JP2518673B2 - Electrochromic display materials - Google Patents
Electrochromic display materialsInfo
- Publication number
- JP2518673B2 JP2518673B2 JP63164653A JP16465388A JP2518673B2 JP 2518673 B2 JP2518673 B2 JP 2518673B2 JP 63164653 A JP63164653 A JP 63164653A JP 16465388 A JP16465388 A JP 16465388A JP 2518673 B2 JP2518673 B2 JP 2518673B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- electrochromic display
- compound
- electrode
- display materials
- 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.)
- Expired - Lifetime
Links
- 239000012769 display material Substances 0.000 title claims description 13
- -1 aromatic nitro compound Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 description 17
- 230000002441 reversible effect Effects 0.000 description 7
- 239000010409 thin film Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003115 supporting electrolyte Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 239000002585 base Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011808 electrode reactant Substances 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 150000005838 radical anions Chemical class 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- SUGXZLKUDLDTKX-UHFFFAOYSA-N 1-(2-nitrophenyl)ethanone Chemical compound CC(=O)C1=CC=CC=C1[N+]([O-])=O SUGXZLKUDLDTKX-UHFFFAOYSA-N 0.000 description 1
- QAFJHDNFUMKVIE-UHFFFAOYSA-N 2,2'-dinitrobiphenyl Chemical group [O-][N+](=O)C1=CC=CC=C1C1=CC=CC=C1[N+]([O-])=O QAFJHDNFUMKVIE-UHFFFAOYSA-N 0.000 description 1
- DGDAVTPQCQXLGU-UHFFFAOYSA-N 5437-38-7 Chemical compound CC1=CC=CC(C(O)=O)=C1[N+]([O-])=O DGDAVTPQCQXLGU-UHFFFAOYSA-N 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- XKHFJJUHLGNTGM-UHFFFAOYSA-N C(CCC)[N+](CCCC)(CCCC)CCCC.B(F)(F)F Chemical compound C(CCC)[N+](CCCC)(CCCC)CCCC.B(F)(F)F XKHFJJUHLGNTGM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- JGNPSJMNGPUQIW-UHFFFAOYSA-N [C].CC=C Chemical group [C].CC=C JGNPSJMNGPUQIW-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WSVDSBZMYJJMSB-UHFFFAOYSA-N octadecylbenzene Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1 WSVDSBZMYJJMSB-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、電気化学的な酸化還元反応により可逆的に
着色消色を示す新規な芳香族ニトロ化合物を主剤とする
エレクトロクロミック表示材料に関する。TECHNICAL FIELD The present invention relates to an electrochromic display material containing a novel aromatic nitro compound as a main component, which exhibits reversible color fading by an electrochemical redox reaction.
（従来の技術） エレクトロクロミック表示は、直流電圧印加により透
明電極上で電気化学的な酸化あるいは還元反応が起こっ
て着色パターンが形成され、これに逆電圧を印加する
か、あるいは放電させることにより着色パターンが消色
するという機構を利用している。エレクトロクロミック
表示は、液晶表示に比べて、発色が鮮明であること、視
野角の依存性がないこと、メモリー機能を有すること、
大面積の表示が可能であることなど優れた特徴を持ち、
また主剤の種類により種々の色彩が得られることから多
色表示が期待されている。(Prior Art) In electrochromic display, when a DC voltage is applied, an electrochemical oxidation or reduction reaction occurs on a transparent electrode to form a colored pattern, which is colored by applying a reverse voltage or discharging it. It uses the mechanism that the pattern disappears. The electrochromic display has clearer color development than the liquid crystal display, has no dependence on the viewing angle, and has a memory function.
It has excellent features such as large area display,
Further, since various colors can be obtained depending on the type of the main agent, multicolor display is expected.
従来知られているエレクトロクロミック表示材料とし
ては、ビオロゲン誘導体などの有機化合物や酸化タング
ステンなどの無機化合物がある。またアゾ化合物誘導体
やアゾキシ化合物誘導体を用いたエレクトロクロミック
表示材料（特開昭57−21481号公報）も知られている。Conventionally known electrochromic display materials include organic compounds such as viologen derivatives and inorganic compounds such as tungsten oxide. Further, an electrochromic display material using an azo compound derivative or an azoxy compound derivative (JP-A-57-21481) is also known.
