【発明の詳細な説明】［産業上の利用分野］本発明はエレクトロクロミック（Ｅ Ｃ）物質を用いた
調光体に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a light control body using an electrochromic (EC) substance.
［従来の技術］近年、ＥＣ物質を用いた調光体が、防眩ミラー、調光窓
等として用いられ始めている。[Prior Art] In recent years, light control bodies using EC substances have begun to be used as anti-glare mirrors, light control windows, and the like.
このようなＥＣ物質を用いた調光体は、通常電極基板間
に酸化タングステン、酸化モリブデン等のＥＣ物質とこ
のＥＣ物質を着色させうるイオンを含む電解質とを介在
させて構成されている。A light control body using such an EC material is usually constructed by interposing an EC material such as tungsten oxide or molybdenum oxide and an electrolyte containing ions capable of coloring the EC material between electrode substrates.
上記電解質としては、プロトンあるいはリチウムイオン
を含む電導性が良好な系として各種組成のものが検討さ
れている。この代表的なものとしては、溶液型電解質で
は例えば特開昭５５−１３８７２０号公報に記載されて
いるように、過塩素酸リチウム等のリチウムイオン源鳴
質を炭酸プロピレン等の溶媒に溶解したものが知られて
いる。他方、リチウム電導性固体電解質としては窒化リ
チウムやヨウ化リチウムを用いたものも知られている。As the above-mentioned electrolyte, various compositions are being considered as systems containing protons or lithium ions and having good conductivity. A typical solution-type electrolyte is one in which a lithium ion source such as lithium perchlorate is dissolved in a solvent such as propylene carbonate, as described in JP-A-55-138720. It has been known. On the other hand, lithium conductive solid electrolytes using lithium nitride or lithium iodide are also known.
［発明の解決しようとする問題点］本発明者達は、特開昭５８−３０７２９号で電解質中に
レドックス剤を添加させることにより、透明電極を対極
として使用する調光体が得られることを示している。こ
の電解質中で用いたレドックス剤のうちヨウ素イオンを
電離するヨウ素イオン源物質が応答性、耐久性の点で他
のレドックス剤より優れた特性を示すことが判明した。[Problems to be Solved by the Invention] The present inventors discovered in Japanese Patent Laid-Open No. 58-30729 that a light control body using a transparent electrode as a counter electrode can be obtained by adding a redox agent to an electrolyte. It shows. Among the redox agents used in this electrolyte, it was found that an iodine ion source material that ionizes iodine ions exhibits superior characteristics in terms of responsiveness and durability compared to other redox agents.
しかるに、このようなヨウ素イオン源物質として例えば
ヨウ化リチウムを溶液状で用いた場合には、溶媒として
炭酸プロピレンを用いると高温で二酸化炭素ガスが発生
しさらに炭酸リチウムが析出し、又、光が照射されたと
きにも二酸化炭素ガスが発生するという欠点があった。However, when lithium iodide is used as an iodine ion source material in the form of a solution, if propylene carbonate is used as a solvent, carbon dioxide gas is generated at high temperatures, and lithium carbonate is further precipitated. The drawback was that carbon dioxide gas was also generated when irradiated.
また、アルコール系溶媒、例えばブチルアルコールを用
いた場合には、光が照射された場合にフォトクロミック
現象、即ち、ＥＣ物質、例えば酸化タングステンの電解
質溶液に接する面のフラットバンドポテンシャルが正方
向にシフトし光により着色しやすくなり、かつ水素ガス
が発生するという欠点があった。Furthermore, when an alcoholic solvent such as butyl alcohol is used, when irradiated with light, a photochromic phenomenon occurs, that is, the flat band potential of the surface of the EC material, such as tungsten oxide, in contact with the electrolyte solution shifts in the positive direction. It has the drawbacks of being easily colored by light and generating hydrogen gas.
また１本発明者達は、これを改良するために特開昭８１
−３２０３６号で電解質としてラクトン系溶媒にヨウ化
リチウムとゲル化用ポリマーを混合した電解質を使用し
た調光体も提案してきている。In addition, in order to improve this, the inventors of the present invention proposed
In No. 32036, a light control body using an electrolyte prepared by mixing lithium iodide and a gelling polymer with a lactone solvent has also been proposed.
