JP2002169187A - Method for manufacturing electrochromic light-control glass cell and electrochromic light-control glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochromic light-controlling glass cell which will not cause nonconformities in coloring irregularities or the like. SOLUTION: In the electrochromic light-control glass cell, produced by disposing two transparent conductive substrates facing each other through a prescribed gap and sealing the peripheral part of the substrates, a first gap control member made of a material which will not collapse, even when external force, a first sealing material and a second sealing material containing a second gap control member are successively disposed in the peripheral part between the substrates of the cell from the inside to the outside. The outer face of the peripheral part of the substrates is pressed to fix the substrates with at least the second sealing material, so that controlled state of the gap between the substrates can be maintained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel electrochromic light control glass cell and a method for producing an electrochromic light control glass.

[0002]

2. Description of the Related Art As a method of manufacturing an electrochromic light control glass, two transparent conductive substrates are opposed to each other at a predetermined interval, and a peripheral portion thereof is partially sealed, and the seal is removed. There is known a method in which a cell having a portion as an electrolyte injection port is formed, and a liquid electrolyte is injected into the cell by, for example, a vacuum injection method. In this vacuum injection method, as shown in FIG. 5 (a), first, a cell 19 is vertically set in a container 17 so that an injection port 18 is located at a lower part, and a lower part of the container 17 below the cell 19 is set. The liquid electrolyte is stored. Then, the inside of the container 17 is evacuated and the cell 19 is exhausted.
After the inside and the liquid electrolyte are degassed, the inlet 18 is immersed in the liquid electrolyte 20 as shown in FIG. After the immersion, the pressure in the container 17 is returned to normal pressure, so that the liquid electrolyte 2
0 is injected into the cell 19. Another method for injecting a liquid electrolyte into a cell for electrochromic light control glass is disclosed in, for example, Japanese Patent Application Laid-Open No. 7-199235.

[0003]

In the conventional method for producing electrochromic light control glass by a vacuum injection method, no consideration is given to the spacing between cell substrates, uneven coloring, and uniform coloring response. In addition, when the cell is enlarged as in the case of electrochromic light control glass, there is a concern that this problem has a significant effect. In order to maintain the spacing between cell substrates, it is known to place spacers between the substrates.However, when the substrate is large, such as in electrochromic dimming glass, or when the substrate has low planar accuracy, it is used. In such a case, the distribution of the intervals between the cell substrates may vary, and in such a case, it is not easy to control the intervals between the substrates simply by disposing the spacers between the substrates. The present invention has been made in view of such circumstances, and an object of the present invention is to provide an electrochromic light control glass cell and a method of manufacturing an electrochromic light control glass in which uniformity of a substrate interval is improved. .

[0004]

In order to achieve the above object, an electrochromic light control glass cell of the present invention comprises:
In an electrochromic dimming glass cell in which two transparent conductive substrates are opposed to each other at a predetermined interval and the peripheral portion between these substrates is sealed, the peripheral portion between the substrates of the cell is formed along the inside from the outside. A primary seal adjusting member, a primary seal member, and a secondary seal member including a secondary seal member are sequentially arranged, and the outer surface of the peripheral portion of the substrate is pressed to maintain a state in which the distance between the substrates is controlled. Thus, the substrate is fixed with at least a secondary sealing material.

Further, according to the method of manufacturing the electrochromic light control glass of the present invention, two transparent conductive substrates are opposed to each other at a predetermined interval, and a force is applied to a peripheral portion between these substrates from inside to outside. A primary spacing adjusting member, a primary sealing material, and a secondary sealing material including a secondary spacing adjusting member, which are made of a material that does not collapse even when added, are sequentially arranged, and the outer surface of the peripheral portion of the substrate is pressed to remove the spacing between the substrates. A cell is formed by fixing the substrate with at least a secondary sealing material so that the controlled state is maintained, and an electrolyte or a precursor thereof is injected into the cell to produce an electrochromic light control glass. .

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the contents of the present invention will be described in detail. In the present invention, at least two transparent conductive substrates are used. The transparent conductive substrate usually has a form in which a transparent electrode layer is provided on a transparent substrate. Here, “transparent” means having a light transmittance of 10 to 100% in a visible light region. The transparent substrate is not particularly limited as long as it is transparent. For example, colorless or colored glass, tempered glass, or the like may be used, and a colorless or colored resin having transparency may be used. Specific examples include polyethylene terephthalate, polyamide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylenesulfide, polycarbonate, polyimide, polymethylmethacrylate, polystyrene, and the like. The shape of the substrate may be either flat or curved.

As the transparent electrode, for example, a metal thin film of gold, silver, chromium, copper, tungsten, or the like, a conductive film made of a metal oxide, or a laminate thereof can be used. As the metal oxide, for example, ITO (In ₂ O ₃ —SnO)
₂ ), tin oxide, silver oxide, zinc oxide, vanadium oxide and the like. The thickness of the electrode film is not particularly limited as long as it is a value having transparency, and is usually 10 to 2000 nm, preferably 50 to 1500 nm. Further, the surface resistance (resistivity) can be appropriately selected depending on the use of the substrate of the present invention, and is usually 0.5 to 500 Ω / sq. , Preferably 1
~ 50Ω / sq. It is desirable that 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 any case, the substrate temperature is usually 100 to
It is desirable to form within the range of 350 ° C.

The transparent electrode layer is provided for the purpose of imparting oxidation-reduction ability, imparting conductivity, and imparting an electric double layer capacity.
A partially opaque electrode active material can also be provided.
At this time, the applied amount is, of course, selected within a range that does not impair the transparency of the entire electrode surface. Examples of the opaque electrode active material include metals such as copper, silver, gold, platinum, iron, tungsten, titanium, and lithium; organic materials having a redox ability such as polyaniline, polythiophene, polypyrrole, and phthalocyanine; activated carbon; and graphite. Carbon materials, metal oxides such as V ₂ O ₅ , WO ₃ , MnO ₂ , NiO, Ir ₂ O ₃ , and mixtures 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 made of activated carbon fiber, graphite, acrylic resin, or the like is formed in a fine pattern such as a dot on the ITO transparent electrode, or gold (Au) is used. ) A composition comprising V ₂ O ₅ , acetylene black, butyl rubber and the like can be formed in a mesh on the thin film.

