JPS5994746A - Electrochromic display element - Google Patents
Electrochromic display elementInfo
- Publication number
- JPS5994746A JPS5994746A JP57204525A JP20452582A JPS5994746A JP S5994746 A JPS5994746 A JP S5994746A JP 57204525 A JP57204525 A JP 57204525A JP 20452582 A JP20452582 A JP 20452582A JP S5994746 A JPS5994746 A JP S5994746A
- Authority
- JP
- Japan
- Prior art keywords
- material layer
- electrochromic
- ion conductive
- conductive material
- transition metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004020 conductor Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 14
- 239000002952 polymeric resin Substances 0.000 claims abstract description 12
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 12
- 239000012463 white pigment Substances 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 5
- 229910001410 inorganic ion Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 abstract description 14
- 239000000758 substrate Substances 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004793 Polystyrene Substances 0.000 abstract description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 abstract description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 abstract description 2
- 229920002223 polystyrene Polymers 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 238000004040 coloring Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 244000101724 Apium graveolens Dulce Group Species 0.000 description 1
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 1
- 235000010591 Appio Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- -1 methyl isobutyl Chemical group 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の属する技術分野〕
本発明は改良されたエレクトロクロミック電気発色表示
素子に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to an improved electrochromic electrochromic display element.
従来エレクトロクロミック材料層として遷移金属酸化物
を用いた電気発色表示素子におけるイオン導電材料層に
ついては液体イオン導電材料層に関するものと、固体イ
オン導電材料層に関するものとに二側される。Conventionally, the ion conductive material layer in an electrochromic display element using a transition metal oxide as an electrochromic material layer is divided into two types: a liquid ion conductive material layer and a solid ion conductive material layer.
液体イオン導電材料層としては、発消色応答速度を大き
くシ、また高いコントラストを得る目的で、硫酸など、
カチオン移動度の大きい酸類を主体とする電解液が用い
られているが、次のような欠点がある。即ち、長期間使
用した時、電気発色表示素子から電解液が漏洩し易いた
め、電気発色表示素子の製作においては、液密に封止す
ることを要し、製造工程が煩雑となシ、作業効率が低い
。For the liquid ionic conductive material layer, sulfuric acid,
Electrolytes mainly composed of acids with high cation mobility are used, but they have the following drawbacks. In other words, when used for a long period of time, the electrolyte tends to leak from the electrochromic display element, so when manufacturing the electrochromic display element, it is necessary to seal it liquid-tight, which makes the manufacturing process complicated and labor intensive. Efficiency is low.
固体イオン導電材料層としては、ｓｉｏ、、 ＭｇＦｚ
。As the solid ion conductive material layer, sio, MgFz
.
ＣａＦ２等の無機物を蒸着等の物理的製膜法によって形
成するものと、パーフルオロスルホン酸重合体、スチレ
ンスルホン酸重合体、アクリル酸重合体等の高分子樹脂
を用いるものがある。しかし、前者は電解質層及び発色
層中に存在するピンホールを介して透明電極と対向電極
間に短絡する欠陥が生じやすく生産性が悪く、実用に適
さない。一方、高分子樹脂等で構成される固体イオン導
電材料は、カチオン移動速度が小さく、固体エレクトロ
クロミック材料層と接する界面の密着性が悪く、界面で
のイオン移動が円滑に行なわれないため、発消色の応答
速度が小さく、約２秒程度を要する。更にイオン導電材
料層が液体又は固体の区別なく、一般に電気発色表示素
子は、副反応によって水素を発生し、この水素によって
、透明電極として用いられている今月酸化物、例えば５
ｎ０２またはＩｎρ２が還元されて金属Ｓｎ又はＩｎを
生じ、長期間使用した場合、前記還元金属Ｓｎ又はＩｎ
によって電気発色表示素子の表示部分が不均一に褐色乃
至黒色化し、表示機能が低下する等の欠点がある。There are those that are formed using an inorganic material such as CaF2 by physical film forming methods such as vapor deposition, and those that use polymeric resins such as perfluorosulfonic acid polymer, styrene sulfonic acid polymer, and acrylic acid polymer. However, the former method is unsuitable for practical use because it tends to cause short-circuit defects between the transparent electrode and the counter electrode through pinholes present in the electrolyte layer and the coloring layer, resulting in poor productivity. On the other hand, solid ion conductive materials made of polymeric resins have a low cation migration speed, poor adhesion at the interface with the solid electrochromic material layer, and ions cannot move smoothly at the interface. The response speed for erasing color is slow and takes about 2 seconds. Furthermore, regardless of whether the ion-conductive material layer is liquid or solid, electrochromic display elements generally generate hydrogen through a side reaction, and this hydrogen causes the oxides used as transparent electrodes, such as 5
n02 or Inρ2 is reduced to produce metal Sn or In, and when used for a long period of time, the reduced metal Sn or In
As a result, the display portion of the electrochromic display element becomes unevenly brown or black, resulting in a disadvantage that the display function is deteriorated.