（発明が解決しようとする課題） 従来のエレクトロクロミック表示材料では、主剤とし
て酸化タングステンを用いた場合は青色、ビオロゲン誘
導体を用いた場合は青色乃至紫色、アゾ化合物誘導体，
アゾキシ化合物誘導体を用いた場合は赤色を中心とした
色彩のものしか得られていない。エレクトロクロミック
表示材料の特徴である多色表示を実現するためにさらに
多様な色彩をもつエレクトロクロミック表示材料の開発
が課題となっている。(Problems to be Solved by the Invention) In a conventional electrochromic display material, blue is used when tungsten oxide is used as a main component, blue to purple when a viologen derivative is used, azo compound derivatives,
When an azoxy compound derivative is used, only those colors centering on red are obtained. The development of electrochromic display materials having a wider variety of colors has been a challenge in order to realize multicolor display, which is a characteristic of electrochromic display materials.
（課題を解決するための手段） 本発明者らは、種々の色彩をもつエレクトロクロミッ
ク表示材料を得る目的で鋭意探索した結果、特定の芳香
族ニトロ化合物が赤，青，緑，オレンジなど多彩な色彩
の着色パターンをもつ多色表示材料として有効な化合物
であることを見出した。このものは電気化学的な還元反
応によって着色し、さらに酸化反応によって消色又は変
色する。しかもニトロ基の強い電子吸引性により、還元
反応によって生じたラジカルアニオンが安定化するため
その可逆性が非常に優れている。(Means for Solving the Problem) The inventors of the present invention have conducted diligent search to obtain electrochromic display materials having various colors, and as a result, specific aromatic nitro compounds have various colors such as red, blue, green, and orange. It was found that the compound is effective as a multicolor display material having a colored pattern. This substance is colored by an electrochemical reduction reaction, and is further decolorized or discolored by an oxidation reaction. In addition, the radical anion generated by the reduction reaction is stabilized by the strong electron-withdrawing property of the nitro group, so that its reversibility is extremely excellent.
本発明は、下記式（Ｉ）又は（II） （但し、（Ｉ）式において、Ｘは−COOR1,−COR2及び−
CNより選ばれた基を表わし、R1はアルキル基、アルケニ
ル基又はアラルキル基を表わし、R2はアルキル基、アル
ケニル基、アラルキル基又は置換基を有していてもよい
アリール基を表わす。ｎ又はｍは１〜２の整数である） で表わされる芳香族ニトロ化合物を主剤とするエレクト
ロクロミック表示材料である。The present invention has the following formula (I) or (II) (However, in the formula (I), X is -COOR 1 , -COR 2 and-
Represents a group selected from CN, R 1 represents an alkyl group, an alkenyl group or an aralkyl group, and R 2 represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group which may have a substituent. n or m is an integer of 1 to 2) An electrochromic display material containing an aromatic nitro compound represented by
本発明の上記式（Ｉ）において、Ｘは −COOR1、−COR2及び−CNより選ばれた基であり、R1と
しては、アルキル基、アルケニル基及びアラルキル基か
ら選ばれ、具体的にはメチル，エチル，プロピル，イソ
プロピル，ブチル，ヘキシル，オクチル，イソオクチ
ル，ドデシル，オクタデシル，ノナデシル，エイコシル
など炭素数１〜20の直鎖もしくは分岐アルキル基、シク
ロペンチル，シクロヘキシル，シクロヘプチルなど炭素
数３〜10のシクロアルキル基、ビニル，アリルなど炭素
数２〜10のアルケニル基、ベンジルなど炭素数７〜20の
アラルキル基がある。またR2としては、上記アルキル
基、アルケニル基、アラルキル基の他アリール基から選
ばれ、アリール基は置換基を有していてもよく、置換基
としてはアルキル基，ビニル基，アシル基，ニトロ基，
シアノ基などが挙げられる。アリール基の具体例として
はベンゼン，トルエン，スチレン，キシレン，ステアリ
ルベンゼン，ニトロベンゼン，ジニトロベンゼン，シア
ノベンゼン，ジシアノベンゼン，アセチルベンゼン，ア
セチルニトロベンゼン，メチルベンゾエート，エチルベ
ンゾエート，メチルニトロベンゾエートなどの残基が挙
げられる。In the above formula (I) of the present invention, X is a group selected from —COOR 1 , —COR 2 and —CN, and R 1 is selected from an alkyl group, an alkenyl group and an aralkyl group, and specifically, Is a linear or branched alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, isooctyl, dodecyl, octadecyl, nonadecyl, and eicosyl, and 3 to 10 carbon atoms such as cyclopentyl, cyclohexyl, and cycloheptyl. Are cycloalkyl groups, alkenyl groups having 2 to 10 carbon atoms such as vinyl and allyl, and aralkyl groups having 7 to 20 carbon atoms such as benzyl. Further, R 2 is selected from the above alkyl group, alkenyl group, aralkyl group and aryl group, and the aryl group may have a substituent, and the substituent may be an alkyl group, a vinyl group, an acyl group, a nitro group. Basis,
And a cyano group. Specific examples of the aryl group include residues such as benzene, toluene, styrene, xylene, stearylbenzene, nitrobenzene, dinitrobenzene, cyanobenzene, dicyanobenzene, acetylbenzene, acetylnitrobenzene, methylbenzoate, ethylbenzoate and methylnitrobenzoate. To be
本発明の上記式（II）で表わされる化合物の具体例と
しては4,4′−ジニトロフェニル， 2,2′−ジニトロジフェニルが挙げられる。Specific examples of the compound represented by the above formula (II) of the present invention include 4,4'-dinitrophenyl and 2,2'-dinitrodiphenyl.
