JPH0432104A - New conductive high polymer and conductive material thereof - Google Patents
New conductive high polymer and conductive material thereofInfo
- Publication number
- JPH0432104A JPH0432104A JP2136269A JP13626990A JPH0432104A JP H0432104 A JPH0432104 A JP H0432104A JP 2136269 A JP2136269 A JP 2136269A JP 13626990 A JP13626990 A JP 13626990A JP H0432104 A JPH0432104 A JP H0432104A
- Authority
- JP
- Japan
- Prior art keywords
- conductive polymer
- compound
- polymer
- conductive
- high polymer
- 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.)
- Pending
Links
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- 239000004020 conductor Substances 0.000 title claims description 13
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000005267 main chain polymer Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 201000002674 obstructive nephropathy Diseases 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical compound N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- VNAUDIIOSMNXBA-UHFFFAOYSA-N pyrazolo[4,3-c]pyrazole Chemical compound N1=NC=C2N=NC=C21 VNAUDIIOSMNXBA-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- GZTPJDLYPMPRDF-UHFFFAOYSA-N pyrrolo[3,2-c]pyrazole Chemical compound N1=NC2=CC=NC2=C1 GZTPJDLYPMPRDF-UHFFFAOYSA-N 0.000 description 1
- MABBLQAEAFNAFU-UHFFFAOYSA-N pyrrolo[3,2-e]indazole Chemical compound C1=CC2=NC=CC2=C2C=NN=C21 MABBLQAEAFNAFU-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、プラスチックの帯電防止材料や、電気、電子
工業の分野において、電池、コンデンサ、電子デバイス
、エレクトロクロミック素子の電極或いは電解質材料又
は面状発熱体及び電磁遮蔽材料等の広範囲な導電性材料
として応用できるものである。Detailed Description of the Invention [Field of Industrial Application] The present invention is applicable to antistatic materials for plastics, and in the fields of electrical and electronic industries, such as electrodes or electrolyte materials or surfaces of batteries, capacitors, electronic devices, and electrochromic devices. It can be applied as a wide range of conductive materials such as shaped heating elements and electromagnetic shielding materials.
電子伝導性を有する有機高分子材料は、近年バッテリー
や種々の機能デバイスとしての応用が検討されている０
例えば、ポリアニリン、ポリチオフェン、ポリピロール
、ポリフェニレンビニレン、ポリフェニレンアセチレン
、ポリアセチレン等が有望で、***特許第３，２２３，
５４４号、同３，３１８，８５６号、同３，３１８．８
５７号、同３，３２５．８９２号、同３，３３８，９０
４号、同３，４２１，２９６号、特開昭５８１８７４３
２号、同５９−４３０６０号、同５９−１１２５８３号
、同５Ｂ−２０９８６４号、同５９−２０７９３３号、
同６０−１２０７２２号、同６０−６７５２７号、同６
２−２２５５１８号、同６２−５３３２８号、同６３−
１９９７２６号、同６０−２２３８１７号、同６１−８
３２２１号、同５９−３１５６５号等に記載されている
。これらの高分子は電子伝導性には優れているものの、
機械的強度に乏しいとか溶媒に溶けにくく成形加工性に
劣る等の欠点を有しており、電子伝導性に優れ、かつ成
形加工性に優れた電子伝導性高分子が望まれていた。Organic polymer materials with electronic conductivity have recently been considered for application as batteries and various functional devices.
For example, polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polyphenylene acetylene, polyacetylene, etc. are promising, and West German Patent No. 3,223,
No. 544, No. 3,318,856, No. 3,318.8
No. 57, No. 3,325.892, No. 3,338,90
No. 4, No. 3,421,296, JP 5818743
No. 2, No. 59-43060, No. 59-112583, No. 5B-209864, No. 59-207933,
No. 60-120722, No. 60-67527, No. 6
No. 2-225518, No. 62-53328, No. 63-
No. 199726, No. 60-223817, No. 61-8
No. 3221, No. 59-31565, etc. Although these polymers have excellent electronic conductivity,
It has drawbacks such as poor mechanical strength, poor solubility in solvents, and poor molding processability, so there has been a desire for an electronically conductive polymer with excellent electronic conductivity and molding processability.
導電性材料としては、これらの電子伝導性高分子と電解
質とをそれぞれ層として組み合わせたものが用いられる
が、デバイス或いはバッテリーとして十分機能するため
には、両者の界面において電子とイオンの交換を速やか
に行わせる必要がある。The conductive material used is a combination of these electronically conductive polymers and an electrolyte as layers, but in order to fully function as a device or battery, it is necessary to quickly exchange electrons and ions at the interface between the two. need to be done.
電解質としては、漏液がないこと、機械的強度が大きい
こと、積層材料のフレキシビリデイ−が大きいことなど
の点から高分子固体電解質が優れており、種々の報告が
されている。As an electrolyte, solid polymer electrolytes are superior in terms of no leakage, high mechanical strength, and high flexibility of laminated materials, and various reports have been made.
このような高分子固体電解質と電子伝導性高分子とを組
み合わせた導電性電子材料としては、ポリマー（ＰＯＬ
ＹＭＥＲ） ２２巻、１４５４〜１４５５頁（１９８１
年１１月）等にポリアセチレンと固体電解質を組み合わ
せた有機電池が提案されているが、この付加重合におい
て作製されたポリアセチレンのフィルムは酸化安定性が
悪く、また、高分子固体電解質との界面での接触が不十
分で良好な導電性が得られないとか、デバイス材料とし
て応答速度が遅いなどの問題があった。As a conductive electronic material that combines such a solid polymer electrolyte and an electronically conductive polymer, polymer (POL
YMER) Vol. 22, pp. 1454-1455 (1981
An organic battery combining polyacetylene and a solid electrolyte has been proposed (November 2013), but the polyacetylene film produced by this addition polymerization has poor oxidation stability, and also There were problems such as insufficient contact and poor conductivity, and slow response speed as a device material.
また特開昭６２−９８５７７号には電解重合した主鎖に
共役二重結合を有する高分子と高分子固体電解質を組み
合わせた積層体の導電性材料が記載されているが、電子
伝導性高分子と高分子固体電解質との界面での密着が不
十分で界面抵抗が大きく、良好な導電性が得られないと
か、機械的強度に乏しくなどの問題がしった。Furthermore, JP-A No. 62-98577 describes a laminate conductive material in which an electrolytically polymerized polymer having a conjugated double bond in its main chain and a solid polymer electrolyte are combined. Problems such as insufficient adhesion at the interface between the solid polymer electrolyte and the solid polymer electrolyte resulted in high interfacial resistance, inability to obtain good conductivity, and poor mechanical strength.
また、機械的強度と導電性の両立を目指した化合物とし
て、第３７回（１９８８年）高分子討論会２Ｈ０４にて
側鎖にカルバゾール基の繰り返し単位を有する化合物、
例えば、
＋ＣＨＣＨｔ −ＣＨＣＨｔ→Ｔ
が検討されているが、その導電率は１０−４〜１Ｏ−Ｓ
Ｓ／ａｌと不十分なものであった。In addition, as a compound aiming to achieve both mechanical strength and conductivity, a compound having a repeating unit of a carbazole group in the side chain,
For example, +CHCHt -CHCHt→T is being considered, but its conductivity is 10-4 to 1O-S
S/al was insufficient.
またポリアニリンあるいはポリへテロ環を電極材料とし
て用いた場合、酸化還元反応に伴ないアニオンがドープ
又は脱ドープされる。この際アニオンの拡散が律速にな
ることが竹原等により第５６回（１９８９年）！気化学
会３Ｇ２４７報告されている。Furthermore, when polyaniline or polyheterocycle is used as an electrode material, anions are doped or dedoped as a result of redox reactions. Takehara et al. 56th (1989) found that the diffusion of anions becomes rate-determining in this case! Reported by Japan Gas Chemistry Society 3G247.