An opening is provided in a part of the conductive substrate,
It is desirable to be an injection port of the electrolyte or its precursor,
The position is preferably a part near the end (peripheral part).

The basic structure of the electrochromic dimming glass cell of the present invention is that two conductive substrates are opposed to each other with a predetermined interval with the electrode surface inside, and the peripheral edge between these substrates is sealed. And The interval,
That is, the substrate spacing is usually 10 to 1000 μm, preferably 100 to 1000 μm, particularly preferably 200 to 700 μm.
μm. Of course, the conductive substrates may be of different types or of the same type. In the present invention, the location of the electrochromic layer is not particularly limited. For example, if the electrochromic layer is formed as an electrochromic layer, at least one or both of the electrode layers of the conductive substrate contain an electrochromic substance. A layer may be provided in advance. In this case, a pair of substrates may be sealed with facing each other, or when an electrochromic electrolyte layer serving as both an electrolyte and an electrochromic substance is used, the conductive substrates may be simply sealed with facing each other. Good.

The above-mentioned electrochromic substance means a substance which shows color, decoloration, color change or the like by electrochemical oxidation or reduction reaction, and is not particularly limited as long as the object of the present invention is achieved. Instead, known compounds can be used. Specifically, Mo ₂ O ₃ , Ir ₂ O ₃ , N
Particularly preferred are iO, V ₂ O ₅ , WO ₃ , polythiophene compounds, polyaniline compounds, polypyrrole compounds, metal phthalocyanine compounds, viologen compounds or salts thereof, ferrocene compounds or derivatives thereof. 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 in a matrix component. The thickness of the electrochromic material layer is generally 10 nm to 1 μm, preferably 50 to 800 nm. The method for forming the layer containing the electrochromic substance is not particularly limited, and includes various well-known methods such as a vapor deposition method, 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 dimming glass cell of the present invention, two transparent conductive substrates are opposed to each other at a predetermined distance, and a primary sealing material, a secondary sealing material, and the like are provided on the periphery between these substrates from the inside toward the outside. In addition to arranging the next seal material in order, a primary gap adjusting member is arranged near the inside of the primary seal material, the secondary seal material includes a secondary gap adjusting member, and
The substrate is fixed with at least a secondary sealing material so that the outer surface of the peripheral portion of the substrate is pressed to maintain a state in which the distance between the substrates is controlled.

First, the primary sealing material will be described. 1
As the next sealing material, it can be processed into a specific shape and can be deformed to adjust the substrate spacing.It seals the inside of the light control glass cell and isolates it from the outside, improving the performance of the light control glass. Electrochromic electrolyte capable of blocking permeation of active components such as moisture, oxygen, carbon monoxide, etc., and also serving as an electrolyte or an electrochromic substance injected into the cell. There is no particular limitation as long as the material does not affect the layer. Specifically, for example, natural rubber or synthetic rubber, for example, isoprene rubber, butadiene rubber, styrene butadiene rubber, butyl rubber, ethylene propylene rubber, chloroprene rubber, chlorosulfonated polyethylene, nitrile rubber, urethane rubber, polysulfide rubber, acrylic rubber , Epichlorohydrin rubber, silicone rubber,
Materials such as fluorine rubber and hydrogenated nitrile rubber can be used. These materials may be used alone or may be used in combination of two or more kinds. In addition, various modifications may be made by modifying these or adding fillers. In addition, although the same or a different gap adjusting member from the primary gap adjusting member to be described later may be mixed and processed in advance, the gap adjusting member may be broken during processing, or the gap adjusting member may be unevenly distributed in the sealing material. Therefore, it is preferable to manufacture without adding an interval adjusting member at the time of processing. The method of the present invention is not affected at all even if a material to which an interval adjusting member is added is used, and it is needless to say that the primary interval adjusting member needs to be sprayed near the inside of a primary sealing material described later.

Next, the secondary sealing material will be described. 2
The next sealing material is not particularly limited as long as it does not affect the electrolyte injected into the cell or the electrochromic electrolyte layer serving also as the electrochromic substance and can add a secondary gap adjusting member. Nevertheless, components that affect the performance of the light control glass, such as moisture and oxygen,
It is preferable to be able to prevent permeation of an active gas such as carbon monoxide, and a curable resin is preferred. In this case, it is usually cured after adjusting the distance between the substrates of the cell. As this curable resin,
Various curable materials such as a thermosetting type, a photocurable type, and an electron beam curable type are available, and are not particularly limited, and the curing method according to the resin may be applied as the curing method. Needless to say. For example, as the thermosetting resin, a resin that can be cured at room temperature can be used,
When heating is usually required, a material which can be cured at a temperature between room temperature and 150 ° C., preferably between room temperature and 100 ° C. is preferable. In this case, the time required for curing is not particularly limited as long as the electrochromic properties are not impaired, but is preferably 24 hours or less, and more preferably 1 hour or less.

As a curing method using a photocurable resin, low-pressure, high-pressure, ultra-high-pressure mercury lamps, xenon lamps, incandescent lamps, lasers can be used as long as the lamps are suitable for the absorption wavelength of the initiator. Light etc. can be used. When curing, the entire surface of the element may be uniformly exposed to cure simultaneously, or the spot light condensed by moving a lamp or light source or using a light-guiding material such as an optical fiber may be scanned. And may be sequentially cured. Further, the resin may be cured by repeating it two or more times. As the curable resin, specifically, for example, a phenol resin, a urea resin,
Epoxy resins, polyvinyl acetate, polyvinyl acetal, polyvinyl alcohol, acrylic acid esters, methacrylic acid esters, cyanoacrylic acid esters, polyamides, butyl rubbers, silicone resins, and the like. These may be used alone or in combination of two or more. You may mix and use more than it. In addition, various modifications may be made by modifying these or adding fillers.