本発明の目的はこれ等の欠点を除去し、実用性の高い電
気発色表示素子を提供することにある。An object of the present invention is to eliminate these drawbacks and provide a highly practical electrochromic display element.
〔発明の概要〕
本発明は、遷移金属酸化物からなるエレクトロクロミッ
ク材１’１Ｊｆｆｉとこれに接するイオン導電材料層と
を具備する電気発色表示素子において、前記イオン導電
材料層が高分子樹脂と無機イオン導電材料からなるイオ
ン導電組成物にエレクトロクロミック材料層として用い
た遷移金属酸化物を加えたことを特徴とし、電気発色表
示素子の寿命の長期化、信頼性の向上に効果あるもので
ある。[Summary of the Invention] The present invention provides an electrochromic display element comprising an electrochromic material 1'1Jffi made of a transition metal oxide and an ion conductive material layer in contact with the electrochromic material 1'1Jffi, in which the ion conductive material layer is made of a polymer resin and an inorganic material. It is characterized by adding a transition metal oxide used as an electrochromic material layer to an ion-conductive composition made of an ion-conductive material, and is effective in extending the life span and improving reliability of electrochromic display elements.
第１図はエレクトロクロミック素子の概略構成を示し、
図中（］）はガラスやポリエステル等の透明基板、（２
）はＩｎ２０３１８ｎＯＩ ＋”等の透明な表示電極層
、（３）はＷＯ３１ＭｎＯ２Ｉ ＴｉＯ２等の遷移金属
酸化物からなるエレクトロクロミック材料層、（４）は
イオン導電材料層、（５）はＩｎ２Ｏ５ｌ ５ｎ０２
、 Ａｕ 、 Ａｇ 、 ＡＩ 、 Ｎｉ等の対向電極
である。このような構成の素子において、複合材料を用
い、発色層上にスピニング塗布法、浸漬法、ローラー塗
布法、スプレー塗布法等の製膜法によって形成すること
によって、ピンホールのない均一なしかも密着性のよい
固体電解質を用いることを特徴とする。Figure 1 shows the schematic structure of an electrochromic element,
In the figure, ( ) indicates a transparent substrate such as glass or polyester, (2
) is a transparent display electrode layer such as In20318nOI+'', (3) is an electrochromic material layer made of a transition metal oxide such as WO31MnO2I TiO2, (4) is an ion conductive material layer, and (5) is In2O5l 5n02.
, Au, Ag, AI, Ni, or the like. In an element with such a structure, by using a composite material and forming a film on the coloring layer by a film forming method such as a spinning coating method, dipping method, roller coating method, or spray coating method, it is possible to achieve uniform and close contact without pinholes. It is characterized by the use of a solid electrolyte with good properties.
複合材料は、高分子樹脂を有機溶媒に溶解した後、無機
イオン性材料及びエレクトロクロミック材料層として用
いた遷移金属酸化物を添加し、充分に混合することによ
って製造することができる。The composite material can be manufactured by dissolving the polymer resin in an organic solvent, adding the inorganic ionic material and the transition metal oxide used as the electrochromic material layer, and thoroughly mixing the mixture.