アニオンの拡散を防止する方法としてはこの具体例が特
開昭６３−２１５７７２号にアニオン性化合物をドーピ
ング剤として用いる方法が開示されている。しかしこの
方法ではドーピングをくり返すに従かいアニオン性化合
物の拡散による濃度勾配が生じ、十分な改良手段とはな
り得なかった。A specific example of a method for preventing the diffusion of anions is disclosed in JP-A-63-215772, in which an anionic compound is used as a doping agent. However, with this method, as doping is repeated, a concentration gradient occurs due to diffusion of the anionic compound, and it could not be a sufficient means for improvement.
本発明の第１の目的は、電子伝導性に優れ、かつ機械的
強度、成形加工性に優れた電子伝導性高分子を提供する
ことにある。A first object of the present invention is to provide an electronically conductive polymer that has excellent electronic conductivity, mechanical strength, and moldability.
本発明の第２の目的は電子伝導性高分子の酸化還元反応
において、アニオンのドープ及び脱ドープ反応がすばや
く生じる電子伝導性高分子を提供することにある。A second object of the present invention is to provide an electron conductive polymer in which anion doping and dedoping reactions occur quickly in the redox reaction of the electron conductive polymer.
本発明の第３の目的は、高分子固体電解質と組み合わせ
たとき、接触界面での抵抗が少なく、電気伝導性に優れ
、かつデバイス材料として応答速度が速い電子伝導性高
分子と高分子固体電解質との積層体の導電性材料を提供
することにある。The third object of the present invention is to provide an electronically conductive polymer and solid polymer electrolyte that, when combined with a solid polymer electrolyte, has low resistance at the contact interface, excellent electrical conductivity, and has a fast response speed as a device material. The object of the present invention is to provide a conductive material for a laminate with a laminate.
本発明の第４の目的は電子伝導性高分子に高分子固体電
解質の機能を持たせ、実質的に電解質層を不要化した導
電性材料を提供することにある。A fourth object of the present invention is to provide an electrically conductive material in which an electronically conductive polymer has the function of a solid polymer electrolyte, thereby substantially eliminating the need for an electrolyte layer.
上記目的は、以下の電子伝導性高分子あるいはそれを用
いた導電性材料によって達成することができた。The above object could be achieved by the following electronically conductive polymer or conductive material using the same.
即ち、少なくとも１つの反応性基を有する電子伝導性高
分子を架橋せしめて得られる導電性高分子材料あるいは
それを用いた導電性材料によって達成することができた
。That is, this can be achieved using a conductive polymer material obtained by crosslinking an electron conductive polymer having at least one reactive group, or a conductive material using the same.
本発明の電子伝導性高分子について、更に詳しく説明す
る。The electron conductive polymer of the present invention will be explained in more detail.
少なくとも１つの反応性基を存する電子伝導性高分子は
架橋剤を介して架橋してイオン結合、共有結合を形成し
てもよいし、分子内あるいは分子間で架橋してイオン結
合、共有結合を形成してもよい。Electron conductive polymers containing at least one reactive group may be crosslinked via a crosslinking agent to form ionic or covalent bonds, or intramolecularly or intermolecularly crosslinked to form ionic or covalent bonds. may be formed.
上記反応性基は具体的には以下のものがあげられるが、
熱論本発明はこれに限定されるものではない。Specific examples of the above-mentioned reactive groups include the following:
Thermal theory The present invention is not limited to this.
アミノ基（例えば−Ｎｌ’ｌｔ、 ＮＨＣＪｓ、 ＮＨ
ＣＪＪＣＩ（３）エポキシ基（例えば−ＣＨ−ＣＴｏ、
Ｃ１（Ｃ−ｃＨｓ＞、＼０′０
しＬ
又はその前駆体（例えば−５Ｏ＊ＣＨ＝ＣＩＩｇ、５Ｏ
ｘＣＨｔＣＨｚＣｊ！、 Ｃ００ＣＨ−ＣＨｘ 、−
ＣＯＯＣ［ＩｇＧＨｚＣｊ！ 。Amino groups (e.g. -Nl'lt, NHCJs, NH
CJJCI(3) Epoxy group (e.g. -CH-CTo,
C1 (C-cHs>, \0'0 ShiL or its precursor (e.g. -5O*CH=CIIg, 5O
xCHtCHzCj! , C00CH-CHx, -
COOC[IgGHzCj! .
ＣＯＯＣＪＣＮ）−アジリジン基（例えば−ｃｏぐ
−ＣＨ！（）、カルボン酸基又はその塩、スルフィン酸
又はその塩、イソシアネート基（例えば−ＮＧＯ、−Ｎ
Ｃ５） 、アジド基（例えば−Ｎ３、−ＣＯＮｓ） 。COOCJCN)-aziridine group (e.g. -cog
-CH! ( ), carboxylic acid group or its salt, sulfinic acid or its salt, isocyanate group (e.g. -NGO, -N
C5), azido groups (e.g. -N3, -CONs).
電子伝導性高分子を架橋する架橋剤は任意のものでよい
が、具体例としては上記反応性基を同じでも異なってい
てもよいが、２つ以上分子内に有する化合物及びペプチ
ド縮合剤があげられる。２つ以上反応性基を有する架橋
剤は高分子化合物でも良い。Any crosslinking agent may be used to crosslink the electron-conductive polymer, but specific examples include compounds having two or more of the above reactive groups in the molecule, which may be the same or different, and peptide condensing agents. It will be done. The crosslinking agent having two or more reactive groups may be a polymer compound.
上記反応性基を有する電子伝導性高分子は具体的にはア
ニリン化合物又はへテロ環化合物の少なくとも１つを繰
り返し単位とする電子伝導性化合物である。またこれら
のアニリン化合物又はヘテロ環化合物の電子導電性部位
を繰り返し単位として側鎖に有するエチレン性繰り返し
単位を有するビニルポリマーでも良い。Specifically, the electron conductive polymer having the above-mentioned reactive group is an electron conductive compound having at least one repeating unit of an aniline compound or a heterocyclic compound. Furthermore, a vinyl polymer having an ethylenic repeating unit having an electronically conductive moiety of these aniline compounds or heterocyclic compounds as a repeating unit in a side chain may also be used.
上記へテロ環の好ましい具体例としては、ゾール、オキ
サゾール（イソを含む）、チアゾール（イソを含む）、
ピリジン、ジアジン、ンゾトリアゾール、ベンゾオキサ
ゾール、ベンゾチアゾール、プリン、キノリン、イソキ
ノリン、ベンゾジアジン、フルオレン、
フェノキサジン、ピラゾロトリアゾール、ピラゾロジア
ゾール、ピラゾロアゾール、ベンゾピラゾロアゾールが
挙げられる。Preferred specific examples of the above heterocycle include zole, oxazole (including iso), thiazole (including iso),
Examples include pyridine, diazine, nzotriazole, benzoxazole, benzothiazole, purine, quinoline, isoquinoline, benzodiazine, fluorene, phenoxazine, pyrazolotriazole, pyrazolodiazole, pyrazoloazole, and benzopyrazoloazole.
Ｚは０、Ｓ又は−Ｎ−Ｒ３（Ｒ３は上記と同義）を表わ
す。Z represents 0, S or -N-R3 (R3 has the same meaning as above).
電子伝導性高分子の繰り返し単位の好ましい例はアニリ
ン化合物、ピロール化合物、チオフェン化合物、フラン
化合物である。Preferred examples of the repeating unit of the electron conductive polymer are aniline compounds, pyrrole compounds, thiophene compounds, and furan compounds.
上記アニリン化合物及びペテロ環化合物はそれぞれ任意
の置換基で置換されているものでもよい。The above-mentioned aniline compound and peterocyclic compound may each be substituted with an arbitrary substituent.
この置換基の例としては、ハロゲン原子、ニトロ基、シ
アノ基、アルキル基、アルコキシ、−ＮＢＣＯＲ４、−
ＮＨ３Ｏ□Ｒ’ −３ＯＲ’、−ｓｏｚｇ’ルキル基
で更に置換されていてもよい）、水酸基や加水分解して
水酸基を形成する基が挙げられる。Examples of this substituent include halogen atom, nitro group, cyano group, alkyl group, alkoxy, -NBCOR4, -
NH3O□R'-3OR',-sozg' (which may be further substituted with an alkyl group), a hydroxyl group, and a group that forms a hydroxyl group by hydrolysis.