The secondary sealing material according to the present invention is characterized in that it includes a secondary spacing adjusting member for adjusting the spacing between the substrates. The secondary spacing adjusting member does not collapse at least even if a force is applied, and is made of a non-conductive material, and its shape may be any shape such as a sheet, a sphere, a fiber, and a rod. Without being limited,
Preferably, a spherical one is desirable. The material of the secondary gap adjusting member is not particularly limited as long as it is a non-conductive material, but usually does not collapse even when a force is applied. Here, a material that does not collapse even when a force is applied is a material that does not lose its original function when sandwiched between substrates, regardless of the presence or absence of the original state. The material whose distance can be adjusted is one type of material that does not collapse even when the force described here is applied. Specific examples of preferred materials include inorganic materials such as glass and ceramics, and organic materials such as polyvinyl divinylbenzene crosslinked resin and acrylic resin.

The proportion of the secondary spacing adjusting member added to the secondary sealing material is not particularly limited. For example, it is usually 0.1 to 10% by mass, preferably 0.3 to 10% by mass based on the sealing material.
8 mass%, more preferably 0.5 to 5 mass% is desirable. The size of the secondary gap adjusting member is not particularly limited and is appropriately selected depending on the target board gap. For example, in the case of a spherical shape, the diameter is usually 200 to 1000.
μm, preferably about 200 to 700 μm,
Even in the case of other shapes, it is desirable to have a dimension within a range that performs a function similar to this. The shape distribution of the secondary gap adjusting member is not particularly limited. For example, in the case of a spherical shape, the variation in diameter is usually ± 100 μm or less, preferably ± 50 μm or less, and more preferably ± 30 μm or less.

Next, the primary space adjusting member will be described.
The primary gap adjusting member is a material that does not affect the electrolyte injected into the cell or the electrochromic electrolyte layer also serving as the electrochromic substance, and has the same conditions as those of the secondary gap adjusting member. It is necessary that the material satisfy the following. That is, the primary spacing adjusting member does not affect the electrolyte injected into the cell or the electrochromic electrolyte layer also serving as the electrochromic substance, does not collapse even when force is applied, and is nonconductive. The material may be any of a sheet shape, a spherical shape, a fibrous shape, and a rod shape, and is not particularly limited, and is preferably a spherical shape.

The size of the shape of the primary spacing adjusting member is not particularly limited, and is appropriately selected depending on the desired substrate spacing. For example, when the primary spacing adjusting member has a spherical shape, the primary spacing adjusting member usually has a diameter of 200 to 1000 μm. Preferably 200 to 700
μm is desirable, and in the case of other shapes, a dimension in a range that performs a function equivalent thereto is desirable, and the shape distribution is not particularly limited. For example, in the case of a spherical shape, variation in diameter is usually ± 100 μm or less, preferably Is preferably ± 50 μm or less, more preferably ± 30 μm or less. The size of the primary spacing adjusting member and the size of the secondary spacing adjusting member may be the same or different. However, when the distribution of the substrate spacing is not uniform, the secondary spacing adjusting member and the primary spacing having different sizes from each other. The non-uniformity can be improved by appropriately selecting the adjusting member. As a typical example, when the distance between the substrates is small near the center of the cell, it can be improved by using a primary gap adjusting member that is larger than the secondary gap adjusting member.

Next, some sealing methods in the present invention will be described. However, the sealing method is not particularly limited, and it goes without saying that various well-known methods can be applied. Regarding the primary sealing material, (1) a method in which a material processed and molded into a seal shape in advance is prepared and then attached to a substrate; (2) a sheet is processed in advance and cut into a predetermined width; (3) Processing in advance into a sheet with an appropriate width for the seal, a rod or string with an appropriate diameter for the seal,
A method of sticking on a substrate; and the like, and the method according to (3) is particularly preferred. Regarding the arrangement shape of the primary sealing material, the thickness is not particularly limited as long as it does not fall below the thickness dimension of the primary spacing adjusting member to be arranged later, and the width is not particularly limited, but is usually It is in the range of 0.5 mm to 20 mm, preferably 1 mm to 10 mm.

As for the secondary sealing material, after mixing the secondary spacing adjusting member, (1) a method in which a material previously processed and molded into a seal shape is prepared and then sandwiched between substrates; (2) A method of forming the paste of the curable resin into a desired shape on the substrate surface by using a known printing method; (3) a method of applying the paste to the substrate surface as needed; (4) discharging the curable resin from a nozzle A method in which an arbitrary pattern is formed on a substrate by sweeping a nara, and the method according to (4) is particularly preferable. The application of the sealant to the substrates may be performed on only one of the two substrates or on both. Regarding the arrangement shape of the secondary sealing material, the thickness is not particularly limited as long as it is not smaller than the dimension in the thickness direction of the secondary gap adjusting member, and the width is not particularly limited, but is usually 0.5 mm to 20 m.
m, preferably in the range of 1 mm to 10 mm. The substrate seal manufactured by the above method may be provided with one or more inlets or outlets. The injection port can be easily formed, for example, by not intentionally applying a sealant, but any shape may be used as long as it simply conducts the two spaces separated by the substrate seal. For example, conduction can be achieved by using a hollow material or the like. Further, an inlet may be provided in at least one of the substrates to be used to seal the entire peripheral edge of the substrate.