しかし、このヨウ化リチウムとラクトン系溶媒を使用し
た場合においても、良好な性能を得るための製造条件の
範囲が狭く、屋外のような強い太陽光を受ける場所で使
用した場合にＥＣ物質のフォトクロミック現象、対向電
極の還元により電解質が分解して発泡するものがかなり
生じるという欠点があった。However, even when using lithium iodide and lactone-based solvents, the range of manufacturing conditions for obtaining good performance is narrow, and the photochromic properties of EC materials may be affected when used outdoors or in places exposed to strong sunlight. There was a drawback that the electrolyte decomposed due to the reduction of the counter electrode and a considerable amount of foaming occurred.
このため、製造条件幅が広く、安定して製造ができ、太
陽光の直射下でも熱的に安定で光による発泡、フォトク
ロミック現象による着色等の現象の発生しない電解質の
調光体が望まれていた。Therefore, there is a need for an electrolyte light control body that can be manufactured stably under a wide range of manufacturing conditions, is thermally stable even under direct sunlight, and does not cause phenomena such as foaming due to light or coloring due to photochromic phenomena. Ta.
［問題を解決するための手段］本発明は、従来の調光体の以上のような欠点を解消する
ためになされたものであり、対向する電極基板間にＥＣ
物質層と電解質とを介在させて成る調光体において、電
解質゛がラクトン系有機溶媒または少くともＳ＝Ｏを含
む有機溶媒（ただしスルホン酸系な除く）と、レドック
ス剤として少なくとも１種のフェロセン系化合物と、カ
チオン源物質と、該電解質をゲル化させるポリマーとを
含むことを特徴とする調光体を提供するものである。[Means for Solving the Problems] The present invention has been made in order to eliminate the above-mentioned drawbacks of conventional light control bodies.
In a light control body comprising a material layer and an electrolyte, the electrolyte contains a lactone-based organic solvent or an organic solvent containing at least S=O (excluding sulfonic acid-based solvents), and at least one type of ferrocene as a redox agent. The present invention provides a light control body characterized by containing a system compound, a cation source substance, and a polymer that gels the electrolyte.
即ち、本発明の調光体は、電解質のレドックス剤として
耐久性の高いフェロセン系化合物の少なくとも１種を使
用し、このレドックス剤を溶解する溶媒としてはラクト
ン系有機溶媒または特に太陽光の直射や熱に安定性で耐
久性の高い溶媒であるＳ＝０構造を有する有機溶媒を使
用し、支持電解質としてカチオン源物質を使用し、さら
にこの電解質をゲル化させるポリマーを添加したもので
ある。That is, the light control body of the present invention uses at least one type of highly durable ferrocene-based compound as a redox agent for the electrolyte, and a lactone-based organic solvent or a lactone-based organic solvent or especially direct sunlight or a solvent for dissolving this redox agent. An organic solvent having an S=0 structure, which is a thermally stable and highly durable solvent, is used, a cation source substance is used as a supporting electrolyte, and a polymer is added to gel the electrolyte.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
電極基板は、ガラス又はプラスチック等の基板表面上に
酸化スズ、酸化インジウム又は酸化スズ−酸化インジウ
ム（ＩＴＯ）等の透明導電膜を塗布、蒸着、スパッタ等
の公知の方法で形成し電極としたもの等を用いる。また
、必要に応じてこの透明導電膜にアルミ、クロム、チタ
ン等の金属や導電ペーストによる細線リードを線状、格
子状等に積層してもよい、。The electrode substrate is an electrode formed by forming a transparent conductive film such as tin oxide, indium oxide, or tin oxide-indium oxide (ITO) on the surface of a substrate such as glass or plastic by a known method such as coating, vapor deposition, or sputtering. etc. are used. Further, if necessary, fine wire leads made of metal such as aluminum, chromium, titanium, or conductive paste may be laminated on this transparent conductive film in the form of a line, a grid, or the like.