Ｒ４は、アルキル基、フェニル基、又はアラルキル基を
表わす Ｒ５及びＲ＆は同じでも異なっていてもよく、
水素原子、アルキル基、フェニル基、又はアラルキル基
を表わす。また、２つの置換基が縮環して炭素環又は複
素環を形成してもよい。R4 represents an alkyl group, a phenyl group, or an aralkyl group; R5 and R& may be the same or different;
Represents a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group. Furthermore, two substituents may be condensed to form a carbocycle or a heterocycle.
さらに上記の化合物の置換基中のアルキル基、アルコキ
シ基、フェニル基、アラルキル基の置換されてもよい置
換基の例としては、水酸基、ニトロ基、炭素数１〜４の
アルコキシ基、炭素数１〜４のアルキル基、 ＮＨ３（
ｈＲ’ ＮＨＣＲ’−ハロゲン原子、シアノ基、
アミノ基（アルキル基で更に置換されていてもよい）等
が挙げられる。Furthermore, examples of substituents that may be substituted for alkyl groups, alkoxy groups, phenyl groups, and aralkyl groups in the substituents of the above compounds include hydroxyl groups, nitro groups, alkoxy groups having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. ~4 alkyl group, NH3(
hR'NHCR'-halogen atom, cyano group,
Examples include an amino group (which may be further substituted with an alkyl group), and the like.
Ｒ７とＲ４と同義である。Ｒｓ及びＲ９は同じであって
も異なっていてもよ（、Ｒ％ と同義である。It has the same meaning as R7 and R4. Rs and R9 may be the same or different (synonymous with R%).
アニリン化合物及びペテロ環化合物の具体例を以下に示
すが、もちろんこれらに限定されるものではない。Specific examples of the aniline compound and the petrocyclic compound are shown below, but the invention is of course not limited to these.
ＣＨ。CH.
ＨｓＣＣＣＨＩ Ｈｓ Ｈ 好ましくは、 アニリン、 チオフェン、 ビロール 及び置換基中にオキシアルキレン基を有するアニリン、 チオフエンピオールである。HsCCCHI Hs H Preferably, Aniline, thiophene, Birol and aniline having an oxyalkylene group in the substituent, It is thiophenepiol.
反応性基を有するアニリン化合物及びペテロ環化合物の
具体例を以下に示すが、
勿論これらに限
定されるものではない。Specific examples of aniline compounds and peterocyclic compounds having reactive groups are shown below, but of course they are not limited to these.
（ＪｌｉＣＨＪＨｚ
ＣＨｚＣＨｚＮＣＯ
υ
ＣＨｚＧＨｚＣｊＩ
ＣＨｚＣｌｈＯＨ
電子伝導性高分子を架橋する架橋剤の具体例を以下に示
すが、勿論これらに限定されるものではない。(JliCHJHz CHzCHzNCO υ CHzGHzCjI CHzClhOH Specific examples of the crosslinking agent that crosslinks the electron conductive polymer are shown below, but the present invention is not limited thereto.
Ｋ−Ｉ Ｋ−２
に−１１
（ｃｙｃｌｏ−ＣＪ＋＋Ｎ ＋ｒＣ
Φ
（Ｃ２Ｉ（ｓ）Ｊｌ”Ｃ−Ｎ（ＣｚＨｓ）ｚ・Ｃｌｅ
Ｃｌ
に−５
に−６
に−７
ＣＨｚ＝ＣＨ３ＯｚＣＨｚＳＯｚＣＨ＝Ｃｔ（ｚＣｌ１
ＣＨｚＣＨ＊Ｃｌｌ
ＣＨｚ−ＣＨ５Ｏ□ＣＨｚＣＨｚＣＯＮＨＣＨｚＣＨＪ
ＨＣＯＣＨｚ−ＣＨｔＳＯ□ＣＨ−ＣＩよ
ｃｔ＋ｔ ＝ ＣｊｌＳＯｚＣｔｌｚＣ［ｌ （ＯＨ）
ＣＨｚＳＯｔＣＨ＝ Ｃｕｔ以下に反応性基を有する
電子伝導性高分子の具体例を示すが、本発明においてこ
れに限定されるものではない。K-I K-2 to -11 (cyclo-CJ++N +rC Φ (C2I(s)Jl''C-N(CzHs)z・Cle Cl to -5 to -6 to -7 CHz=CH3OzCHzSOzCH=Ct(zCl1
CHzCH*Cll CHz-CH5O□CHzCHzCONHCHzCHJ
HCOCHz-CHtSO□CH-CIyoct+t = CjlSOzCtlzC[l (OH)
Specific examples of electron conductive polymers having reactive groups below CHzSOtCH=Cut are shown below, but the present invention is not limited thereto.
ＣＩ（ｚｃＨｚＯＨ
ＣＨｚＧＨｚＭＨｚ
Ｐ−１５
Ｐ−１９
しｆｌ富しυＵ１１
反応性基を有するアニリン化合物及びヘテロ環化合物は
電子伝導性高分子中で任意の比率で有してよい。好まし
くは０．１〜１０重量％である。CI (zcHzOH CHzGHzMHz P-15 P-19 Fl-enriched υU11 The aniline compound and the heterocyclic compound having a reactive group may be present in an arbitrary ratio in the electron-conducting polymer. Preferably 0.1 to 10 Weight%.
架橋剤は電子伝導性高分子にたいし任意の比率で有して
よい、好ましくは０〜ｌＯ重量％である。The crosslinking agent may be present in any proportion to the electron conductive polymer, preferably 0 to 10% by weight.
本発明の電子伝導性高分子を得る合成法は、般に用いら
れている合成法、例えば、公知の重合法、化学的酸化重
合法、電解酸化重合法、Ｃ−Ｃカップリング反応等を用
いることができる。The synthesis method for obtaining the electron conductive polymer of the present invention uses commonly used synthesis methods, such as known polymerization methods, chemical oxidation polymerization methods, electrolytic oxidation polymerization methods, C-C coupling reactions, etc. be able to.
例えば、電子伝導性部位を側鎖に有するように主鎖の重
合を行った後、化学的酸化重合法、電解酸化重合法、Ｃ
−Ｃカップリング反応等の電子伝導性部位の重合を行っ
て本発明の化合物を得ることができる。この際、異なっ
た電子伝導性部位で重合してもよい、また、電子伝導性
部位の重合を化学的酸化重合法、電解酸化重合法、Ｃ−
Ｃカップリング反応等で行った後で主鎖ポリマーに高分
子反応で電子伝導性部位の繰り返し単位を有する側鎖を
導入してもよい、また、化学的酸化重合法、電解酸化重
合法、Ｃ−Ｃカップリング反応等で電子伝導性部位の重
合を行ったブレモノマーで、主鎖の重合を行ってもよい
。この際、電子伝導性部位の重合を行ったプレモノマー
の単独重合でもよいし、他の任意のモノマーとの共重合
でもよい。For example, after polymerizing the main chain so that the side chain has an electron conductive site, chemical oxidative polymerization, electrolytic oxidative polymerization, C
The compounds of the present invention can be obtained by polymerization of the electron conductive site, such as a -C coupling reaction. At this time, polymerization may be performed at different electron conductive sites, and the polymerization at the electron conductive sites may be carried out by chemical oxidation polymerization, electrolytic oxidation polymerization, C-
A side chain having a repeating unit of an electron-conducting moiety may be introduced into the main chain polymer by a polymer reaction after the C coupling reaction. The main chain may be polymerized using a bremonomer whose electron conductive site has been polymerized by -C coupling reaction or the like. At this time, the premonomer that has undergone polymerization of the electron conductive site may be homopolymerized, or it may be copolymerized with any other monomer.
上記の化学的酸化重合法は、水又は任意の有機溶媒中（
含水しても良い）に単量体化合物を溶解または分散し、
６０°Ｃ〜−２０°Ｃ（好ましくは２０°Ｃ〜０℃）で
触媒（酸化側）溶液を徐々に滴下して行われる。この場
合、適当な分散剤や界面活性剤を用いることでポリマー
の水分散液を得ることもでき、成形加工性に優れており
好ましい。The above chemical oxidative polymerization method can be carried out in water or any organic solvent (
Dissolving or dispersing the monomer compound in the solution (which may contain water),
This is carried out by gradually dropping the catalyst (oxidation side) solution at 60°C to -20°C (preferably 20°C to 0°C). In this case, an aqueous dispersion of the polymer can be obtained by using an appropriate dispersant or surfactant, which is preferable because it has excellent moldability.