According to the present invention, after the primary and secondary seal materials are applied to the substrate, it is necessary to spray or dispose the primary gap adjusting member near the inside of the primary seal material.
The method of dispersing or arranging the primary gap adjusting member is not particularly limited, but it is important that the primary gap adjusting member is adhered at least near the inner side of the primary seal material. Absent. However, when the primary interval adjusting member is large, it is preferable that the primary interval adjusting member does not remain in the cell from the viewpoint of the visibility of the electrochromic light control glass. Regarding the method of spraying or arrangement, there is no particular limitation as long as spraying or arrangement can be performed,
For example, (1) a method in which a predetermined amount is put on a spatula, and is appropriately sprayed and adhered in the vicinity of the adhered primary seal material; (2) after a predetermined amount is sprayed on the substrate to which the primary seal material is adhered A method in which the substrate is vibrated and adhered to the vicinity of the primary seal material; and a method of applying the primary gap adjusting member onto the substrate and spraying and adhering to the vicinity of the inside of the primary seal material. Can be. The method according to (2) is particularly preferable as the method of spraying or disposing.

Next, a case where the distance between the substrates is controlled will be described. In the cell of the present invention, a primary sealing material and a secondary sealing material including a secondary spacing adjusting member are sequentially arranged from the inner side to the outer side on the periphery of at least one of the transparent conductive substrates, and After arranging the primary gap adjusting member near the inside of the sealing material, the two substrates are opposed to each other, the substrates are positioned to a predetermined interval, the sealing material is crushed, and the outer surface of the peripheral edge of the substrate is pressed. Then, the distance between the substrates is controlled, and the substrates are fixed with at least a secondary sealing material so that this state is maintained. In the present invention, controlling the interval between the substrates means that when two transparent conductive substrates forming a cell are arranged at a predetermined interval or overlap each other, the maximum at any of a plurality of measurement points between the substrates is obtained. It means that the difference between the value and the minimum value does not exceed a predetermined value. The predetermined value is a numerical value that does not cause problems such as poor color responsiveness and uneven color, and specifically, for example, usually 120 μm or less, and preferably 100 μm or less.
It is desirable that: The point for measuring the substrate interval is not particularly limited, and an arbitrary plurality of points can be selected. For example, when measuring whether or not the difference between the maximum value and the minimum value exceeds a predetermined value, it is preferable to use a plurality of locations where the entirety can be substantially grasped at predetermined intervals vertically, horizontally, and horizontally. When measuring whether or not the interval is controlled, the difference between the maximum value and the minimum value may be a place where the difference exceeds a predetermined value or a plurality of places around the place, and the whole is almost grasped. There may be a plurality of places as possible. A method for measuring the substrate interval is not particularly limited, but a method using a laser displacement meter, which can be optically observed from outside the cell, is exemplified.

The distance between the substrates is controlled by pressing the outer surface of the peripheral portion of the substrate. The pressing means for pressing the outer surface of the peripheral portion of the substrate is provided by pressing an appropriate position on the outer surface of the peripheral portion of the substrate. Since the primary space adjusting member and the secondary space adjusting member are provided in the peripheral portion of the substrate, the distance between the central portions of the substrate is changed by the principle of leverage, and there is no particular limitation. As the pressing means, those which can be freely attached to and detached from the substrate are preferable. For example, those having a structure for sandwiching the substrate are preferable. Specifically, a small clipping device such as a clip or a length longer than one side of the substrate is preferable. A holding jig having a holding member may be used.
The pressing means preferably has a structure capable of changing the pressing force, and examples thereof include a method of pressing with a pressing jig using air pressure. The size and shape of the pressing means are not particularly limited. When the substrate is pressed by the pressing means, a high molecular material such as a fluororesin may be interposed between at least one of the substrates and the pressing means.
The pressing force at the time of pressing may be appropriately selected depending on the type, shape, thickness and strength of the substrate.

When the interval is controlled by using the pressing means,
The distance between the substrates is measured while pressing the outer surface of the substrate peripheral portion by the pressing means, and when the distance between the substrates exceeds a predetermined value, the pressing position of the pressing means is shifted or the pressing force of the pressing means is variable. In the case where the pressing force is changed or a plurality of small holding members are used as the pressing means, it is preferable to control the substrate interval to a predetermined value by attaching another holding member to another portion. With this configuration, the interval can be adjusted while observing the measured value, so that the substrate interval can be reliably controlled. Thus, by pressing the outer surface of the substrate peripheral portion,
The substrate is fixed with at least a secondary sealing material so that the state where the substrate interval is controlled is maintained. That is, by pressing the outer surface of the peripheral portion of the substrate and controlling the substrate interval, 2
By solidifying the secondary sealing material or the primary sealing material and the secondary sealing material, the substrate is maintained in a state where the substrate spacing is maintained at a predetermined value. The electrolyte or a precursor thereof is vacuum-injected into the cell thus manufactured. When the vacuum injection is performed, if the substrate is securely fixed, the pressing means is kept attached (when the peripheral portion of the substrate is removed). The outer surface may be kept pressed) or it may be removed.

Next, the electrolyte will be described. The electrolyte used in the present invention is not particularly limited as long as it can color, decolor, and change the color of the electrochromic substance, but is usually 1 × 10 ⁻⁷ S / cm at room temperature.
A substance that exhibits the above-described ionic conductivity is preferable.
The electrolyte is not particularly limited, and examples thereof include a liquid electrolyte, a gelled liquid electrolyte, and a solid electrolyte. In the present invention, a solid electrolyte is particularly desirable. As the liquid-based electrolyte, those 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 solvent having polarity is particularly preferable. Specifically, water, methanol, ethanol, propylene carbonate, ethylene carbonate,
Organic polar solvents such as dimethylsulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, sulfolane, 1,3-dioxane, N, N-dimethylformamide, 1,2-dimethoxyethane, tetrahydrofuran and the like, preferably propylene carbonate, Organic polar solvents such as ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, γ-butyrolactone, sulfolane, 1,3-dioxane, N, N-dimethylformamide, 1,2-dimethoxyethane, and tetrahydrofuran are preferable. These can be used alone or as a mixture when used.