なお、調光ミラー等の光が調光体を透過することを要し
ない場合には、基板の一方は透明でなくてもよく、セラ
ミック又はアルミ、チタンなどの全屈を用いても良いし
、電極としては窒化チタン、窒化ジルコニウム、窒化ハ
フニウム等の反射性の電極を用いても良い、更に、調光
ミラーとして用いる場合には、電極基板を２枚とも透明
のものを用い、一方の電極基板の裏面に鏡面を形成して
も良い。Note that if the light of a light control mirror or the like does not need to pass through the light control body, one of the substrates does not need to be transparent, and a fully reflective material such as ceramic, aluminum, or titanium may be used. As the electrode, a reflective electrode such as titanium nitride, zirconium nitride, or hafnium nitride may be used.Furthermore, when used as a light control mirror, both electrode substrates should be transparent, and one electrode substrate A mirror surface may be formed on the back surface.
ＥＣ物質は、酸化タングステン、酸化モリブデン、酸化
チタン、酸化イリジウム等の公知のＥＣ物質が用いられ
るが、酸化タングステンまたはこれを主成分とする酸化
タングステン系の物質が望ましい。As the EC material, known EC materials such as tungsten oxide, molybdenum oxide, titanium oxide, and iridium oxide are used, but tungsten oxide or a tungsten oxide-based material containing tungsten oxide as a main component is preferable.
本発明の有機溶媒としては、ラクトン系の有機溶媒また
はスルホン酸系以外のＳ＝ｏ基を含有する有機溶媒が使
用できる。As the organic solvent of the present invention, a lactone-based organic solvent or a sulfonic acid-based organic solvent containing an S=o group can be used.
有機溶媒であり、スルホンアミド、スルホキシド等があ
る。Organic solvents include sulfonamides, sulfoxides, etc.
本発明ではヨウ素化合物をレドックス剤として使用する
のではないため、ラクトン系の有機溶媒を使用しても太
陽光下での劣化は殆ど問題とならない。もっとも、この
Ｓ−〇基を含有する有機溶媒は太陽光の直射下でも安定
であり、高温下にさらされても安定なため、調光体の耐
候性を向上させることができ、特に好ましい。In the present invention, since an iodine compound is not used as a redox agent, deterioration under sunlight hardly poses a problem even if a lactone-based organic solvent is used. However, organic solvents containing this S-0 group are stable even under direct sunlight and stable even when exposed to high temperatures, so they can improve the weather resistance of the light control body, and are particularly preferred.
このため、これらの有機溶媒を単独または混合して使用
するものであり、通常はこれらのみで使用されるが、電
解質の耐候性や他の成分の効果を悪化させない限り、５
０ｗｔ％以下の範囲内で他の有機溶媒を混合してもよい
。For this reason, these organic solvents are used alone or in combination, and are usually used alone, but as long as they do not deteriorate the weather resistance of the electrolyte or the effects of other components,
Other organic solvents may be mixed within a range of 0 wt% or less.
本発明では、電解質のレドックス剤としては少なくとも
１種のフェロセン系化合物を使用するものである。In the present invention, at least one ferrocene compound is used as a redox agent for the electrolyte.
このフェロセン系化合物としては、具体的にはフェロセ
ン、ジメチルフェロセン、コープチルフェロセン、アミ
ルフェロセン、ｔ−アミルフェロセン、ベンゾイルフェ
ロセン、アセチルフェロセン、ジアセチルフェロセン、
ビニルフェロセン等が用いられる。Examples of the ferrocene compounds include ferrocene, dimethylferrocene, coptylferrocene, amylferrocene, t-amylferrocene, benzoylferrocene, acetylferrocene, diacetylferrocene,
Vinylferrocene etc. are used.
このフェロセン化合物は、ＥＣ物質を着消色させた場合
に、耐久性に優れた特性、特に太陽光下での駆動や高温
下での駆動に優れた特性をを有しており、対向電極に特
別のＥＣ物質やカーボン等の電極を形成しなくてもよい
、ＩＴＯ対向電極上でのＬｉｌ系のレドックス電位は約
０．６ｖなのに対し、フェロセンは約０．４ｖになって
おり、そのレドックス反応がＬｉｌより速いためフェロ
センを用いると応答性が速くなる。This ferrocene compound has excellent durability when coloring and decoloring the EC material, especially when driven under sunlight and at high temperatures, and is suitable for use as a counter electrode. The Li-based redox potential on the ITO counter electrode, which does not require the formation of a special EC material or electrode such as carbon, is about 0.6 V, whereas the redox potential of ferrocene is about 0.4 V, and the redox potential of ferrocene is about 0.4 V. Since ferrocene is faster than Lil, the response becomes faster when ferrocene is used.