上記の電解酸化重合法は、水又は導電性の塩を溶解でき
る有機溶媒中、単量体化合物と導電性塩を溶解又は分散
し、正、負極を浸漬して８０℃〜−２０℃（好ましくは
３０℃〜０°Ｃ）で定電圧法、定電位法又は定電流法に
て行われる。好ましくは定電圧法である。The above electrolytic oxidation polymerization method involves dissolving or dispersing the monomer compound and the conductive salt in water or an organic solvent capable of dissolving the conductive salt, and dipping the positive and negative electrodes at 80°C to -20°C (preferably (30° C. to 0° C.) by a constant voltage method, a constant potential method, or a constant current method. Preferably, a constant voltage method is used.
上記のＣ−Ｃカップリング反応は、主にチオフェン系化
合物に適用され（アニリン系化合物やピロール系化合物
に通用してもよい）、ハロゲン化チオフェン系化合物に
グリニヤール反応剤又は金属ハロゲン化物等を作用させ
得ることができる。The above C-C coupling reaction is mainly applied to thiophene compounds (it may also be applied to aniline compounds and pyrrole compounds), and a Grignard reagent or metal halide is applied to a halogenated thiophene compound. can be obtained.
具体的には、シンセシスメタルズ（Ｓｙｎ ｔｈｅｓ
ｉｓＭｅｔａｌｓ） ２６巻、２６７頁（１９８８年）
等に記載されている。また、本発明の化合物は任意のド
ーパント（例えば、ハロゲン又は前記重合時に用いる塩
）でドーピングされていてもよい。Specifically, Synthesis Metals
isMetals) Volume 26, Page 267 (1988)
It is described in etc. Further, the compound of the present invention may be doped with an arbitrary dopant (for example, a halogen or a salt used during the polymerization).
化学的酸化重合法で用いることのできる触媒としては、
例えば、塩化第二鉄、塩化第二銅などの塩化物、硫酸第
二鉄、硫酸第二銅などの硫酸塩、二酸化鉛、二酸化マン
ガンなどの金属酸化物、過硫酸カリウム、過硫酸アンモ
ニウム、過硫酸水素などの過酸化物、ベンゾキノンなど
のキノン類、沃素、臭素などのハロゲン、フェリシアン
化カリウムなどが挙げられる。これらの具体例は、特開
昭６３−２１３５１８号、同６３−１９３９２６号、同
６２−１１６６６５号、同６２−１０４８３２号、同６
３−２１５７１７号、同６３−６９８２３号、同６３−
１０１４１５号、同６０−５８４３０号等にも記載され
ている。触媒の量は、単量体の化合物の特性と使用され
る触媒により変化するが、触媒／単量体の化合物のモル
比率で０゜０１から１０の範囲で使用することができる
。Catalysts that can be used in chemical oxidative polymerization methods include:
For example, chlorides such as ferric chloride and cupric chloride, sulfates such as ferric sulfate and cupric sulfate, metal oxides such as lead dioxide and manganese dioxide, potassium persulfate, ammonium persulfate, and persulfate. Examples include peroxides such as hydrogen, quinones such as benzoquinone, halogens such as iodine and bromine, and potassium ferricyanide. Specific examples of these are JP-A Nos. 63-213518, 63-193926, 62-116665, 62-104832, and 6
No. 3-215717, No. 63-69823, No. 63-
It is also described in No. 101415, No. 60-58430, etc. The amount of catalyst varies depending on the characteristics of the monomer compound and the catalyst used, but can be used in a molar ratio of catalyst/monomer compound in the range of 0.01 to 10.
電解酸化重合法で用いることのできる電極材料としては
、金属電極（例えば、Ａｕ、Ｐｔ、Ｎｉ、Ｃｕ、Ｓｎ、
Ｚｕ、Ａｇ、Ｒｕ、ステンレス等）、炭素電極（例えば
、グラッシーカーボン）、金属酸化物含有電極（例えば
、Ｓｎｏｗ、ｒｎｏｓ）等が挙げられる。また、別に参
照電極を用いると好ましい。Electrode materials that can be used in the electrolytic oxidation polymerization method include metal electrodes (for example, Au, Pt, Ni, Cu, Sn,
(Zu, Ag, Ru, stainless steel, etc.), carbon electrodes (eg, glassy carbon), metal oxide-containing electrodes (eg, Snow, rnos), and the like. Further, it is preferable to use a separate reference electrode.
化学的酸化重合法及び電解酸化重合法で使用することき
できる溶媒としては、有機溶媒（例えばアセトニトリル
、ジメチル硫酸、Ｎ、Ｎ−ジメチルアセトアミド、Ｎ、
Ｎ−ジメチルホルムアミド、ジメチルスルホキサイド、
スルフオラン、ホルムアミド、ジメトキシエタン、プロ
ピレンカーボネート、ジオキサン、メタノール、エタノ
ール、γ−プチルラクトン、ニトロベンゼン、テトラヒ
ドロフラン、ニトロメタン等が挙げられる）、水あるい
は両者の混合物を挙げることができる。Examples of solvents that can be used in the chemical oxidative polymerization method and the electrolytic oxidative polymerization method include organic solvents (such as acetonitrile, dimethyl sulfate, N,N-dimethylacetamide, N,
N-dimethylformamide, dimethyl sulfoxide,
sulfuran, formamide, dimethoxyethane, propylene carbonate, dioxane, methanol, ethanol, γ-butyllactone, nitrobenzene, tetrahydrofuran, nitromethane, etc.), water, or a mixture of both.
また、化学的酸化重合や電解酸化重合の際に、導電性化
合物を加えて重合してもよい。導電性化合物としては、
無機酸（例えば、ＨＣｆ、Ｈ，Ｓｏ、 、ＨＣｌ、Ｏ，
、ＨＢＦ４ ） 、有機酸（例えば、トルエンスルホン
酸、トリフルオロメチルスルホン酸、ポリスチレンスル
ホン酸のようなスルホン酸、ギ酸、酢酸、ポリアクリル
酸のようなカルボン＃）、有機塩基（例えば、ピリジン
、トリジン、トリエタノールアミン）、導電性の塩（例
えば、アルカリ金属カチオン（Ｌ ｉ” 、Ｎａ”Ｋ１
等）、ＮＯ” 、Ｎｏ、”カチオン、オニウムカチオン
ＣＥｔ４ Ｎ” 、Ｂｕ４ Ｎ” 、Ｂｕｓ ｐ”等）
と負イオン（ＢＦ４−１ＡＳＦ４
ＡｓＦ−−１ＳｂＦｓ−１ＳｂＣＮｉ−１ＰＦ６ＣｆＯ
ｎ −、ＡｌＦｍ −、ＡｌＦｍ −、Ｎ１Ｆａ”Ｚ
ｒ Ｆａ”−、Ｔ ｉ Ｆａ”−、Ｂ＋ｅＣｊ！＋ｏ”
−２ＨＳ Ｏ４ＳＯ４”−、Ｃ１１−、Ｂｒ−、Ｆ−、
Ｉ−）からなる塩、スルホン酸アニオン（ｃ ｎ ｓ
ｃ ｈ ｎ ａ Ｓ□ ｓ −ＣａＨｓＳＯｓ −、Ｃ
ＦｓＳＯ３−、ポリスチレンスルホン酸等）を含む塩、
ＨＣＯＯＬｒ、ポリアクリル酸ソーダのようなカルボン
酸アニオンを含む塩、ＦｅＣｌ３のような塩化物、ピリ
ジン塩酸塩のような有機アミン塩）が挙げられる。Furthermore, a conductive compound may be added during chemical oxidative polymerization or electrolytic oxidative polymerization. As a conductive compound,
Inorganic acids (e.g. HCf, H, So, , HCl, O,
, HBF4), organic acids (e.g. sulfonic acids such as toluenesulfonic acid, trifluoromethylsulfonic acid, polystyrene sulfonic acid, carboxylates such as formic acid, acetic acid, polyacrylic acid), organic bases (e.g. pyridine, tolidine , triethanolamine), conductive salts (e.g. alkali metal cations (L i” , Na”K1
etc.), NO”, No, “cation, onium cation CEt4 N”, Bu4 N”, Bus p”, etc.)
and negative ions (BF4-1ASF4 AsF--1SbFs-1SbCNi-1PF6CfO
n −, AlFm −, AlFm −, N1Fa”Z
r Fa"-, T i Fa"-, B+eCj! +o”
-2HS O4SO4"-, C11-, Br-, F-,
I-), a salt consisting of a sulfonic acid anion (c n s
c h n a S s −CaHsSOs −, C
FsSO3-, polystyrene sulfonic acid, etc.),
HCOOLr, salts containing carboxylic acid anions such as sodium polyacrylate, chlorides such as FeCl3, and organic amine salts such as pyridine hydrochloride).