The salts as the supporting electrolyte are not particularly limited, and include various inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts and cyclic quaternary ammonium salts. Is LiClO ₄ , LiSC
N, LiBF ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiP
F ₆ , LiI, NaI, NaSCN, NaClO ₄ , Na
Li, N such as BF ₄ , NaAsF ₆ , KSCN, KCl
a, K alkali metal salts, etc., (CH ₃ ) ₄ NBF ₄ ,
(C ₂ H ₅ ) ₄ NBF 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. Acids as a supporting electrolyte are not particularly limited, and include inorganic acids, organic acids, and the like. Specifically, sulfuric acid,
Examples include hydrochloric acid, phosphoric acids, sulfonic acids, carboxylic acids and the like. The alkalis as the supporting electrolyte are not particularly limited, and include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like.

As the gelled liquid electrolyte, a viscous or gel-like liquid electrolyte containing a polymer or a gelling agent in the liquid electrolyte may be used. The polymer is not particularly limited, for example, polyacrylonitrile, carboxymethylcellulose, polyvinyl chloride, polyethylene oxide, polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, cellulose,
Examples include polyester, polypropylene oxide, and Nafion. The gelling agent is not particularly limited, oxyethylene methacrylate, oxyethylene acrylate, urethane acrylate, acrylamide,
Agar, and the like. The gelled liquid electrolyte is prepared by mixing the liquid monomer with a polymer precursor monomer or a gelling agent precursor, and then injecting the mixture into the cell by a specific method as described above, and then gelling the liquid electrolyte. Between the conductive substrates.

The solid electrolyte is not particularly limited as long as it is solid at room temperature and has ionic conductivity. Polyethylene oxide, oxyethylene methacrylate polymer, Nafion, polystyrene sulfonic acid, Li ₃ N, Na-β-Al ₂ O ₃ , Sn (HPO ₄ )
₂ , H ₂ O, etc., and in particular, a polymer compound obtained by polymerizing the precursor with an oxyalkylene methacrylate-based compound, an oxyalkylene acrylate-based compound, or a urethane acrylate-based compound as a main component of the precursor Polymer solid electrolytes using such as are preferred. As a first example of the polymer solid electrolyte, a composite material including a urethane acrylate represented by the following general formula (1), the organic polar solvent, and the supporting electrolyte (hereinafter, referred to as a solid electrolyte)
Abbreviated as "composition A". ) As a precursor, and a solid polymer electrolyte obtained by solidifying the precursor.

[0030]

Embedded image (In the formula (1), R ¹ and R ² are the same or different groups and represent a group selected from the following general formulas (2) to (4).
R ³ and R ⁴ are the same or different groups and 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. M is 1 to 1
00, preferably 1 to 50, more preferably 1 to 20
Indicates an integer in the range. )

[0031]

Embedded image (In the general formula (2) ~ (4), R 5 ~R 7 are the same or different groups, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The R ⁸ to 20 carbon atoms, Preferably 2 carbon atoms
1 to 8 are shown. R ⁹ represents a trivalent organic residue having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms. R ¹⁰ represents a tetravalent organic residue having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms. )

Examples of the divalent hydrocarbon residue represented by R ³ and R ⁴ in the general formula (1) include a chain divalent hydrocarbon group, an aromatic hydrocarbon group and an alicyclic hydrocarbon group. . The molecular weight of the urethane acrylate represented by the general formula (1) is
Although not particularly limited, preferably 2,500 to 30,0
00, more preferably 3,000 to 20,000. The amount of the organic polar solvent added is urethane acrylate 1
The ratio is usually 100 to 1,200 parts by weight, preferably 200 to 900 parts by weight, based on 00 parts by weight. If the amount of the organic polar solvent is too small, the ionic conductivity is not sufficient, and if the amount of the organic non-aqueous solvent is too large, the mechanical strength may be reduced.

The supporting electrolyte is appropriately selected depending on the 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. However, those exemplified above are preferred. Can be The addition amount is 0.1 to 30% by weight, preferably 1 to 20% by weight based on the organic polar solvent. Needless to say, other optional components that do not impair the object of the present invention can be added as needed. Examples of such optional components include a crosslinking agent, a polymerization initiator (light or heat), and an ultraviolet absorber. No.

A second example of the polymer solid electrolyte is a monofunctional acryloyl-modified polyalkylene oxide, polyfunctional acryloyl-modified polyalkylene oxide represented by the following general formula (5), an organic polar solvent, (Hereinafter, abbreviated as “composition B”) as a precursor, and a solid polymer electrolyte obtained by solidifying the precursor.

[0035]

Embedded image (Wherein, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
n shows the integer of 1 or more. )

In the general formula (5), R ¹¹ , R ¹² and R ¹³
And R ¹⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which may be the same or different, and in particular, R ¹¹ is a hydrogen atom, a methyl group, R ¹² is a hydrogen atom, a methyl group , R ¹³ are preferably a hydrogen atom, a methyl group, and R ¹⁴ is preferably a hydrogen atom, a methyl group, or an ethyl group. In the general formula (5), n represents an integer of 1 or more, usually 1 ≦ n ≦ 100, preferably 2 ≦ n ≦ 50, and more preferably 2 ≦ n ≦ 30. When n is 2 or more, oxyalkylene units may have so-called copolymerized oxyalkylene units different from each other.
As the polyfunctional acryloyl-modified polyalkylene oxide used in the present invention, preferred are a compound represented by the general formula (6), a so-called bifunctional acryloyl-modified polyalkylene oxide and a compound represented by the general formula (7), A so-called trifunctional or higher polyfunctional acryloyl-modified polyalkylene oxide may be used.

[0037]

Embedded image (Wherein, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
p represents an integer of 1 or more. )

[0038]

Embedded image (In the formula, R ¹⁹ , R ²⁰ and R ²¹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and q represents 1
The above integers are shown, r is an integer of 2 to 4, and L represents an r-valent linking group. The linking group L is usually a divalent, trivalent or tetravalent hydrocarbon group having 1 to 30, preferably 1 to 20 carbon atoms.

