polypyrrole powder having a surface area of 73 m ² / g obtained by electrolytic polymerization was placed on ITO glass of 10 × 10 cm in Example 1.
Using a conductive adhesive similar to that described above, they were bonded in the form of horizontal stripes. At this time, the line spacing was 1 cm, the line width was 0.5 mm, and the amount of polypyrrole powder used was 0.65 mg / cm. Next, a polyester film was adhered on the polypyrrole layer to provide an insulating layer, which was used as a counter electrode. Preparation of ion-conductive gel precursor methoxytetraethylene glycol methacrylate 10
g, γ-butyrolactone 40 g, lithium perchlorate 4 g
And under light shielding, the photopolymerization initiator Darocur 117
3 (manufactured by Ciba-Geigy) 0.2 g was added. Preparation of light control body In the same manner as in Example 8, the ion-conductive gel precursor was placed in a vacuum to prepare a light control body. When a color- discoloration test was performed under the same conditions as in Example 1, a color-discoloration test was performed.
It was colored blue uniformly, and the optical density at the time of coloring was 0.65. Subsequently, when a voltage of 1 V was applied for 60 seconds so that the color-forming material electrode side became a positive electrode and the counter electrode side became a negative electrode, the coloring disappeared immediately, and the optical density at this time was 0.20. At this time, the difference in optical density between coloring and decoloring is 0.4
It was 5. Cycling test under ultraviolet irradiation The coloring test and the decoloring test were performed 1200 times in a sun tester, but the coloring remained, disappearance of the response, decrease of the optical density difference, etc. were hardly observed, and extremely stable. It was cycle characteristics.

Comparative Example 1 Production of Coloring Material Electrode On a 10 × 10 cm ITO glass, W was formed in the same manner as in Example 1.
O ₃ was vapor-deposited to produce a coloring material electrode. Preparation of Counter Electrode Activated carbon fibers were arranged in the same manner as in Example 2 to prepare a counter electrode. Preparation of Light Modulator In the same manner as in Example 1, an electrolytic solution was put in vacuum to prepare a light modulator. Coloring / Decoloring Test Next, when a voltage of 1 V was applied for 120 seconds so that the color material electrode side was a negative electrode and the counter electrode side was a positive electrode, the color was uniformly colored blue, and the optical density at the time of coloring was 1.08. . Subsequently, when a voltage of 1 V was applied for 60 seconds so that the color-forming material electrode side became a positive electrode and the counter electrode side became a negative electrode, the coloring disappeared immediately, and the optical density at this time was 0.20.
At this time, the difference in optical density between coloring and decoloring was 0.88. Cycling test under ultraviolet irradiation The coloring test and the decoloring test were performed 1200 times in a sun tester.
The optical density difference has been reduced to 0.25.

Comparative Example 2Preparation of inorganic ultraviolet absorbing layer ZnO ultrafine particle dispersion paint (Resino Color
Industrial Co., UV-S-400) by dip coating
Apply and heat cure at 200 ° C for 20 minutes.
Thus, an ultraviolet absorbing layer having a thickness of about 2 μm was produced.Preparation of transparent conductive film On top of this, ITO sputtering is performed at a substrate temperature of 250 ° C or less.
Film thickness 2050 Å, surface resistance
9.5Ω / cm^TwoTransparent electrode transparent with ultraviolet blocking ability
A conductive substrate was obtained. FIG. 1 shows the spectral transmittance of the transparent conductive substrate.
2 is shown. Production of coloring material electrode WO as in Example 1_ThreeTo form a color material electrode
Was.Fabrication of counter electrode Activated carbon fibers were arranged in the same manner as in Example 2 to produce a counter electrode.
did.Fabrication of dimmer As in Example 8, the ion-conductive gel precursor was placed in a vacuum.
Then, a light control body was produced.Coloring test When a color erasing test was performed under the same conditions as in Example 1,
It is uniformly colored blue, and the optical density at the time of coloring is 1.15.
Was. Subsequently, the color material electrode side is a positive electrode, and the counter electrode side is a negative electrode.
When a voltage of 1 V was applied for 60 seconds so that
The coloring disappears promptly, and the optical density at this time is 0.25.
there were. At this time, the difference in optical density between coloring and decoloring was 0.9
It was 0.Cycle test under UV irradiation The coloring test and the decoloring test were performed 1200 times in a sun tester.
Although the coloration disappeared, a decrease in responsiveness was observed,
The optical density difference decreased to 0.65.

[Brief description of the drawings]

FIG. 1 is a structural explanatory view of an electrochromic device of the present invention.

FIG. 2 is a structural explanatory view of another electrochromic device of the present invention.

FIG. 3 is a structural explanatory view of another electrochromic device of the present invention.

FIG. 4 is a structural explanatory view of another electrochromic device of the present invention.

FIG. 5 is a structural explanatory view of another electrochromic device of the present invention.

FIG. 6 is a graph showing the spectral transmittance of the transparent conductive substrate manufactured in Example 1.

FIG. 7 is a graph showing the spectral transmittance of the transparent conductive substrate manufactured in Example 3.

FIG. 8 is a graph showing the spectral transmittance of the transparent conductive substrate manufactured in Example 4.

FIG. 9 is a graph showing the spectral transmittance of the transparent conductive substrate manufactured in Example 5.

FIG. 10 is a graph showing the spectral transmittance of the transparent conductive substrate manufactured in Example 6.

11 is a graph showing the spectral transmittance of the transparent conductive substrate manufactured in Example 7. FIG.

FIG. 12 is a graph showing the spectral transmittance of the transparent conductive substrate manufactured in Comparative Example 2;

[Explanation of symbols]

 1a, 1b Transparent substrate 2a, 2a 'Transparent electrode 3 Ultraviolet absorbing layer 4 Electrochromic layer 5 Sealant 6 Ion conductive material 7 Intermediate layer 8 Overcoat layer 9 Opaque substrate

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Yoshinori Nishikiya 8 Chidori-cho, Naka-ku, Yokohama, Japan Central Research Laboratory of Petroleum Corporation

Claims (2)

[Claims] A pair of opposing conductive substrates having electrodes on at least inner surfaces thereof, an ion conductive material sandwiched between the opposing conductive substrates, and an ion conductive material between the electrodes on the inner surface of the conductive substrate and the ion conductive material. An electrochromic element comprising: a layer containing an electrochromic substance provided on at least one side; and at least one of the counter electrodes is a transparent substrate and a transparent conductive substrate including a transparent electrode disposed inside the transparent substrate, An ultraviolet absorbing layer between at least one of the transparent conductive substrates and the transparent electrode, the ultraviolet absorbing layer comprising: (a) an aminosilane compound represented by the general formula (1) or a derivative thereof; ] (Wherein, R ¹ represents an alkylene group having 1 to 10 carbon atoms, or a divalent group represented by the general formula — (CH ₂ ) _m —NH— [m is an integer of 1 ≦ m ≦ 4], Each R ² is the same or different and represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, provided that at least one of all R ² is One represents an alkoxy group or a hydroxyl group, and n represents n ≧ 0.
Indicates an integer. (B) a component produced by reacting with an ultraviolet absorber having a carboxyl group in the molecule to form an amide bond derived from the aminosilane compound or a derivative thereof on a transparent substrate and curing the component; An electrochromic device characterized by being dipped. 2. The electrochromic device according to claim 1, wherein an overcoat layer is provided between the ultraviolet absorbing layer and the transparent electrode.