分散剤としては、カチオン、アニオン、ノニオン、ベタ
インのそれぞれポリマー及び界面活性剤（乳化剤）を用
いることができる。これらの具体例としては、ポリビニ
ルアルコール、ポリエチレンオキサイド、ポリプロピレ
ンオキサイド、ヒドロキシエチルセルロース、カルボキ
シメチルセルロース、メチルセルロース、デキストリン
、ポリビニルピロリドン、ポリスチレンスルホン酸ナト
リウム、ポリアクリル酸、ポリアクリルアミド、ゼラチ
ン、コラーゲン、３級又は４級アンモニウム塩サイトを
有するポリマー、オキソニウム塩サイトを有するポリマ
ー、スルホニウム塩サイトを存するポリマー、４級アン
モニウム塩サイトを有する長鎖アルキル化合物、高級脂
肪酸アルカリ塩（例えば、Ｃ＋ ＋ＨｚｚＣＯＯＮａ）
、アルキル硫酸塩（例えば、ラウリル硫酸ソーダ）、ア
ルキルスルホン酸塩（例えば、ラウリルスルホン酸ソー
ダ）、アルキルアリールスルホン酸塩（例えば、ドデシ
ルベンゼンスルホン酸ソーダ）、スルホコハク酸エステ
ル塩、高級アミンハロゲン酸塩、ハロゲン化アルキルピ
リジニウム（例えば、塩化ドデシルピリジニウム）、第
四級アンモニウム塩（例えば、塩化トリメチルアンモニ
ウム）、ポリエチレングリコールアルキルエーテル、ポ
リエチレングリコール脂肪酸エステル、ソルビタン脂肪
酸エステル、脂肪酸モノグリセリド、アミノ酸等が挙げ
られる。As the dispersant, cationic, anionic, nonionic, betaine polymers and surfactants (emulsifiers) can be used. Specific examples of these include polyvinyl alcohol, polyethylene oxide, polypropylene oxide, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, dextrin, polyvinylpyrrolidone, sodium polystyrene sulfonate, polyacrylic acid, polyacrylamide, gelatin, collagen, tertiary or quaternary Polymers having ammonium salt sites, polymers having oxonium salt sites, polymers having sulfonium salt sites, long chain alkyl compounds having quaternary ammonium salt sites, higher fatty acid alkali salts (e.g. C+ +HzCOONa)
, alkyl sulfates (e.g. sodium lauryl sulfate), alkyl sulfonates (e.g. sodium lauryl sulfonate), alkylaryl sulfonates (e.g. sodium dodecylbenzenesulfonate), sulfosuccinate ester salts, higher amine halogenates , halogenated alkylpyridinium (e.g. dodecylpyridinium chloride), quaternary ammonium salts (e.g. trimethylammonium chloride), polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, fatty acid monoglyceride, amino acids and the like.
分散剤を使用する際には、モノマーに対して１〜３００
重量％、好ましくは５〜２００重量％で使用する。界面
活性剤を使用する際には、モノマーに対して０．０１〜
５０重量％、好ましくは０゜１〜２０重量％で使用する
。When using a dispersant, the amount is 1 to 300% based on the monomer.
It is used in weight percent, preferably from 5 to 200 weight percent. When using a surfactant, the amount of surfactant is 0.01~
It is used in an amount of 50% by weight, preferably 0.1 to 20% by weight.
これらの水分散液は、透析や限外濾過等の処理をして用
いてもよい。These aqueous dispersions may be used after being subjected to treatments such as dialysis and ultrafiltration.
これらの水分散液には、前記の導電性化合物を添加して
もよいし、ポリ酢酸ビニルポリマーなどの高分子化合物
をブレンドしてもよい。The above-mentioned conductive compound may be added to these aqueous dispersions, or a polymer compound such as polyvinyl acetate polymer may be blended therein.
本発明の電子伝導性高分子は、高分子固体電解質と積層
してポリマー電池のような導電性材料として使用できる
。本発明の電子伝導性高分子は複数層を形成してもよく
、また公知の電子伝導性高分子とで複数層を形成しても
よい。また、周期律表Ｉａ族又はＩ［ａ族の金属イオン
の塩との積層を更に有してもよい、しかし、高分子固体
電解質と本発明の電子伝導性高分子が直接接触している
ものが好ましい。The electron conductive polymer of the present invention can be laminated with a solid polymer electrolyte and used as a conductive material such as a polymer battery. The electron conductive polymer of the present invention may form a plurality of layers, or may form a plurality of layers with a known electron conductive polymer. Further, it may further have a lamination with a salt of a metal ion of Group Ia or Group I[a of the periodic table, but the solid polymer electrolyte and the electron conductive polymer of the present invention are in direct contact with each other. is preferred.
本発明の電子伝導性高分子との積層導電性材料を得る高
分子固体電解質は、カチオンポリマーアニオンポリマー
、ポリアクリロニトリル、ポリアルキレンオキシドポリ
マー（ＰＥＯｌＰＰＯやＰＥＯを含むケイ素化合物及び
フォスフアゼン等）、ポリビニルアルコール等と塩を組
み合わせたものが挙げられる。これらの具体例は、特開
昭６１２５６５７３号、同６１−１２４００１号、同６
２−２０２６３号、同６２−１３９２６６号、同６３−
２４１０６６号、同６３−２４１０２６号、同６３−１
３５４７７号、同６３−１４２０６１号、同６３−１３
０６１３号、同６０−２．３９７４号、同６３−１３６
４０９号、同６３−１９３９５４号、同６３−１８６７
６６号、同６３−２０５３６４号、米国特許筒４，８２
２．’７０１号、マクロモレキューシス２１壱６４８真
に記載されている。Polymer solid electrolytes for obtaining the laminated conductive material with the electron conductive polymer of the present invention include cation polymer anion polymer, polyacrylonitrile, polyalkylene oxide polymer (silicon compound including PEOlPPO and PEO, phosphazene, etc.), polyvinyl alcohol, etc. and salt. Specific examples of these are JP-A-61256573, JP-A No. 61-124001, JP-A No. 6
No. 2-20263, No. 62-139266, No. 63-
No. 241066, No. 63-241026, No. 63-1
No. 35477, No. 63-142061, No. 63-13
No. 0613, No. 60-2.3974, No. 63-136
No. 409, No. 63-193954, No. 63-1867
No. 66, No. 63-205364, U.S. Patent No. 4,82
2. '701, Macromolecusis 21, No. 648.
高分子固体電解質を構成する塩としては、前記の化学的
酸化重合法や電解重合法における重合時に用いられる導
電性の塩を挙げることができる。Examples of the salt constituting the solid polymer electrolyte include conductive salts used during polymerization in the chemical oxidation polymerization method and electrolytic polymerization method described above.
好ましくは、周期律表１ａ又はＩＩａ族の金属イオンの
塩であり、更に好ましくは、Ｌｉ塩である。Preferably, it is a salt of a metal ion of group Ia or IIa of the periodic table, and more preferably a Li salt.