溶液中の高分子樹脂の濃度は１０ ｍｏｔ／Ｌから飽
和溶液までの範囲が考えられるが、実際の濃度について
は重要とは考えられない。無機イオン性導電材料の濃度
は、高分子樹脂に対して０．１〜１０００重量％が適当
であり、それ以下であると着色時の色が薄く見えにくい
。それ以上であると複合材として製膜性が悪く、均一な
膜が形成されない。エレクトロクロミック材料層として
用いた遷移金属酸化物は、高分子樹脂に対して０．０１
〜１０重量％が適当である。この遷移金属酸化物の添加
によって、セルの寿命の長期化がはかられるわけである
が、その効果の原因、＠構に対しては不明であるが、添
加量が０．０１重１ｆｔ％以下であると、寿命の長期化
に全く効果が々くなり、１０重量％以上にすると、複合
材として製膜性が悪く々る。The concentration of the polymer resin in the solution may range from 10 mot/L to a saturated solution, but the actual concentration is not considered important. The appropriate concentration of the inorganic ionic conductive material is 0.1 to 1000% by weight based on the polymer resin, and if it is less than that, the color will be too pale and difficult to see. If it is more than that, the film forming properties of the composite material will be poor and a uniform film will not be formed. The transition metal oxide used as the electrochromic material layer has a ratio of 0.01 to the polymer resin.
~10% by weight is suitable. By adding this transition metal oxide, the life of the cell can be extended, but the cause of this effect and the structure are unknown, but if the amount added is less than 0.01w/1ft% If it is, it will not be effective at all in prolonging the life, and if it is more than 10% by weight, the film forming properties of the composite material will be poor.
尚、本発明において用いる無機イオン材料としては、例
えば、ＬｉＣｌＯ４、ＬｉＩ 、 ＬｉＯＨ、ＬｉＦ、
ＮａＣｆｆ１４ＮａＯＨ，ＮａＩ 、ＮａＦなどが挙げ
られ、いずれもＬｉ Ｎａが発消色に関与するものであ
る。The inorganic ionic materials used in the present invention include, for example, LiClO4, LiI, LiOH, LiF,
Examples include NaCff14NaOH, NaI, NaF, etc., all of which involve LiNa in color development and fading.
高分子樹脂としては、ポリスチレン、ポリ塩化ビニル、
塩化ビニル−酢酸ビニル共重合体、ポリ酢酸ビニル、ポ
リビニルアセタール、フェノール樹脂・“″″′″′′
″′樹脂′トド７ ｐ Ｉ） 、ｎ、 、。Polymer resins include polystyrene, polyvinyl chloride,
Vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinyl acetal, phenolic resin/“″″′″′′
″′Resin′ Todo 7 p I), n, .
樹脂、ボリアクリロントリル、プタシニン系合成ゴム、
ポリオレフィンなど、特に限定するものではない。また
高分子樹脂を溶解する溶媒としては、メチルイソブチル
、ケトン、メタノール、エタノ−、ｎ、 、 ７ ＊
）二） ！Ｊ ）” ｌクレゾール、トルエン。Resin, polyacrylontrile, ptacinine synthetic rubber,
Polyolefin and the like are not particularly limited. In addition, examples of solvents for dissolving polymer resins include methyl isobutyl, ketone, methanol, ethanol, n, , 7 *
)2)! J)” l Cresol, toluene.
ブチルセロリ、ルプアセテート、エチルセロリルブアセ
テート、プロピレンカーボネート、アセト□ントリル、
ジメチルアセトアミド、Ｎ−メチルピロリドン、ジメチ
ルホルムアミドなどの非水溶媒が好ましく、樹脂を溶解
しうるもので、乾燥が製品であればよい。Butyl celery, lupuacetate, ethyl celeryl buacetate, propylene carbonate, acetontril,
Non-aqueous solvents such as dimethylacetamide, N-methylpyrrolidone, and dimethylformamide are preferred, as long as they can dissolve the resin and can be dried as a product.
また必要に応じて背景となる顔料を樹脂に対して５〜５
０重景チ添加することによって、反射型のＥＣセルの形
成が可能である。背景となる顔料としては、Ｔｉ０ｇ
、 Ａ１２０Ｂ 、ＭｇＯ，ＺｒＯ２，ｙρａ 、Ｔａ
２Ｑ５．Ｓｉｎ。Also, if necessary, add 5 to 5 % of the background pigment to the resin.