Of course, 2 represented by the general formula (6)
The functional acryloyl-modified polyalkylene oxide may be used in combination with the trifunctional or higher polyfunctional acryloyl-modified polyalkylene oxide represented by the general formula (7). When the compound represented by the general formula (6) and the compound represented by the general formula (7) are used in combination, the weight ratio is usually 0.1 / 99.9.
９９99.9 / 0.1, preferably 1/99 to 99/1,
More preferably, the range is 20/80 to 80/20. The weight ratio of the compound represented by the general formula (5) to the polyfunctional acryloyl-modified polyalkylene oxide used in the present invention is usually 1 / 0.001 to 1/1, preferably 1 / 0.001.
It is in the range of 0.05 to 1 / 0.5. The compounding ratio of the organic polar solvent is usually 50 to 800% by weight, preferably 10 to 100% by weight of the compound represented by the general formula (5) and the polyfunctional acryloyl-modified polyalkylene oxide.
A range of 0 to 500 wt% is desirable.

The mixing ratio of the supporting electrolyte is usually 1 to 30% by weight, preferably 3 to 3% by weight based on the weight of the compound represented by the general formula (5), the polyfunctional acryloyl-modified polyalkylene oxide and the organic polar solvent. The range is 20 wt%. Examples of the optional component include, but are not particularly limited to, a photopolymerization initiator for photopolymerization, a thermal polymerization initiator for thermal polymerization, and an ultraviolet absorber. The amount of the polymerization initiator used in the present invention is usually 0.005 to 5 wt% based on the weight of the compound represented by the general formula (5) and the polyfunctional acryloyl-modified polyalkylene oxide.
%, Preferably in the range of 0.01 to 3 wt%. This type of solid polymer electrolyte is described in detail in, for example, JP-A-11-282022, and the solid polymer electrolyte according to the present invention can be suitably used. Of course, the electrolyte used in the present invention is not limited to these.

Further, as the electrolyte used in the present invention, a so-called electrochromic electrolyte in which an electrochromic substance is contained in the electrolyte may be used. The method for incorporating the electrochromic substance into the polymer solid electrolyte is not particularly limited, but a method of mixing and containing the electrochromic substance in its precursor and then solidifying it is preferable. Although the content of the electrochromic substance is not particularly limited, it is usually 0.1 mM.
Desirably, it is about 100 mM.

Next, the method of injecting the electrolyte or its precursor will be described. Any method may be used as long as the electrolyte or its precursor can be injected into the cell. The method is not particularly limited, and various well-known methods may be used. Needless to say, the method described above is applicable. For example, a cell provided with an inlet is placed in a container, and the inside of the cell is evacuated under vacuum. Then, the inlet is immersed in an electrolyte or its precursor solution, and then the container is filled with an inert gas such as nitrogen or argon. To return to normal pressure,
A vacuum injection method or the like that allows injection is preferable. In addition, the cell may be vertically set in the container, and the injection port may be installed at the lower or upper part, and the cell may be injected.The cell may be installed in a horizontal or inclined state and injected. In consideration of the influence of the hydrostatic pressure of the liquid electrolyte, it is preferable to install the cell in a horizontal or inclined state. When an electrolyte or an electrolyte precursor is used as an electrolyte, an operation for converting the precursor into an electrolyte, such as photopolymerization, photocrosslinking, thermal polymerization, or thermal crosslinking, needs to be performed. It is preferably performed after a sealing operation described later.

After the electrolyte or its precursor is injected into the cell, the injection port of the cell is usually sealed with a sealing material or the like. Although the sealing operation is not particularly limited, the vacuum injection method is usually performed by opening a vacuum container. In this case, it is desirable to carry out the reaction in an atmosphere of an inert gas or in an extremely low humidity as much as possible. The sealing agent is not particularly limited, but is, for example, a component that seals the inside of the device and isolates the outside from the outside by injecting, filling, or applying to an injection port portion to affect the performance of the device, for example, moisture or oxygen. The material is not particularly limited as long as it is a material that can prevent permeation of active gases such as carbon monoxide and the like.

For example, an inorganic material capable of filling the injection port without gaps, for example, glass or ceramic, or a polymer material such as resin or rubber, for example, polyester such as polyethylene terephthalate, polyamide, polysulfone,
Polyether sulfone, polyether ether ketone,
Polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, polystyrene, cellulose triacetate, polymethylpentene, polysiloxane, polyethylene, polypropylene, cellulose acetate, phenolic resin, urea resin, epoxy resin, polyvinyl acetate, polyvinyl acetal, polyvinyl alcohol , Acrylate, methacrylate, cyanoacrylate, polyamide, natural rubber and synthetic rubber such as isoprene rubber, butadiene rubber, styrene butadiene rubber, butyl rubber, ethylene propylene rubber, chloroprene rubber, chlorosulfonated polyethylene, nitrile rubber , Urethane rubber, polysulfide rubber, acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorine rubber, hydrogenated Materials such as Rirugomu and the like.

Alternatively, a curable resin may be used as a sealing material, and these may be injected into the sealing port, filled or applied, attached, cured, and closed. As the curable resin used in this method, various curable materials such as a thermosetting type, a photo-curing type, and an electron beam-curing type can be used, and there is no particular limitation. It goes without saying that a corresponding curing method is applied. Specific examples of the curable resin include phenol resin, urea resin, epoxy resin, polyvinyl acetate, polyvinyl acetal, polyvinyl alcohol, acryl and methacrylate, cyanoacrylate, polyamide and the like. May be used alone or as a mixture of two or more. In addition, various modifications may be made by modifying these or adding fillers. In the case of thermal curing, a material that can be cured at room temperature can be used. However, if heating is necessary, heating may be performed using various ovens, infrared heaters, electric heaters, sheet heating elements, and the like.
It is sufficient that the composition can be cured between 0 ° C., preferably between room temperature and 100 ° C. The time required for curing is not particularly limited as long as the electrochromic property is not impaired, but is preferably within 24 hours, more preferably within 1 hour. In the case of photocuring, a low-pressure, high-pressure, ultrahigh-pressure mercury lamp, xenon lamp, incandescent lamp, laser light, or the like can be used as long as the lamp is suitable for the absorption wavelength of the initiator. At the time of curing, the entire surface of the element may be uniformly exposed, and the entire surface may be simultaneously cured, or a lamp or a light source may be moved, or a light guide material such as an optical fiber may be used, or a mirror may be used to collect light. The light may be sequentially cured by scanning with a spot light. The above-mentioned sealing material may be used alone or in combination of two or more appropriately selected.