積層体導電性材料は、本発明の化学的酸化重合法で、得
られた電子伝導性高分子が粉末又は塊状であるときには
、圧縮成形で加工したフィルムを高分子固体電解質膜に
圧着せしめて作成することができる。また得られた電子
伝導性高分子が水分散物であるときには、ローラーコー
ト、スピンコード、ギーサーコート、デイツプコート、
スプレーによるコート、押出形成等の公知の塗布方法、
及び公知の乾燥方法を用いることができる。When the electronically conductive polymer obtained by the chemical oxidation polymerization method of the present invention is in the form of powder or lumps, the laminate conductive material is produced by pressing a film processed by compression molding onto a solid polymer electrolyte membrane. can do. Moreover, when the obtained electron conductive polymer is an aqueous dispersion, roller coating, spin cord, Giesser coating, dip coating,
Known application methods such as spray coating, extrusion, etc.
And known drying methods can be used.
また、電解酸化重合法で電極上に形成した電子伝導性高
分子膜や、上記手段等でフィルム化された電子伝導性高
分子膜上に、溶解又は溶融された高分子固体電解質を塗
布等で密着積層してもよい。In addition, it is also possible to apply a dissolved or melted polymer solid electrolyte onto an electron conductive polymer film formed on an electrode by electrolytic oxidation polymerization method or an electron conductive polymer film formed into a film by the above method. They may be laminated in close contact.
また本発明の化合物は高分子固体電解質の機能を持たす
ことで実質的に電解層を不要化することも可能である。Further, the compound of the present invention can substantially eliminate the need for an electrolytic layer by having the function of a solid polymer electrolyte.
すなわち正極（本発明の化合物）と負極との間にセパレ
ーターを用いるだけでバッテリーとしての機能を発現す
ることができる。That is, the battery function can be achieved simply by using a separator between the positive electrode (the compound of the present invention) and the negative electrode.
該積層材料はそれぞれのコンポーネントを独自に作成し
た後積層させても良いし、またセパレーター上に正極材
料を塗布あるいは圧着した後負極を積層させてもよい。The laminated material may be formed by individually creating each component and then laminating them, or by applying or pressing a positive electrode material onto a separator and then laminating the negative electrode.
セパレーターは負極材料のイオン（例えばＬｉ“）が拡
散しゃすい様任意の有機溶媒（例えばプロピレンカーボ
ネート、エチレンカーボネート、γブチルラクトン、ジ
メトキシエタン、メチルテトラヒドロフラン等）を含浸
させておくのが好ましい。The separator is preferably impregnated with any organic solvent (eg, propylene carbonate, ethylene carbonate, γ-butyl lactone, dimethoxyethane, methyltetrahydrofuran, etc.) so that ions (eg, Li'') of the negative electrode material can diffuse.
上記有機溶媒にはリチウム塩を入れても良い。A lithium salt may be added to the organic solvent.
セパレーター材料としては、ポリオレフィン、ポリエス
テル、塩化ビニル、フッ素樹脂、ポリアミド、ポリスル
ホン、セルロース、ポリウレタン等任意の材料を用いる
ことができる。またこれらにプラズマ処理、グロー処理
、放射線処理、プラズマ重合、プラズマ開始重合、放射
線重合、放射線開始重合等の処理をしても良い。As the separator material, any material such as polyolefin, polyester, vinyl chloride, fluororesin, polyamide, polysulfone, cellulose, polyurethane, etc. can be used. Further, these may be subjected to treatments such as plasma treatment, glow treatment, radiation treatment, plasma polymerization, plasma initiated polymerization, radiation polymerization, and radiation initiated polymerization.
また本発明の電子伝導性高分子電池として用いる場合、
正極活物質として、マンガン、モリブデン、バナジウム
、チタン、クロム、ニオブなどの酸化物、硫化物やセレ
ン化物、活性炭（特開昭６０−１６７．２８０号記Ｉり
、炭素繊維（特開昭６１−１０，８８２号記ｉｆ）、ポ
リアニリン、アミノ基置換芳香族ポリマー、複素環ポリ
マー、ポリアセン、ポリイン化合物などを併用すること
ができる。なかでも、活性炭、１− Ｍ ｎ Ｏｚ
（特開昭６２−１０８，４５５号、同６２−１０８，４
５７号に記１ａ）、γ−β−ＭｎＯｔとＬｉｔＭｎ０３
の混合物（米国特許４，７５８，４８４号）、アモルフ
ァス状ＶｇＯｓ（特開昭６１−２００．６６７号）、Ｖ
ｉＯ＋３、Ｍｏｂ、（特開昭６１−６４．０８３号）、
ＴＩＳ！（特開昭６２−２２２゜５７８号）、ポリアニ
リン（特開昭６０−６５０３１号、同６０−１４９．６
２８号、同６１−２８１．１２８号、同６１−２５８，
８３１号、同６２−９０．８７８号、同６２−９３，８
６８号、同６２−１１９，２３１号、同６２−１８１゜
３３４号、同６３−４６，２２３号）、ポリピロール（
***特許３，３０７，９５４Ａ１号、同３３１８．８５
７号、同３，３３８，９０４号、同３．４２０，８５４
Ａ１号、同３，６０９，１３７Ａ１号、特開昭６０−１
５２，６９０号、同６２−７２，７１７号、同６２−９
３，８６３号、同６２−１４３，３７３号）、ポリアセ
ン、ポリアセチレン（特開昭５７−１２１．１６８号、
同５７−１２３，６５９号、同５８−４０，７８１号、
同５８−４０，７８１号、同６０−１２４゜３７０号、
同６０−１２７．６６９号、同６１−２８５．６７８号
）、ポリフェニレンが特に有効である。Furthermore, when used as the electron conductive polymer battery of the present invention,
As positive electrode active materials, oxides such as manganese, molybdenum, vanadium, titanium, chromium, and niobium, sulfides and selenides, activated carbon (JP-A No. 60-167.280 I), carbon fiber (JP-A No. 61-1986), No. 10,882 if), polyaniline, amino group-substituted aromatic polymer, heterocyclic polymer, polyacene, polyyne compound, etc. Among them, activated carbon, 1-M n Oz
(Unexamined Japanese Patent Publication No. 62-108,455, No. 62-108,4
No. 57, 1a), γ-β-MnOt and LitMn03
(U.S. Pat. No. 4,758,484), amorphous VgOs (JP 61-200,667), V
iO+3, Mob, (Unexamined Japanese Patent Publication No. 61-64.083),
TIS! (JP 62-222゜578), polyaniline (JP 60-65031, JP 60-149.6)
No. 28, No. 61-281.128, No. 61-258,
No. 831, No. 62-90.878, No. 62-93, 8
No. 68, No. 62-119,231, No. 62-181゜334, No. 63-46,223), polypyrrole (
West German Patent No. 3,307,954A1, 3318.85
No. 7, No. 3,338,904, No. 3,420,854
No. A1, No. 3,609,137A1, JP-A-60-1
No. 52,690, No. 62-72,717, No. 62-9
3,863, 62-143,373), polyacene, polyacetylene (JP-A-57-121.168,
No. 57-123,659, No. 58-40,781,
No. 58-40,781, No. 60-124゜370,
60-127.669, 61-285.678) and polyphenylene are particularly effective.
電極活物質には、通常、カーボン、銀（特開昭６３−１
４８，５５４号）あるいはポリフェニレン誘導体（特開
昭５９−２０，９７１号）などの導電性材料やテフロン
などの接合剤を含ませることができる。Electrode active materials are usually carbon, silver (Japanese Unexamined Patent Publication No. 63-1
48,554) or polyphenylene derivatives (Japanese Unexamined Patent Publication No. 59-20,971), or a bonding agent such as Teflon.