A reflective EC cell can be formed by adding zero or more. The background pigment is Ti0g
, A120B, MgO, ZrO2, yρa, Ta
2Q5. Sin.
等白色顔料が最も見ばえが良く適当であると思われるが
、他に所望の色の顔料金用いることも充分可能である。Equiwhite pigments are believed to be the most aesthetically pleasing and suitable, but pigments of other desired colors may well be used.
この複合材料は、ポリマー溶液中に無機イオン拐料、遷
移金属酸化物を添加後、ロールミル、サンドミル、ボー
ルミル、ミキサー等があり、いずれかの方法を用いて、
充分、分散した後発色層上にスピニング塗布浸漬法、ロ
ーラ塗布法などで形成することによって、ピンホールの
ない均一な薄膜を形成しうる。−！た薄膜中に残存する
有機溶媒を除去する目的で薄膜を５０〜１５０℃で加熱
処理することによシ、基板との密着性がよくなる。This composite material is produced by adding an inorganic ion additive and a transition metal oxide to a polymer solution, and then using any of the following methods: roll mill, sand mill, ball mill, mixer, etc.
A uniform thin film without pinholes can be formed by forming on a sufficiently dispersed post-coloring layer by a spinning coating dipping method, a roller coating method, or the like. -! By heating the thin film at 50 to 150° C. for the purpose of removing the organic solvent remaining in the thin film, the adhesion to the substrate can be improved.
本発明によれば、すなわち高分子樹脂に無機イオン導電
材料からなるイオン導電組成物に、エレクトロクロミッ
ク材料層として用いた遷移金属酸化物を添加することに
よって、寿命の長いセルが安定して供給できるようにな
った。According to the present invention, by adding a transition metal oxide used as an electrochromic material layer to an ion conductive composition made of a polymer resin and an inorganic ion conductive material, cells with a long life can be stably supplied. It became so.
また、溶液状複合材料を塗布法によって形成するため、
製造工程が簡単で、しかも均一なピンホールのない薄膜
状固体電解質を用いたエレクトロクロミック素子を形成
しうる。In addition, since the solution-form composite material is formed by a coating method,
The manufacturing process is simple, and an electrochromic device using a uniform pinhole-free thin film solid electrolyte can be formed.
また発消色は、無機イオン中のＬｉ 、Ｎａ を用い
ておシ、副反応による水素の発生等の問題もなく実用性
の高いものである。In addition, color development and fading is highly practical because it uses Li and Na in inorganic ions, and there are no problems such as generation of hydrogen due to side reactions.
実施例１
ガラス基板上にバタン化された透明導電膜を用意し、導
電膜上に厚さ０．３μｍの酸化タングステン膜を蒸着法
で設けた。Example 1 A transparent conductive film was prepared on a glass substrate, and a tungsten oxide film having a thickness of 0.3 μm was provided on the conductive film by vapor deposition.
一方、ポリメチルメタクリレ−） ５ ｆ １Ｌ１ｃＺ
Ｏ４５ｔ、酸化タングステンｌｆをＭＩＢＫ ５０９に
溶解し、充分混合させて複合材料を作った。この複合材
料を上記ガラス基板の酸化タングステン層上にスピンコ
ードして、膜厚２μの固体電解質層を設けた。On the other hand, polymethyl methacrylate) 5 f 1L1cZ
O45t and tungsten oxide lf were dissolved in MIBK 509 and thoroughly mixed to produce a composite material. This composite material was spin-coded onto the tungsten oxide layer of the glass substrate to provide a solid electrolyte layer with a thickness of 2 μm.
これを７００℃オープン中で加熱して充分固体電解質層
を乾燥させた。次いで固体電解質層上にＡｕを蒸着して
、対向電極を設けた。This was heated at 700° C. in an open environment to sufficiently dry the solid electrolyte layer. Next, Au was deposited on the solid electrolyte layer to provide a counter electrode.
また比較例として、酸化タングステンを除いた、上記と
同様の組成の複合材料を固体電解質層として同様なセル
を形成した。As a comparative example, a similar cell was formed using a composite material having the same composition as above but excluding tungsten oxide as a solid electrolyte layer.