このフェロセン化合物の添加量は、前記溶媒に対して０
．００１Ｍ／ｕから飽和量までの範囲内で添加されれば
よく、通常は０．１−１８／Ｊｌ程度とされればよい。The amount of this ferrocene compound added is 0 relative to the solvent.
．． The amount may be added within the range from 0.001 M/u to saturation amount, and usually about 0.1-18/Jl.
なお、本発明ではフェロセン化合物をレドックス剤とし
て用いるため、ＥＣ物質層を発色させるプロトンやリチ
ウムイオン等のカチオンを含むカチオン源物質をＥＣ物
質層へのイオン注入のために添加する。In the present invention, since a ferrocene compound is used as a redox agent, a cation source material containing cations such as protons and lithium ions that cause the EC material layer to develop color is added for ion implantation into the EC material layer.
このカチオン源物質とルては、過塩素酸リチウム、過塩
素酸ナトリウム、四フッ化ホウ素化リチウム、四フッ化
ホウ素化ナトリウム等がある。このカチオン源物質の添
加量も、溶媒に対して０．００１Ｍ／ｉから飽和量まで
の範囲内で添加されればよく、通常は０．１〜ＩＮ／Ｊ
ｌ程度とされればよい、さらにこれらに第四級アンモニ
ウム塩を添加することもできる。Examples of the cation source substance include lithium perchlorate, sodium perchlorate, lithium boron tetrafluoride, and sodium boron tetrafluoride. The amount of the cation source substance to be added to the solvent may range from 0.001 M/i to saturation, and is usually 0.1 to IN/J.
A quaternary ammonium salt may be added to these.
また、本発明ではフェロセン系化合物にさらに２番目の
レドックス剤を添加してその応答性や安定性を向上させ
ることもできる。このためには、そのレドックス電位が
Ｏ〜１．２５Ｖの範囲にあるキノン系化合物を併用する
ことが好ましい、なお、このキノン系の化合物は酸化体
で使用する。具体的には、キノン系の化合物の中でもベ
ンゾキノン若しくは置換ベンゾキノンであるキシロキノ
ン、クロルアニル、クロルアニル酸等またはフェロセン
系の化合物であるフェロセン若しくは置換フェロセンが
好ましい。この併用するレドックス剤も０．００１〜０
．ＩＮ／ｉ程度添加されればよい。Furthermore, in the present invention, a second redox agent can be further added to the ferrocene compound to improve its responsiveness and stability. For this purpose, it is preferable to use a quinone compound having a redox potential in the range of 0 to 1.25 V. Note that this quinone compound is used in an oxidized form. Specifically, among quinone-based compounds, benzoquinone or substituted benzoquinones such as xyquinone, chloranil, chloranilic acid, etc., or ferrocene-based compounds such as ferrocene or substituted ferrocene are preferred. The redox agent used in combination is also 0.001 to 0.
．． It is sufficient to add about IN/i.
このキノン系化合物の添加により、ＩＴＯ等の電極より
もこのキノン系化合物の方が還元されやすいことにより
、電極の還元、ガスの発生等を防止できる。By adding this quinone compound, the quinone compound is more easily reduced than an electrode such as ITO, so that reduction of the electrode, generation of gas, etc. can be prevented.
特に、Ｓ＝０基を含有する有機溶媒に上記の２種のレド
ックス剤を添加することにより、応答特性が良好であり
、長寿命であって、かつ太陽光の直射下においても劣化
を生じにくい調光体が容易に得られる。In particular, by adding the two types of redox agents mentioned above to an organic solvent containing an S=0 group, it has good response characteristics, long life, and does not easily deteriorate even under direct sunlight. A light control body can be easily obtained.
このようなレドックス剤を含有する電解質は、通常の表
示素子のように不透明の対向電極を形成することができ
ない、即ち、対向電極を透明又は反射性電極とする調光
鏡、調光窓等の調光体に用いて特に有効な結果が得られ
る。また、本発明の調光体は、小型の透過型表示素子と
して用いた場合にも１０６回以上の発消色のサイクル寿
命を有し、表示素子としても駆動方式の工夫により十分
に実用に耐え得る。An electrolyte containing such a redox agent cannot form an opaque counter electrode like a normal display element; in other words, it cannot be used in devices such as dimming mirrors and dimming windows in which the counter electrode is a transparent or reflective electrode. Particularly effective results can be obtained when used in light control bodies. In addition, the light control body of the present invention has a cycle life of 106 times or more for color development/decolorization even when used as a small transmission type display element, and can be used as a display element in practical use by devising a driving method. obtain.
