JP2003277500A - Electrically conductive polyaniline solution and method of producing the same - Google Patents
Electrically conductive polyaniline solution and method of producing the sameInfo
- Publication number
- JP2003277500A JP2003277500A JP2002079270A JP2002079270A JP2003277500A JP 2003277500 A JP2003277500 A JP 2003277500A JP 2002079270 A JP2002079270 A JP 2002079270A JP 2002079270 A JP2002079270 A JP 2002079270A JP 2003277500 A JP2003277500 A JP 2003277500A
- Authority
- JP
- Japan
- Prior art keywords
- solution
- polyaniline
- surfactant
- conductive polyaniline
- polyaniline solution
- 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
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title description 3
- 239000004094 surface-active agent Substances 0.000 claims abstract description 42
- -1 alkylene ether Chemical class 0.000 claims abstract description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 48
- 239000002904 solvent Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 125000002270 phosphoric acid ester group Chemical group 0.000 claims 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract description 99
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 63
- 239000003960 organic solvent Substances 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000008346 aqueous phase Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 239000003849 aromatic solvent Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000003014 phosphoric acid esters Chemical group 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 150000001448 anilines Chemical class 0.000 description 3
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- LFINSDKRYHNMRB-UHFFFAOYSA-N diazanium;oxido sulfate Chemical compound [NH4+].[NH4+].[O-]OS([O-])(=O)=O LFINSDKRYHNMRB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- PPOCFSJSVCAFQQ-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical compound C1CC2(C)C(=O)CC1C2(C)C.C1CC2(C)C(=O)CC1C2(C)C PPOCFSJSVCAFQQ-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910006127 SO3X Inorganic materials 0.000 description 1
- 101150051106 SWEET11 gene Proteins 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MIOPJNTWMNEORI-UHFFFAOYSA-N camphorsulfonic acid Chemical compound C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、導電性ポリアニリ
ン溶液およびその製法に関するものであり、詳しくは、
電気、電子、材料等の諸分野において、高分子表面の金
属めっきや導電性化および各種絶縁材料の導電性化に特
に有用な、導電性ポリアニリン溶液およびその製法に関
するものである。TECHNICAL FIELD The present invention relates to a conductive polyaniline solution and a method for producing the same.
The present invention relates to a conductive polyaniline solution and a method for producing the same, which are particularly useful for metal plating of a polymer surface and for conductivity and conductivity of various insulating materials in various fields such as electricity, electrons and materials.
【０００２】[0002]
【従来の技術】ポリアニリン、ポリフェニレン、ポリチ
オフェン、ポリピロール等の芳香族系の導電性高分子
は、空気中における安定性に優れ、また合成も容易であ
ることから、その活用が注目されている。これら導電性
高分子の中でも、ポリアニリンは、空気中における安定
性に特に優れ、また安価な材料であるため、二次電池の
正極材料として実用化されている。2. Description of the Related Art Aromatic conductive polymers such as polyaniline, polyphenylene, polythiophene, and polypyrrole have been attracting attention because of their excellent stability in air and easy synthesis. Among these conductive polymers, polyaniline has been particularly put into practical use as a positive electrode material of a secondary battery because it has excellent stability in air and is an inexpensive material.
【０００３】しかし、従来、上記ポリアニリン等の芳香
族系導電性高分子は、どの溶媒にも不溶、不融であっ
て、成形性に劣るため、その応用分野は限られていた。
このため、溶解性の良好な導電性高分子の実現が求めら
れていた。最近になって、ドデシルベンゼンスルホン酸
（ＤＢＳＡ）もしくはカンファー（しょうのう）スルホ
ン酸を、ドーパントとして取り込んだポリアニリンにお
いて、それぞれのスルホン酸と錯体を形成したポリアニ
リンが、クロロホルムのような有機溶剤に可溶であるこ
とが報告された。However, conventionally, the above-mentioned aromatic conductive polymers such as polyaniline are insoluble or infusible in any solvent and are inferior in moldability, so that their application fields have been limited.
Therefore, it has been required to realize a conductive polymer having good solubility. Recently, in polyaniline in which dodecylbenzene sulfonic acid (DBSA) or camphor (camphor) sulfonic acid is incorporated as a dopant, polyaniline complexed with each sulfonic acid is compatible with organic solvents such as chloroform. It was reported to be molten.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記の
ようなドデシルベンゼンスルホン酸もしくはカンファー
（しょうのう）スルホン酸を、ドーパントとして取り込
んだポリアニリンは、クロロホルムのような有機溶剤に
は可溶であるが、水に可溶でないため、水溶液として用
いることができないという難点があった。However, polyaniline incorporating the above dodecylbenzenesulfonic acid or camphor sulphonic acid as a dopant is soluble in an organic solvent such as chloroform. However, since it is not soluble in water, it cannot be used as an aqueous solution.