本発明のエレクトロクロミック表示材料を用いた表示
素子は、上記式（Ｉ）又は（II）の化合物を主剤として
電気化学的なセルを構築することによって得ることがで
きる。基本的エレクトロクロミック表示用電気化学的セ
ルは、透明電極とそれに対向した電極間にエレクトロク
ロミックな主剤を含んだ電解質層を挟み込んだ構造を持
つ。本発明の主剤化合物はこれを電解質の溶液、ペース
ト、固体あるいは半固体として用いることができる。溶
液として用いる場合の例としては、炭素プロピレン，ジ
メチルホルムアミド，アセトニトリル，ベンゾニトリル
などの溶剤に主剤を１〜100mmol/lの濃度で溶かし、こ
れに支持電解質を加えたものが用いられる。支持電解質
としては、アルカリ金属イオン，四級アンモニウムイオ
ンなどの陽イオンと、過塩素酸イオン，ホウフッ化イオ
ンなどの陰イオンからなる塩が用いられる。具体的に
は、過塩素酸リチウム，テトラブチルアンモニウムボロ
ンフルオライド，テトラブチルアンモニウムパークロレ
ート，テトラエチルアンモニウムパークロレートなどを
１〜100mmol/lの濃度になるように加えられる。ペース
ト状にして用いる場合には、上記溶剤溶液に高分子有機
化合物や無機化合物のコロイドなどを加えて用いる。A display device using the electrochromic display material of the present invention can be obtained by constructing an electrochemical cell using the compound of the above formula (I) or (II) as a main component. A basic electrochemical cell for electrochromic display has a structure in which an electrolyte layer containing an electrochromic main agent is sandwiched between a transparent electrode and an electrode facing the transparent electrode. The base compound of the present invention can be used as an electrolyte solution, paste, solid or semi-solid. As an example of the case of using as a solution, a solution obtained by dissolving the main agent in a solvent such as carbon propylene, dimethylformamide, acetonitrile and benzonitrile at a concentration of 1 to 100 mmol / l and adding a supporting electrolyte thereto is used. As the supporting electrolyte, a salt composed of cations such as alkali metal ions and quaternary ammonium ions and anions such as perchlorate ions and borofluoride ions is used. Specifically, lithium perchlorate, tetrabutylammonium boron fluoride, tetrabutylammonium perchlorate, tetraethylammonium perchlorate and the like are added so as to have a concentration of 1 to 100 mmol / l. When used in the form of a paste, a colloid of a high molecular weight organic compound or an inorganic compound is added to the solvent solution for use.
上記調製した溶液あるいはペーストを脱酸素下で透明
電極と対向電極との間に封入して電気化学的セルとすれ
ばエレクトロクロミック表示素子となる。すなわち、電
圧印加により透明電極上で上記主剤が還元されて着色パ
ターンを形成し、逆電圧を印加することにより酸化され
て消色又は変色する。このとき対向電極上で逆反応が生
じるので可逆的に酸化一還元される対向電極反応物質を
添加することが好ましい。このような反応物質としては
フェロセンや塩化第一鉄などの２価の鉄化合物などがあ
る。The prepared solution or paste is sealed under deoxidation between a transparent electrode and a counter electrode to form an electrochemical cell, which serves as an electrochromic display element. That is, by applying a voltage, the base material is reduced on the transparent electrode to form a colored pattern, and when a reverse voltage is applied, the base material is oxidized to be decolored or discolored. At this time, since a reverse reaction occurs on the counter electrode, it is preferable to add a counter electrode reactant that is reversibly oxidized and reduced. Examples of such reactants include divalent iron compounds such as ferrocene and ferrous chloride.