本発明ではさらに、この電解質にゲル化剤を１ｗｔ％か
ら飽和量まで添加して、該電解質溶液の粘度を増しゲル
化させる。これは本発明の調光体はフェロセン系化合物
を使用することにより、太陽光直射下でも安定ではある
が、反面、メモリー性が低下する欠点を有るためである
。In the present invention, a gelling agent is further added to the electrolyte from 1 wt % to a saturation amount to increase the viscosity of the electrolyte solution and cause it to gel. This is because the light control body of the present invention is stable even under direct sunlight due to the use of a ferrocene compound, but on the other hand, it has the disadvantage of poor memory performance.
このため、電解質中にゲル化剤を添加することによりこ
のメモリー性を向上させることができる。このゲル化剤
としてのポリマーは有機溶媒に溶解した際に１０３〜１
０５ｃｐｓ程度の粘度となるように調整されることが製
造プロセス及び電極の短絡防止の点からみて好ましい。Therefore, this memory property can be improved by adding a gelling agent to the electrolyte. This polymer as a gelling agent has a concentration of 103 to 1 when dissolved in an organic solvent.
It is preferable to adjust the viscosity to about 0.05 cps from the viewpoint of the manufacturing process and prevention of electrode short circuits.
このゲル化剤としては、種々のポリマーが使用できるが
、耐候性特に太陽光の直射による耐候性が良く、前記の
溶媒に対して安定に溶解して、電気化学的に安定なもの
で電極基板に接着性があるものが望ましい。具体的には
、ポリエチレンオキシド系、ポリアクリロニトリル系、
ポリメチルメタクリレート系またはポリビニルピロリド
ン系のポリマーが好ましい。Various polymers can be used as this gelling agent, but one that has good weather resistance, especially against direct sunlight, is stably soluble in the above-mentioned solvent, and is electrochemically stable. It is desirable that the material has adhesive properties. Specifically, polyethylene oxide type, polyacrylonitrile type,
Polymethyl methacrylate-based or polyvinylpyrrolidone-based polymers are preferred.
また、調光体は比較的面積が広く立てて使用されること
が多く、静水圧のために、電解質溶液が下方に下がって
来て調光体の下方が膨らんでしまうことが多いこと及び
外部から押圧されると２枚の電極基板が接触しショート
してしまうおそれがある。しかし、電解質中にポリマー
を添加してゲル状の電解質にしておくことにより、この
ような事故を防止することができる。In addition, the dimmer has a relatively large surface area and is often used standing up, and due to hydrostatic pressure, the electrolyte solution often falls downward, causing the lower part of the dimmer to swell and the outside of the dimmer. If pressed from above, there is a risk that the two electrode substrates will come into contact and cause a short circuit. However, such accidents can be prevented by adding a polymer to the electrolyte to form a gel electrolyte.
さらに何らかの原因で電極基板が破損した場合において
も、電解質や電極基板が飛散しにくく安全である。さら
には電解質が漏れにくくなるため、シールの強度が低く
てもよく、シール部の面積を小さくでき、基板にかかる
応力を減らし、光学的な歪を減少させるという利点も有
する。Furthermore, even if the electrode substrate is damaged for some reason, the electrolyte and the electrode substrate are unlikely to scatter and are safe. Furthermore, since the electrolyte is less likely to leak, the strength of the seal does not need to be low, and the area of the seal portion can be reduced, which has the advantage of reducing stress on the substrate and optical distortion.
この外、電解質には、本発明の効果を損しない範囲で他
の添加剤、例えば１着色剤、光を散乱させるための微細
な粒子、基板間隙を規制するためのスペーサー、紫外線
吸収剤等を添加してもよい。また、基板にカラーフィル
ター、赤外線反射膜、ガラスの飛散防止膜を設けたり、
調光体の内部をシールで複数の部分にわけて夫々に電解
質を配置する等してもよい。In addition, the electrolyte may contain other additives within the range that does not impair the effects of the present invention, such as a coloring agent, fine particles for scattering light, spacers for controlling the gap between the substrates, and ultraviolet absorbers. May be added. In addition, we provide color filters, infrared reflective films, and glass shatterproof films on the substrate.