Next, the present invention will be specifically described with reference to the accompanying drawings. FIG. 1 is a view showing an example of the electrochromic light control glass cell of the present invention, and FIG. 2 is a schematic view showing an example of a liquid electrolyte injection apparatus into the electrochromic light control glass cell used in the present invention. . As shown in FIG. 1, two transparent conductive substrates 1 and 1 are opposed to each other at a predetermined interval, and a peripheral portion between the substrates 1 and 1 is preliminarily processed with a primary sealing material 2 as shown in FIG. For example, 2
A secondary sealing material 3 including a secondary spacing adjusting member such as a glass bead of 00 to 700 μm and a primary spacing adjusting member 4 such as a glass bead of 200 to 700 μm are scattered and adhered near the inside of the primary sealing material. Thereafter, the outer surface of the peripheral portion of the substrate (the seal material mounting portion) is externally pressed (pressed) to reduce the distance between the substrates 1 and 1 to the size of the primary distance adjusting member 4 (crushing). Then 1
When the next interval adjusting member 4 is not sprayed, depending on the position where pressure is applied from the outside to press the substrates 1 and 1 to a predetermined interval, for example, only the secondary interval adjusting member in the secondary sealing material 3, for example, beads alone Even if a predetermined interval is set using
If the distribution of the intervals between the substrates 1 and 1 sometimes varies, the intervals in the cell plane may not be equal to the intervals corresponding to the bead diameter and may vary. That is, the substrates 1 and 1 used for cell fabrication are usually preferably glass, but if the glass is particularly tempered glass, even if the glass is flat or curved in the process, the distance between the cells becomes flat when the two substrates used are combined. It is very difficult to make it uniform within. In particular, when the size is increased, the uniformity of the spacing in the cell plane is further deteriorated. Therefore, in the present invention, the outer surface of the seal portion at the peripheral portion of the substrates 1 and 1 is pressed by applying pressure from the outside in a state where the primary gap adjusting member 4 is sprayed and adhered to the vicinity of the inside of the primary seal material. Thereby, the substrate interval can be controlled. By fixing with the sealing materials 2 and 3 so that this state is maintained, the cell 5 in which the distance between the substrates is controlled is manufactured. In addition, the cell 5 thus manufactured
Is placed, for example, in the container 6 shown in FIG. Thereafter, the container 6 is evacuated to vacuum and the electrolyte or its precursor is charged into the cell 5.
Inject into. Next, the container 6 is returned to normal pressure with an inert gas, and the inlet 7 (see FIG. 1) is sealed. This method can also make the in-plane coloring response uniform. Therefore, in the method of manufacturing the electrochromic light control glass of the present invention, since the cells are manufactured by the above-described method, the fluctuation of the cell interval is suppressed. Further, the in-plane coloring response of the produced electrochromic light control glass can be made uniform. Further, when the electrochromic light control glass is enlarged, it is possible to achieve uniform coloring response within the cell plane, which cannot be obtained by the conventional method. From these facts, as a result, it becomes possible to obtain an electrochromic light control glass in which the coloring response within the cell surface is uniform.

[0047]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to those described in the examples.

Example 1 A substrate with an electrochromic conductive film was manufactured as follows. 80x at 3mm thickness
On a tempered glass of 40 cm, the resistance was 5 Ω / sq. An ITO film was formed such that The electrochromic color-forming electrode was produced as follows. The conductive film substrate is made of the above ITO glass (having an opening of 4 mmφ at a distance of about 25 mm from the side of the glass as shown in FIG. 2) and has a thickness of 1 to 3 nm at room temperature.
Under the condition of s, tungsten oxide was deposited to a thickness of 500 nm to produce an electrochromic coloring electrode, which was used as a coloring electrode substrate. As a primary sealing material, butyl rubber having a thickness of 1 mm and a width of 5 mm was stuck 15 mm inward from the outer periphery of the substrate on the counter electrode substrate produced as described above. Next, a room-temperature-curable epoxy-based sealing material containing 2% of 300 μm glass beads, which is a secondary spacing adjusting member, was applied as a secondary sealing material to the outer peripheral portion of the primary sealing material using a dispenser. Next, 400 as a primary gap adjusting member is provided inside the substrate on which the primary and secondary sealing materials are provided.
μm glass beads were sprayed, the substrate was swung horizontally, and the glass beads were attached near the inside of the primary sealing material. Next, the coloring electrode substrates are opposed to each other, a pressure is applied to the outside of the sealing portion of these substrates with a clip, and the sealing material is crushed. Then, the distance between the substrates is controlled, and the secondary sealing material is cured while maintaining this state. I let it. As a result, the entire peripheral portion between the substrates is adhered by the sealing material, and the 80 × 40c having the liquid electrolyte injection port on the cell surface, not on the cell cross section.
An m-size electrochromic dimming glass cell was obtained. Next, the distance in the cell plane obtained using a laser displacement meter was measured. FIG. 3 shows the measurement positions, and Table 1 shows the measurement results. Next, in this state, an injection jig 9 with an injection pipe 8 was attached to the injection port 7 as shown in FIG. At this time, the distal end opening of the injection pipe 8 is arranged near the bottom of the storage container 10 in the container 6, and the conduit 13 is connected to the external liquid storage 12 of the liquid electrolyte with the injection valve 11 installed outside. Was also placed above the container 10. Next, a liquid electrolyte (concentration: 0.6 mol / L) containing LiI electrolyte using γ-butyrolactone as a solvent 14
Was placed in the external liquid storage container 12, and the liquid electrolyte was degassed in advance. After the above loading was completed, the exhaust valve 15 was opened and the inside of the container 6 was evacuated with a rotary pump for 30 minutes.
Next, after closing the exhaust valve 15, the injection valve 11 is opened, and a predetermined amount of the liquid electrolyte 14 necessary for injecting the electrolyte into the cell 5 is introduced into the storage container 10 in the container 6, and the valve 11 is closed. Was. At this time, the opening at the tip of the injection pipe 8 connected to the cell injection port 7 is immersed in the liquid electrolyte and
The inside and the cell 5 are isolated. In this state, the leak valve 16
Was released, and the pressure was returned to normal pressure by introducing nitrogen into the vessel 6. The container 6 was released, the cell 5 was taken out, and the inlet 7 was sealed. The cell 5 thus obtained is
It was left in an oven at a temperature of 100 ° C. for 100 hours to produce an electrochromic light control glass.