上記透明電極としては、ガラス基板あるいはポリマー
フィルム上に金属，金属酸化物あるいは導電性高分子化
合物を薄く被覆した透明性の電極が用いられる。上記金
属，金属酸化物としては、通常金，白金，銅，アルミニ
ウム，パラジウムなどの金属あるいはイリジウム，スズ
の酸化物が用いられる。また導電性高分子化合物として
は、ポリピロール，ポリチオフェン，ポリアニリンなど
が挙げられる。対向電極としては、上記透明電極と同じ
ものあるいは上記金属，金属酸化物あるいは導電性高分
子化合物単独で用いられる。As the transparent electrode, a transparent electrode in which a metal, a metal oxide or a conductive polymer compound is thinly coated on a glass substrate or a polymer film is used. As the metal or metal oxide, a metal such as gold, platinum, copper, aluminum or palladium, or an oxide of iridium or tin is usually used. Examples of the conductive polymer compound include polypyrrole, polythiophene, polyaniline and the like. As the counter electrode, the same electrode as the transparent electrode, or the metal, metal oxide, or conductive polymer compound alone is used.
主剤化合物を固体として用いる場合には、これに有機
高分子化合物及び支持電解質を混合して用いる。有機高
分子化合物としては、ポリエチレンオキサイド，ポリフ
ッ化ビニリデン，ポリアクリロニトリル，ポリプロピレ
ンオキサイド，ポリエピクロルヒドリン，エピクロルヒ
ドリン−エチレンオキサイド共重合体などが挙げられ
る。この場合、電極上に主剤を含む薄膜を形成させるこ
とが容易である。透明電極上に薄膜を形成させる方法と
してはキャスチング法，スピンコート法などがあり、膜
厚0.01mm以下の薄膜を形成させて用いられる。薄膜形成
後さらに架橋反応などにより不溶化させることもでき
る。さらに本発明の主剤化合物、即ち前記（Ｉ）式化合
物が重合性の置換基を有するものである場合、これを重
合して高分子化合物として用いることも可能である。例
えば、ビニル基，アリル基を有する化合物の場合、光重
合法などにより電極上でパターン形成しながら重合する
ことができる。When the main agent compound is used as a solid, it is mixed with an organic polymer compound and a supporting electrolyte. Examples of the organic polymer compound include polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, polypropylene oxide, polyepichlorohydrin, epichlorohydrin-ethylene oxide copolymer and the like. In this case, it is easy to form a thin film containing the main agent on the electrodes. As a method for forming a thin film on the transparent electrode, there are a casting method, a spin coating method and the like, and a thin film having a thickness of 0.01 mm or less is formed and used. After forming the thin film, it can be further insolubilized by a crosslinking reaction or the like. Furthermore, when the main compound of the present invention, that is, the compound of formula (I) has a polymerizable substituent, it can be polymerized and used as a polymer compound. For example, a compound having a vinyl group or an allyl group can be polymerized while forming a pattern on the electrode by a photopolymerization method or the like.
上記薄膜被覆した透明電極と対向電極間に、脱酸素
後、前記支持反応電解質を含む電解液や対向電極反応物
質を封入して電気化学的セルとする。対向電極上に前記
可逆的に酸化一還元される反応物質を薄膜として電極被
覆することもできる。上記電解液の代りに金属酸化物な
どの無機固体電解質あるいは高分子固体電解質を用いる
ことによって全固体型エレクトロクロミック表示素子を
構築することができる。Between the transparent electrode coated with the thin film and the counter electrode, after deoxidation, the electrolytic solution containing the supporting reaction electrolyte and the counter electrode reactant are sealed to form an electrochemical cell. It is also possible to coat the counter electrode with a thin film of the above-mentioned reaction substance that is reversibly oxidized or reduced. An all-solid-state electrochromic display device can be constructed by using an inorganic solid electrolyte such as a metal oxide or a polymer solid electrolyte instead of the electrolytic solution.