The inside of the light control body may be divided into a plurality of parts using seals, and an electrolyte may be placed in each part.
［実施例］以下、本発明の詳細な説明する。[Example]The present invention will be explained in detail below.
実施例１１０ｃｍ角のガラス製裏基板上に蒸着法によりＩＴＯ膜
を膜厚１５００人にコートし透明電極を形成した。更に
、該裏基板上の透明電極上に膜厚５０００人のＷＯ＋膜
を蒸着してＥＣ物質層を形成した。Example 1 A 10 cm square glass back substrate was coated with an ITO film to a thickness of 1500 mm by vapor deposition to form a transparent electrode. Further, a WO+ film having a thickness of 5000 was deposited on the transparent electrode on the back substrate to form an EC material layer.
また、１０ｃｍ角のガラス製の表基板上にＩＴＯ膜を膜
厚１５００人に蒸着し透明電極を形成した。Further, an ITO film was vapor-deposited to a thickness of 1500 mm on a 10 cm square glass front substrate to form a transparent electrode.
電解質として、γ−ブチロラクトンにレドックス剤とし
て０．１５）４ｉのフェロセン、 ０．５Ｍ／１の過塩
素酸リチウム及び３０ｗｔ％のポリビニルブチラールを
溶解したゲル状物質を用い、該電解質層の厚さが約５０
ルｍとなるように、裏基板のＥＣ物質層と表基板の透明
電極との間に挿入し圧若固定して調光体を製造した。As an electrolyte, a gel-like substance in which 0.15)4i ferrocene as a redox agent, 0.5M/1 lithium perchlorate, and 30 wt% polyvinyl butyral were dissolved in γ-butyrolactone was used, and the thickness of the electrolyte layer was Approximately 50
A light control body was manufactured by inserting the light control material between the EC material layer on the back substrate and the transparent electrode on the front substrate and fixing it under pressure so that the light intensity was 1.
このようにして作成した調光体は、太陽光の直射下にお
いて着消色駆動した場合にも１０５回以上駆動しても発
泡等の外観上の劣化及び応答特性の異常を生じなかった
。The thus-prepared light control body did not exhibit deterioration in appearance such as bubbling or abnormality in response characteristics even when driven for 105 times or more, even when it was driven for coloring and decoloring under direct sunlight.
従来のヨウ化リチウムの電解質を用いた調光体の場合に
は、太陽光の直射下において着消色駆動した場合にも１
０５回以上駆動しても発泡等の外観上の劣化を生じない
ものもかなりみられたが、駆動条件やセル化条件による
固体差があり、劣化を生じないものを安定に製造するこ
とに問題があった。しかし、この実施例１の調光体はこ
の固体差が少なく、耐候性の高い調光体を容易に製造す
ることができた。In the case of conventional dimmers using lithium iodide electrolytes, even when driven under direct sunlight,
Although there were quite a few products that did not show any appearance deterioration such as foaming even after being driven for more than 5 times, there were individual differences depending on the driving conditions and cell formation conditions, making it difficult to stably manufacture products that did not cause deterioration. was there. However, in the light control body of Example 1, this individual difference was small, and it was possible to easily manufacture a light control body with high weather resistance.
また、ウェザ−０メーター中での放置試験では実施例１
の調光体もヨウ化リチウムの電解質を用いた調光体も２
０００時間程度たっても劣化をほとんど生じなかった。In addition, in the standing test in a weather-0 meter, Example 1
Both the dimmer and the dimmer using lithium iodide electrolyte are 2
Almost no deterioration occurred even after approximately 1,000 hours.
しかし、ウェザＰＯメーター中での着消色駆動試験にお
いてはその差が顕著に現れた。即ち、ヨウ化リチウムの
電解質を用いた調光体では、フォトクロミック現象によ
り完全消色しにくくなり（消色反応性の低下）、５０〜
１００時間程度で発泡したのに対し、実施例１の調光体
は５００時間たってもフォトクロミック現象を殆ど生じ
ないし発泡も生じなかった。However, the difference was noticeable in the coloring/decoloring drive test in a weather PO meter. That is, in a light control body using a lithium iodide electrolyte, it becomes difficult to completely erase the color due to the photochromic phenomenon (reduction in color erasing reactivity), and the
While foaming occurred after about 100 hours, the light control body of Example 1 hardly caused any photochromic phenomenon and did not foam even after 500 hours.