Coloring Test Next, a coloring test was performed on the obtained electrochromic light control glass. The change in the coloring response of the light control glass was determined in the following manner. 633nm of He-Ne laser expanded to about 20mm in diameter by beam expander
Of light f was passed through the electrochromic light control glass, and the transmitted light was measured by a Si photodiode. A coloring voltage is applied to the light control glass, and the time when the transmittance reaches 55% to 20% is determined. The change in transmittance during coloring was measured at five points as shown in FIG. 4, and the uniformity in the light control glass surface was measured. A voltage of 1.5 V and a current of 0.5 A were applied so that the electrochromic coloring electrode side was a negative electrode and the counter electrode side was a positive electrode, and a coloring time at which the transmittance became 50% to 20% was determined. Table 2 shows the coloring time. As is clear from Table 2, an electrochromic light control glass having uniform coloring response was obtained.

(Example 2) In Example 1, 20 wt% of methoxytetraethylene glycol methacrylate was added to the liquid electrolyte, and Darocur 11 was used as a photocuring catalyst.
73 (manufactured by Ciba Specialty Chemicals) to 0.02
A photopolymerizable liquid electrolyte to which wt% was added was prepared. The procedure was performed in the same manner as in Example 1 except that this liquid electrolyte was used. After injecting the liquid electrolyte in the same manner as in Example 1, the injection port was sealed, and the cell was irradiated with 20 J using a high-pressure mercury lamp to polymerize the liquid electrolyte. The device thus obtained was subjected to the measurement of the cell interval and the coloring test in the same manner as in Example 1.
The results are shown in Tables 1 and 2. As is clear from Table 2, an electrochromic light control glass having uniform coloring response was obtained.

(Comparative Example 1) In Example 1, 400 μm glass beads were not sprayed around the inside of the primary sealing material.
The same method was used except that a cell was prepared using a room-temperature-curable epoxy-based sealing material containing 2% of 400 μm glass beads as a spacer material as a secondary sealing material. The device thus obtained was subjected to the measurement of the spacing in the cell plane and the coloring test in the same manner as in Example 1. The results are shown in Tables 1 and 2. As can be seen from Table 2, no uniform coloring response is achieved.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

As described above, according to the present invention, it is possible to improve the non-uniformity of the cell spacing depending on the substrate used for the electrochromic light control glass. In addition, an excellent electrochromic light control glass can be obtained, for example, there is no color unevenness and uniform coloring response in the cell plane is achieved.

[Brief description of the drawings]

FIG. 1 is a view showing an example of an electrochromic light control glass cell of the present invention, in which (a) is a plan view and (b) is a cross-sectional view.

FIG. 2 is a schematic diagram showing an example of a liquid electrolyte injection apparatus for an electrochromic light control glass cell used in the present invention.

FIG. 3 is a diagram showing positions of measurement points of a substrate interval in Examples and Comparative Examples of the present invention.

FIG. 4 is a diagram showing measurement positions of transmittance in Examples and Comparative Examples of the present invention.

FIGS. 5A and 5B are process diagrams showing a conventional method for injecting a liquid electrolyte into a cell for an electrochromic element, in which FIG. 5A is a diagram showing a pressure reduction process, and FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent conductive substrate 2 Primary sealing material 3 Secondary sealing material 4 Primary spacing adjusting member 5 Electrochromic light control glass cell 6 Container 7 Inlet 8 Injection pipe 9 Injection jig 10 Storage container 11 Injection valve 12 External liquid storage container 13 Conduit 14 Electrolyte or precursor thereof 15 Exhaust valve 16 Leak valve

Continuing from the front page (72) Inventor Shibata, Adult 426-1, Ozawa Uehara, Kakuda, Aikawa-cho, Aiko-gun, Kanagawa Prefecture Inside Asahi Glass Co., Ltd. F term in the company (reference) 2K001 AA08 BB43 BB49 CA02 CA04 CA08 CA09 CA30 CA34 CA35 CA45 DA02 DA23 DA25

Claims (2)

[Claims] 1. An electrochromic dimming glass cell having two transparent conductive substrates facing each other at a predetermined interval and sealing a peripheral portion between the substrates, wherein an inner peripheral portion between the substrates of the cell is provided inside. 2 including a primary interval adjusting member, a primary sealing material, and a secondary interval adjusting member
An electrochromic tone, wherein a second sealing material is sequentially arranged, and the substrate is fixed with at least a secondary sealing material so as to maintain a state in which a distance between the substrates is controlled by pressing an outer surface of a peripheral portion of the substrate. Light glass cell. 2. A primary spacing adjusting member made of a material that is not collapsed even when a force is applied to the two transparent conductive substrates facing each other at a predetermined interval from the inside to the outside along a peripheral portion between the substrates. 2 including a primary sealing material and a secondary gap adjusting member
A cell is formed by sequentially arranging the next sealing material and fixing the substrate with at least a secondary sealing material so as to maintain a state in which the distance between the substrates is controlled by pressing the outer surface of the peripheral portion of the substrate. A method for producing an electrochromic light control glass, comprising: injecting an electrolyte or a precursor thereof into the inside to produce an electrochromic light control glass.