負極活物質としては、金属リチウム、ポリアセン、ポリ
アセチレン、ポリフェニレンの他、リチウム合金として
、アルミニウムやマグネシウムなどの合金（特開昭５７
−６５，６７０号、同５７−９８，９７７号）、水銀合
金（特開昭５８−１１１．２６５号）、Ｐｔなどの合金
（特開昭６０−７９．６７０号）、５ｎ−Ｎｉ合金（特
開昭６０−８６，７５９号）やウッド合金（特開昭６０
−１６７．２７９号）、導電性ポリマーとの合金（特開
昭６０−２６２，３５１号Ｌ Ｐｄ−Ｃｄ−Ｂ１合金（
特開昭６１−２９，０６９号）、Ｇａ−Ｉｎ合金（特開
昭６１−６６．３６８号）、Ｐｂ−Ｍｇなどの合金（特
開昭６１−６６．３７０号）、Ｚｎなどの合金（特開昭
６１−６８，８６４号）、Ａｉ、−Ａｇなどの合金（特
開昭６１−７４．２５８号）、Ｃｄ−３ｎなどの合金（
特開昭６１−９１，８６４号）、ＡＩ！、−Ｎｉなどの
合金（特開昭６２−１１９．８６５号、同６２−１１９
．８６６号）、Ａｊｌ！−Ｍｎなどの合金（米国特許４
，８２０，５９９号）などが用いられている。なかでも
、リチウム金属あるいはそのＡｆｆｉ合金を用いること
が有効である。As negative electrode active materials, in addition to metallic lithium, polyacene, polyacetylene, and polyphenylene, lithium alloys include alloys such as aluminum and magnesium (Japanese Patent Laid-Open No. 57
-65,670, 57-98,977), mercury alloy (Japanese Patent Application Laid-open No. 58-111.265), alloys such as Pt (Japanese Patent Application Laid-open No. 60-79.670), 5n-Ni alloy ( JP-A-60-86,759) and wood alloys (JP-A-60-86,759) and wood alloys (JP-A-60-86,759)
-167.279), alloy with conductive polymer (JP-A-60-262,351 L Pd-Cd-B1 alloy (
JP-A-61-29,069), Ga-In alloy (JP-A-61-66,368), alloys such as Pb-Mg (JP-A-61-66,370), and alloys such as Zn (JP-A-61-66,370). JP-A-61-68,864), alloys such as Ai, -Ag (JP-A-61-74,258), alloys such as Cd-3n (JP-A-61-74,258),
JP-A No. 61-91,864), AI! , -Ni and other alloys (JP-A No. 62-119.865, No. 62-119)
．． No. 866), Ajl! - Alloys such as Mn (U.S. Patent 4)
, 820, 599), etc. are used. Among these, it is effective to use lithium metal or its Affi alloy.
以下に本発明の化合物及びその作成例を示すが本発明の
化合物はこれらに限定されるものではない。Compounds of the present invention and preparation examples thereof are shown below, but the compounds of the present invention are not limited thereto.
〔作成例１；本発明の化合物１の作成〕Ｐ−１（ｍ／ｎ
−９５１５モル比）、Ｌｏｇを１００ｍに分散したのち
テフロン板上にバーコード塗布した。さらにに−１３の
水溶液をＰ−１／に一１３＝９５１５ （重量比）とな
るようオーバーコートした。窒素気流下６０℃で１Ｂ１
いたのちテフロン板上より引き剥がして、目的とする本
発明の化合物１の薄膜を得た。[Preparation Example 1; Preparation of compound 1 of the present invention] P-1 (m/n
-9515 molar ratio) and Log were dispersed over 100 m and then coated with a bar code on a Teflon plate. Furthermore, P-1/ was overcoated with an aqueous solution of -13 at a weight ratio of -13=9515. 1B1 at 60℃ under nitrogen flow
After that, it was peeled off from the Teflon plate to obtain the desired thin film of Compound 1 of the present invention.
〔作成例２；本発明の化合物２の作成〕Ｐ−１８（ｍ／
ｐ／ｎ／ｑ＝７５１５／１０／１０モル比）の１０％Ｎ
、 Ｎ−ジメチルホルムアミド溶液をテフロン板上にバ
ーコード塗布した後に−９の水溶液をＰ−１／に一９＝
９５１５ （重量比）となるようオーバーコートした。[Preparation Example 2; Preparation of compound 2 of the present invention] P-18 (m/
p/n/q=7515/10/10 molar ratio) 10%N
, After coating the N-dimethylformamide solution with a bar code on a Teflon plate, the aqueous solution of -9 was applied to P-1/.
It was overcoated to a weight ratio of 9515.
窒素気流下６０°Ｃで１Ｂ１いたのちテフロン板上より
引き剥がして、目的とする本発明の化合物１の薄膜を得
た。After heating 1B1 at 60°C under a nitrogen stream, it was peeled off from the Teflon plate to obtain the desired thin film of Compound 1 of the present invention.
〔作成例３；本発明の化合物３〜２０の作成〕作成例１
及び２に準じて、本発明の化合物３〜２０を作成した。[Preparation example 3; Preparation of compounds 3 to 20 of the present invention] Preparation example 1
Compounds 3 to 20 of the present invention were prepared according to Example 1 and 2.
（表１）
〔作成例４；比較化合物Ａ−Ｃの作成〕ポリアニリン、
ポリピロール及びポリチオフェンを架橋剤なしで作成例
１に準じて薄膜の作成を試みたものの脆くてテフロン板
より引き剥がし可能な薄膜は得られなかった。(Table 1) [Preparation Example 4; Preparation of Comparative Compounds A-C] Polyaniline,
Although an attempt was made to prepare a thin film of polypyrrole and polythiophene according to Preparation Example 1 without a crosslinking agent, a thin film that could be peeled off from the Teflon plate was not obtained because it was brittle.
そこでポリアニリン、ポリピロール及びポリチオフェン
の粉体を圧力をかけ形成加工することにより、それぞれ
厚み０．２閣のプレートを得た。Therefore, by pressurizing and forming powders of polyaniline, polypyrrole, and polythiophene, plates each having a thickness of 0.2 mm were obtained.
これをそれぞれ比較化合物Ａ、Ｂ、Ｃとした。These were designated as comparative compounds A, B, and C, respectively.
以下、実施例により本発明を更に詳細に説明するが、本
発明はこれらに限定されるものではない。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
里蓋斂皇度盪定
本発明の化合物１．２．７．８．１０．１２．１５．２
０の薄膜及び比較化合物Ａ−Ｃのプレートをドーピング
したのちＡ ｐｒｏｂｅ法で測定した電気伝導度を表２
に示した。Compounds of the present invention 1.2.7.8.10.12.15.2
Table 2 shows the electrical conductivity measured by the A probe method after doping the thin film of No. 0 and the plate of comparative compounds A-C.
It was shown to.
ｍ度±ス上
上記サンプルをそのまま１閣径のサファイア針を用い耐
引掻テストを行い、フィルムが破壊し傷あとが残った時
に針にかけた荷重を求め、引掻強度とし、表２に示した
。A scratch resistance test was performed on the above sample using a sapphire needle with a diameter of 1 mm, and when the film was destroyed and a scar remained, the load applied to the needle was determined, and the scratch strength was determined as shown in Table 2. .
・の パ
得たサンプルを下記で示す高分子固体電解質のキャスト
フィルム（厚さ２００μ程度）を積層させ、ステンレス
板ではさみ積層材料を作成した。・The obtained sample was laminated with a polymer solid electrolyte cast film (approximately 200μ thick) shown below, and sandwiched between stainless steel plates to create a laminated material.
この積層材料のそれぞれの導電率（Ｃｏｌｅ−Ｃｏｌｅ
プロット法）を測定した結果を表２に示した。The conductivity of each of this laminated material (Cole-Cole
Table 2 shows the results of the measurements (plot method).
（高分子固体電解質フィルム）
ベンジルメタクリレート０．９ｇ、）リメチロールプロ
パントリメタクリレート０．１ｇをプロピレンカーボネ
ート３ｇに溶解し、これにアゾビスイソブチロニトリル
０．１ｇを添加して均一溶液とした。この溶液をテフロ
ン板上にキャストし１２５℃で１時間加熱した。得られ
た薄膜をＬｉＢＦ。(Polymer Solid Electrolyte Film) 0.9 g of benzyl methacrylate and 0.1 g of rimethylolpropane trimethacrylate were dissolved in 3 g of propylene carbonate, and 0.1 g of azobisisobutyronitrile was added thereto to form a homogeneous solution. This solution was cast on a Teflon plate and heated at 125°C for 1 hour. The obtained thin film was coated with LiBF.