（実施例） 実施例１〜14 ホウフッ化テトラーｎ−ブチルアンモニウムを支持電
解質として用い、これを炭酸プロピレンに溶かして濃度
0.1mmol/lの電解液を調製した。これに表１の各主剤化
合物を濃度20mmol/lとなるように加え、窒素気流下でサ
イクリックボルタモグラムを測定した。(Examples) Examples 1 to 14 Tetra-n-butylammonium borofluoride was used as a supporting electrolyte, which was dissolved in propylene carbonate to obtain a concentration.
An electrolytic solution of 0.1 mmol / l was prepared. Each main compound shown in Table 1 was added to this so that the concentration was 20 mmol / l, and the cyclic voltammogram was measured under a nitrogen stream.
作用極及び対極は白金を用い、参照電極として飽和カ
ロメル電極（以下SCEと略称する）を用いた。得られた
サイクリックボルタモグラムはいずれも可逆な酸化還元
波を示し、酸化還元電位Ｅ1/2（V.S SCE）は表１のとお
りであった。Platinum was used as the working electrode and the counter electrode, and a saturated calomel electrode (hereinafter abbreviated as SCE) was used as the reference electrode. All the obtained cyclic voltammograms showed a reversible redox wave, and the redox potential E 1/2 (VS SCE) was as shown in Table 1.
また上記各主剤化合物を含む炭酸プロピレン電解液
を、二枚のインジウムースズ酸化物蒸着ガラス透明電極
により作製したセル（セル間隔0.05mm）に脱酸素下で封
入し、このセルに表１に示された各化合物の還元電圧を
印加し着色化させた。またこれに逆電圧を印加するか放
電させると消色又は変色した。この着色−消色（変色）
反応は可逆的であった。表１にこの色彩の変化を示し
た。Further, the propylene carbonate electrolyte containing each of the main ingredient compounds was encapsulated under deoxidation in a cell (cell spacing 0.05 mm) made of two indium oxide oxide glass-deposited glass transparent electrodes. A reducing voltage of each compound was applied to cause coloration. Further, when a reverse voltage was applied to this or it was discharged, it discolored or discolored. This coloring-discoloration (discoloration)
The reaction was reversible. Table 1 shows the change in color.
（発明の効果） 本発明のエレクトロクロミック表示材料は、電気化学
的な酸化還元反応により、青，赤，オレンジ，緑など多
彩で鮮明な表示が得られる。生成したラジカルアニオン
がニトロ基の強い電子吸引効果により安定化されるため
着色が非常に安定しており、この安定化により還元−酸
化のサイクルの可逆性が高くなり繰り返し使用が可能で
ある。 (Effects of the Invention) The electrochromic display material of the present invention can provide a variety of clear displays such as blue, red, orange, and green by an electrochemical redox reaction. Since the generated radical anion is stabilized by the strong electron-withdrawing effect of the nitro group, the coloring is very stable, and this stabilization makes the reversibility of the reduction-oxidation cycle high and allows repeated use.
Claims (1)
族ニトロ化合物を主剤とするエレクトロクロミック表示
材料。 （但し、（Ｉ）式において、Ｘは−COOR1,−COR2及び−
CNより選ばれた基を表わし、R1はアルキル基、アルケニ
ル基又はアラルキル基を表わし、R2はアルキル基、アル
ケニル基、アラルキル基又は置換基を有していてもよい
アリール基を表わす。ｎ又はｍは１〜２の整数である） 1. An electrochromic display material containing an aromatic nitro compound represented by the following formula (I) or (II) as a main component. (However, in the formula (I), X is -COOR 1 , -COR 2 and-
Represents a group selected from CN, R 1 represents an alkyl group, an alkenyl group or an aralkyl group, and R 2 represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group which may have a substituent. n or m is an integer of 1 to 2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63164653A JP2518673B2 (en) | 1988-06-30 | 1988-06-30 | Electrochromic display materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63164653A JP2518673B2 (en) | 1988-06-30 | 1988-06-30 | Electrochromic display materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0214283A JPH0214283A (en) | 1990-01-18 |
| JP2518673B2 true JP2518673B2 (en) | 1996-07-24 |
Family
ID=15797268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63164653A Expired - Lifetime JP2518673B2 (en) | 1988-06-30 | 1988-06-30 | Electrochromic display materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2518673B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6026824B2 (en) * | 2012-09-04 | 2016-11-16 | 紀本電子工業株式会社 | Method for producing radical anion of aromatic nitro compound |
-
1988
- 1988-06-30 JP JP63164653A patent/JP2518673B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0214283A (en) | 1990-01-18 |
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