このようにして得た２ａのエレクトロクロミック素子を
１．５Ｖ １．ＯＨ，Ｏ方形波で駆動試験を行なった。The electrochromic device 2a thus obtained was heated to 1.5V 1. A drive test was conducted using OH and O square waves.
着消色回数と発色濃度の変化を第２図に示す。第２図か
ら明らかなように、ｗＯ３の添加によって寿命が延びる
ことが明らかとなった。Figure 2 shows the number of times of coloring/decoloring and changes in color density. As is clear from FIG. 2, it has become clear that the addition of wO3 extends the life.
実施例２
複合材料として、ポリメチルメタクリレート５２゜ＬＬ
Ｉ６ｆ 、タングステン酸リチウムｌｆｆ！：ＭＩＢ
と５０２に溶解させた後、背景材としてＴｉＯ２５１を
加え充ρに分散させた。このようにして得た複合材を用
いて実施例１と同様の方法で、エレクトロクロミック素
子を形成した。ＷＯ３無添加のセルと共に２ｖＯ，５Ｈ
，の方形波で駆動試験を行なつ穴。発消色回数と着色濃
度の変化を第３図に示す。ＷＯ＝添加による寿命の長期
化は顕著なものである。Example 2 Polymethyl methacrylate 52°LL as a composite material
I6f, lithium tungstate lff! :MIB
After dissolving in 502 and 502, TiO251 was added as a background material and dispersed in ρ. An electrochromic device was formed using the composite material thus obtained in the same manner as in Example 1. 2vO, 5H with WO3-free cell
, the hole is tested with a square wave of . Figure 3 shows the number of times of color development and fading and changes in color density. The lifespan is significantly extended by adding WO=.
第１図は、本発明の電気発色表示素子の一構成例を示す
断面図、第２図および第３図は本発明の効果ヶ示す線図
である。
ｌ・・・ガラス基板
２・・・透明電極
３・・・エレクトロクロミック材料層
４・・・イオン導電材料層
５・・・対向電極
代理人 弁理士 則 近 憲 佑 （はが１名）第１図
第２図
１哨色＠叡
第８図
１消色回敷FIG. 1 is a sectional view showing an example of the structure of an electrochromic display element according to the present invention, and FIGS. 2 and 3 are diagrams showing the effects of the present invention. l...Glass substrate 2...Transparent electrode 3...Electrochromic material layer 4...Ion conductive material layer 5...Counter electrode representative Patent attorney Noriyuki Chika (1 person) 1st Fig. 2 Fig. 1 Stainless color @ Ei Fig. 8 1 Erased color
Claims (1)
料層と、これに接するイオン導電材料層とを具備する電
気発色表示素子において、前記イオン導電材料層として
、高分子樹脂と無機イオン導電材料からなるイオン導電
組成物に、エレクトロクロミック材料層として用いた遷
移金属酸化物を添加し、分散又は混合させた複合材を用
いること白色顔料を添加することを特徴とする電気発色
表示素子。(1) In an electrochromic display element comprising an electrochromic material layer made of a transition metal oxide and an ion conductive material layer in contact therewith, the ion conductive material layer is an ion conductive material made of a polymer resin and an inorganic ion conductive material. An electrochromic display element characterized by using a composite material in which a transition metal oxide used as an electrochromic material layer is added to a conductive composition and dispersed or mixed therein, and a white pigment is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57204525A JPS5994746A (en) | 1982-11-24 | 1982-11-24 | Electrochromic display element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57204525A JPS5994746A (en) | 1982-11-24 | 1982-11-24 | Electrochromic display element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5994746A true JPS5994746A (en) | 1984-05-31 |
| JPH0363726B2 JPH0363726B2 (en) | 1991-10-02 |
Family
ID=16491974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57204525A Granted JPS5994746A (en) | 1982-11-24 | 1982-11-24 | Electrochromic display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5994746A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03504050A (en) * | 1988-04-29 | 1991-09-05 | コアト イ ゲーテボーリ アクチ ボラゲット | Electrochromic device and its manufacturing method |
-
1982
- 1982-11-24 JP JP57204525A patent/JPS5994746A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03504050A (en) * | 1988-04-29 | 1991-09-05 | コアト イ ゲーテボーリ アクチ ボラゲット | Electrochromic device and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0363726B2 (en) | 1991-10-02 |
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