のプロピレンカーボネート／ジメトキシエタン溶液（Ｌ
ｉＢＦｎ ； １． ４モル、プロピレンカーボネー
ト；５００ｍ、ジメトキシエタン；５００ｍ）に１時間
浸漬した。この浸漬操作を計３回繰り返し高分子固体電
解質フィルムを得た。propylene carbonate/dimethoxyethane solution (L
iBFn; 1. 4 mol, propylene carbonate; 500 m, dimethoxyethane; 500 m) for 1 hour. This dipping operation was repeated three times in total to obtain a polymer solid electrolyte film.
（Ｃｏｌｅ−Ｃｏｌｅプロット法で得た導電率は２Ｘ１
０−”５７ｃｍであった。）
゛ −ス
得た積層材料にリチウムシートを圧着したものをステン
レス缶に入れ、口を絶縁性の合成ゴムによって封じ、圧
縮成形して第１図のような電池を作成した。この電池を
２次電池として連続充放電テスト（電流密度１．１ｍＡ
／ｄ、充放電深度３゜５〜２．ＯＶ）を行ないｌサイク
ル目及び５ｏサイクル目の放電容量を２０℃で測定し表
２に示した。(The conductivity obtained by Cole-Cole plot method is 2X1
0-"57cm) ゛ -The obtained laminated material was crimped with a lithium sheet, then placed in a stainless steel can, the mouth of which was sealed with insulating synthetic rubber, and compression molded to form a battery as shown in Figure 1. This battery was used as a secondary battery for continuous charging and discharging tests (current density 1.1mA).
/d, charge/discharge depth 3°5~2. OV), and the discharge capacity at the 1st cycle and the 50th cycle was measured at 20°C and is shown in Table 2.
一ス
得た積層材料にリチウムシートを圧着したものを用いて
、図２に示す単３型電池を作成した。この電池を２次電
池として連続充放電テスト（電流密度１．１ｍＡ／ｃｊ
、充放電深度３．５〜２．ＯＶ）を行ない１サイクル目
及び５０サイクル目の放電容量を２０℃で測定し表２に
示した。A AA-sized battery shown in FIG. 2 was created using the obtained laminated material with a lithium sheet crimped onto it. Continuous charge/discharge test using this battery as a secondary battery (current density 1.1 mA/cj
, charge/discharge depth 3.5-2. OV), and the discharge capacities at the 1st and 50th cycles were measured at 20°C and are shown in Table 2.
表１の本発明の化合物１．２．２０と比較化合物Ａの比
較、本発明の化合物１１と比較化合物Ｂ、及び本発明の
化合物１３と比較化合物Ｃの比較より本発明の化合物が
積層材料の導電性、放電容量、充放電サイクル特性のい
ずれの性質も損なうことなしに機械的強度が著しく向上
していることが明らかになった。Comparisons between Compound 1.2.20 of the present invention and Comparative Compound A, Compound 11 of the present invention and Comparative Compound B, and Compound 13 of the present invention and Comparative Compound C in Table 1 show that the compound of the present invention is suitable for laminated materials. It was revealed that the mechanical strength was significantly improved without impairing any properties such as conductivity, discharge capacity, and charge/discharge cycle characteristics.
さらに本発明の化合物８．９．１６は比較化合物Ａと比
較して、機械的強度、積層材料の導電性、放電容量、充
放電サイクル特性のいずれの性質も優れていることが明
らかになった。Furthermore, Compound 8.9.16 of the present invention was found to be superior to Comparative Compound A in terms of mechanical strength, conductivity of the laminated material, discharge capacity, and charge/discharge cycle characteristics. .
第１図は実施例中の連続充放電テスト１で作成した電池
構成を示す。
第２図は実施例中の連続充放電テスト２で作成した電池
構成を示す。FIG. 1 shows a battery configuration prepared in continuous charge/discharge test 1 in the example. FIG. 2 shows a battery configuration prepared in continuous charge/discharge test 2 in the example.
Claims (7)
分子を架橋せしめて得られる導電性高分子材料。(1) A conductive polymer material obtained by crosslinking an electron conductive polymer having at least one reactive group.
は／及び水に可溶であるところの請求項（１）記載の導
電性高分子材料。(2) The conductive polymer material according to claim (1), wherein the electron conductive polymer having a reactive group is soluble in an organic solvent and/or water.
は／及び水に分散されているところの請求項（１）記載
の導電性高分子材料。(3) The conductive polymer material according to claim (1), wherein the electron conductive polymer having a reactive group is dispersed in an organic solvent and/or water.
キレン基又は／及びアニオン性基を有するところの請求
項（１）記載の導電性高分子材料。(4) The conductive polymer material according to claim (1), wherein the electron conductive polymer having a reactive group has an oxyalkylene group and/or an anionic group.
合物又はヘテロ環化合物の少なくとも１つからなる電子
伝導性部位を繰り返し単位として側鎖に有するエチレン
系化合物の少なくとも１つを繰り返し単位として有する
重合体であるところの請求項（１）記載の導電性高分子
材料。(5) The electron-conductive polymer having a reactive group has as a repeating unit at least one ethylene-based compound having an electron-conducting moiety made of at least one of an aniline compound or a heterocyclic compound in its side chain as a repeating unit. The conductive polymer material according to claim 1, which is a polymer.
体電解質との積層体よりなる導電性材料。(6) A conductive material comprising a laminate of the conductive polymer material according to claim (1) and a solid polymer electrolyte.
ターとの積層体よりなる導電性材料。(7) A conductive material comprising a laminate of the conductive polymer material according to claim (1) and a separator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2136269A JPH0432104A (en) | 1990-05-25 | 1990-05-25 | New conductive high polymer and conductive material thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2136269A JPH0432104A (en) | 1990-05-25 | 1990-05-25 | New conductive high polymer and conductive material thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0432104A true JPH0432104A (en) | 1992-02-04 |
Family
ID=15171244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2136269A Pending JPH0432104A (en) | 1990-05-25 | 1990-05-25 | New conductive high polymer and conductive material thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0432104A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995000882A1 (en) * | 1993-06-22 | 1995-01-05 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Soluble, conductive copolymer, the preparation and use thereof |
| WO1997021228A1 (en) * | 1995-12-02 | 1997-06-12 | Bicc Public Limited Company | Electrically conducting polymers and their manufacture |
| WO2006095549A1 (en) * | 2005-03-04 | 2006-09-14 | Honda Motor Co., Ltd. | Polymer actuator |
| US8986488B2 (en) | 2010-07-28 | 2015-03-24 | Kabushiki Kaisha Toshiba | Pattern formation method and polymer alloy base material |
| US20150289589A1 (en) * | 2012-10-24 | 2015-10-15 | Asics Corporation | Upper Provided With Sponge Member in Heel Part |
| JP2017160449A (en) * | 2011-03-28 | 2017-09-14 | ヒタチ ケミカル リサーチ センター インコーポレイテッド | Network conjugated polymer of improved solubility |
-
1990
- 1990-05-25 JP JP2136269A patent/JPH0432104A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995000882A1 (en) * | 1993-06-22 | 1995-01-05 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Soluble, conductive copolymer, the preparation and use thereof |
| NL9301085A (en) * | 1993-06-22 | 1995-01-16 | Tno | Soluble conductive copolymer, its preparation and application. |
| WO1997021228A1 (en) * | 1995-12-02 | 1997-06-12 | Bicc Public Limited Company | Electrically conducting polymers and their manufacture |
| WO2006095549A1 (en) * | 2005-03-04 | 2006-09-14 | Honda Motor Co., Ltd. | Polymer actuator |
| US8986488B2 (en) | 2010-07-28 | 2015-03-24 | Kabushiki Kaisha Toshiba | Pattern formation method and polymer alloy base material |
| JP2017160449A (en) * | 2011-03-28 | 2017-09-14 | ヒタチ ケミカル リサーチ センター インコーポレイテッド | Network conjugated polymer of improved solubility |
| US20150289589A1 (en) * | 2012-10-24 | 2015-10-15 | Asics Corporation | Upper Provided With Sponge Member in Heel Part |
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