この実施例の調光体は、電解質をゲル化しているため、
垂直に配置しても膨らみ等の変形を生じなく、石により
意図的にガラス基板を破損した場合にも、ゲル状電解質
自身はもとより、ガラス基板も飛散することがなかった
。Since the light control body of this example has gelled electrolyte,
Even when placed vertically, no deformation such as bulges occurred, and even when the glass substrate was intentionally damaged by a stone, not only the gel electrolyte itself but also the glass substrate did not scatter.
実施例２〜２０第１表に示すような電解質を使用して実施例１と同様に
して調光体を製造した。Examples 2 to 20 Light control bodies were manufactured in the same manner as in Example 1 using the electrolytes shown in Table 1.
この結果、これらの調光体はいずれも太陽光の直射下に
おいて１０５回以上着消色駆動した場合にも発泡等の外
観上の劣化及び応答特性の異常を生じなく、ウェザ−Ｏ
メーター中での着消色駆動試験においても実施例１と同
等乃至より優れた特性を示した。また、垂直に配置して
も膨らみ等の変形を生じなく、石により意図的にガラス
基板を破損した場合にも、ゲル状電解質自身はもとより
、ガラス基板も飛散することがなかった。As a result, all of these dimmers do not cause any deterioration in appearance such as foaming or abnormalities in response characteristics even when driven for coloring and decoloring more than 105 times under direct sunlight, and weather-O
Also in the coloring/decoloring drive test in a meter, it showed characteristics equivalent to or better than those of Example 1. Further, even when placed vertically, no deformation such as bulges occurred, and even when the glass substrate was intentionally damaged by a stone, not only the gel electrolyte itself but also the glass substrate did not scatter.
特に、有機溶媒としてＳ＝Ｏ基を含有するテトラメチレ
ンスルホン、テトラエチルスルファミドを使用し、ポリ
マーとしてポリエチレンオキシド系、ポリアクリロニト
リル系、ポリメチルメタクリレート系またはポリビニル
ピロリドン系のポリマーを使用したものは、太陽光直射
下での駆動寿命が長く、高温下での駆動寿命も長いもの
であった・実施例２１〜２３実施例９のレドックス剤に０．０ＩＮ／Ｊｌのベンゾキ
ノン（実施例２１）、クロラニル（実施例２２）、クロ
ラニル酸（実施例２３）を併用した外は実施例９と同様
にして調光体を製造した。In particular, those that use tetramethylene sulfone or tetraethyl sulfamide containing an S=O group as the organic solvent and polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, or polyvinylpyrrolidone as the polymer, The drive life under direct sunlight was long, and the drive life at high temperatures was also long. Examples 21 to 23 0.0 IN/Jl of benzoquinone (Example 21) and chloranil (Example 21) were added to the redox agent of Example 9. A light control body was produced in the same manner as in Example 9 except that Example 22) and chloranilic acid (Example 23) were used together.
この調光体は実施例９に比して消色時、対極に作用する
電圧を更に低下できるため、還元されにくくなっており
、より消色反応が速くなるため、太陽光直射下での駆動
寿命が長かった。Compared to Example 9, this dimmer can further reduce the voltage applied to the counter electrode during decoloring, making it less likely to be reduced and resulting in a faster decoloring reaction, making it easier to drive under direct sunlight. It had a long lifespan.
実施例２４実施例９の支持電解質に過塩素酸テトラメチルアンモニ
ウムを０．５Ｍ／Ｊｌ併用した外は実施例９と同様にし
て調光体を製造した。この調光体は実施例９と同等の特
性を有した。Example 24 A light control body was produced in the same manner as in Example 9 except that 0.5 M/Jl of tetramethylammonium perchlorate was used in combination with the supporting electrolyte. This light control body had characteristics equivalent to those of Example 9.
［発明の効果］以上説明したように、本発明になる調光体においては、
ラクトン系またはＳ＝０系の有機溶媒にレドックス剤と
してフェロセン系化合物の少なくとも１種と、カチオン
源物質と、ポリマーとを溶解した電解質を用いたので、
応答性が速くなり太陽光の直射下で駆動しても電解質の
発泡等の劣化を生じにくい、さらに、他の構成材料であ
る電極、ＥＣ物質等の影響や駆動条件の影響を受けにく
く、安定して特性の良いものが容易に製造できる。[Effect of the invention] As explained above, in the light control body of the present invention,
Since we used an electrolyte in which at least one ferrocene compound as a redox agent, a cation source substance, and a polymer were dissolved in a lactone-based or S=0-based organic solvent,
The response is fast, and deterioration such as electrolyte foaming is less likely to occur even when driven under direct sunlight.Furthermore, it is less susceptible to the effects of other constituent materials such as electrodes and EC substances, as well as driving conditions, and is stable. It is easy to manufacture products with good characteristics.
特に、Ｓ−〇系の有機溶媒を使用することにより、高温
下での駆動時にも発泡を生じにくいため、より太陽光直
射下での使用においても安定である。In particular, by using an S-0 series organic solvent, foaming is less likely to occur even when driven at high temperatures, making it more stable even when used under direct sunlight.
また、本発明では電解質にポリマーを添加することより
ゲル化させることにより、フェロセン系レドックス剤の
問題点であるメモリー性の低下を少なくすることができ
、かつ面積の大きい調光体として用いても、スペーサを
必要とせず、電極基板の変形、短絡等の問題を生じにく
い。また、基板が破損したとしても、電解質や基板が飛
散しにくい。さらに、電解質自身が流動しにくくなって
いるため、強固なシールを必要としないので、調光体の
製造が容易となり、かつ基板に対するシールの応力が低
下するため光学的な歪も生じにくい。In addition, in the present invention, by gelling the electrolyte by adding a polymer, it is possible to reduce the decrease in memory properties, which is a problem with ferrocene redox agents, and it can also be used as a light control body with a large area. , no spacer is required, and problems such as deformation of the electrode substrate and short circuits are less likely to occur. Furthermore, even if the substrate is damaged, the electrolyte and the substrate are unlikely to scatter. Furthermore, since the electrolyte itself is difficult to flow, a strong seal is not required, making it easy to manufacture the light control body, and reducing the stress of the seal on the substrate, making optical distortion less likely to occur.
特に、本発明ではポリエチレンオキシド系、ポリアクリ
ロニトリル系、ポリメチルメタクリレート系またはポリ
ビニルピロリドン系のポリマーを使用することにより、
耐熱性も向上し、従来のポリビニルブチラール系が９０
℃程度までしか安定して使用できなかったのに対し、
１２０°Ｃ程度まで充分使用可能となる。In particular, in the present invention, by using polyethylene oxide-based, polyacrylonitrile-based, polymethyl methacrylate-based, or polyvinylpyrrolidone-based polymers,
The heat resistance has also been improved, and the conventional polyvinyl butyral type is 90%
Whereas it could only be used stably up to about ℃,
It can be used up to about 120°C.
また、ポリマーや溶媒がＯＨ基を多く含むと太陽光照射
下で対極の還元、発泡をしやすくなるが、上述の系では
それをかなり軽減できる。Furthermore, if the polymer or solvent contains a large amount of OH groups, the counter electrode tends to be reduced and foamed under sunlight irradiation, but this can be considerably reduced in the above-mentioned system.
これにより、太陽光の直射下において強い光と高温にさ
らされるような用途にも使用可能となり、家屋や自動車
の屋根に調光体を設けて使用することも可能となる。This makes it possible to use it in applications where it is exposed to strong light and high temperatures under direct sunlight, and it also becomes possible to use it by installing a light control body on the roof of a house or car.
本発明はこの外、本発明の効果を損しない範囲内で種々
の応用が可能なものであり、各種建築物、車両、船舶等
の窓、天井、間仕切、調光体を組み合せた大型表示装置
等に使用が可能なものである。In addition to this, the present invention can be applied in various ways without detracting from the effects of the present invention, and can be applied to large display devices that combine windows, ceilings, partitions, and light control bodies for various buildings, vehicles, ships, etc. It can be used for such purposes.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| Publication Number | Publication Date |
|---|---|
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|---|---|---|---|
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