【０００５】そこで、本発明者は、界面活性剤を持った
アニリンを重合してなるポリアニリンが、水や有機溶剤
に可溶であることを突き止め、このポリアニリンについ
て特許出願を行った（特開平６−２７９５８４号）が、
その後、さらに研究開発を続けた結果、上記ポリアニリ
ンは、メチルエチルケトン（ＭＥＫ）のようなケトン系
溶剤や、トルエンのような芳香族系溶剤への分散（溶
解）性がやや劣り、均一溶液になりにくいということを
突き止めた。Therefore, the present inventor found out that polyaniline obtained by polymerizing aniline having a surfactant is soluble in water and an organic solvent, and filed a patent application for this polyaniline (Japanese Patent Laid-Open Publication No. 6-58242). -279584),
After that, as a result of further research and development, the polyaniline is slightly inferior in dispersibility (solubility) in a ketone solvent such as methyl ethyl ketone (MEK) or an aromatic solvent such as toluene, and is unlikely to be a uniform solution. I found out that.
【０００６】本発明は、このような事情に鑑みなされた
もので、水に可溶で、しかもメチルエチルケトン（ＭＥ
Ｋ），トルエン等の汎用の有機溶剤にも可溶で、導電性
にも優れた、導電性ポリアニリン溶液およびその製法の
提供をその目的とする。The present invention has been made in view of the above circumstances, and it is soluble in water and is methyl ethyl ketone (ME).
It is an object of the present invention to provide a conductive polyaniline solution which is soluble in general-purpose organic solvents such as K) and toluene and has excellent conductivity, and a method for producing the same.
【０００７】[0007]
【課題を解決するための手段】上記の目的を達成するた
め、本発明は、界面活性剤構造を有する導電性ポリアニ
リンの溶液であって、上記界面活性剤構造を形成するた
めに用いられる界面活性剤が、分子構造中に、アルキレ
ンエーテルの繰り返し構造を有するものである導電性ポ
リアニリン溶液を第１の要旨とする。To achieve the above object, the present invention provides a solution of a conductive polyaniline having a surfactant structure, which is used for forming the above surfactant structure. The first gist is a conductive polyaniline solution in which the agent has a repeating structure of alkylene ether in the molecular structure.
【０００８】また、上記導電性ポリアニリン溶液の製法
であって、上記界面活性剤構造を有する導電性ポリアニ
リンを水溶液で合成した後、ケトン系溶剤または芳香族
系溶剤に転相する導電性ポリアニリン溶液の製法を第２
の要旨とする。In the method for producing the electroconductive polyaniline solution, the electroconductive polyaniline solution is prepared by synthesizing the electroconductive polyaniline having the above-mentioned surfactant structure in an aqueous solution and then inverting the phase into a ketone solvent or an aromatic solvent. Second production method
The summary of
【０００９】すなわち、本発明者らは、水に可溶で、し
かもメチルエチルケトン（ＭＥＫ），トルエン等の汎用
の有機溶剤にも可溶で、導電性にも優れた、導電性ポリ
アニリン溶液を得るべく、鋭意研究を重ねた。その結
果、分子構造中にアルキレンエーテルの繰り返し構造を
有する特定の界面活性剤を用いると、この界面活性剤構
造を有するポリアニリンが、水に可溶で、しかもメチル
エチルケトン（ＭＥＫ）のようなケトン系溶剤やトルエ
ンのような芳香族系溶剤等の汎用の有機溶剤にも可溶で
あり、導電性にも優れていることを見いだし、本発明に
到達した。[0009] That is, the present inventors have aimed to obtain a conductive polyaniline solution which is soluble in water, soluble in general-purpose organic solvents such as methyl ethyl ketone (MEK) and toluene, and excellent in conductivity. , Repeated intensive research. As a result, when a specific surfactant having a repeating structure of alkylene ether in the molecular structure is used, the polyaniline having this surfactant structure is soluble in water and is a ketone solvent such as methyl ethyl ketone (MEK). The inventors have found that they are soluble in general-purpose organic solvents such as aromatic solvents such as toluene and toluene, and have excellent conductivity, and have reached the present invention.
【００１０】[0010]
【発明の実施の形態】つぎに、本発明の実施の形態につ
いて説明する。BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described.
【００１１】本発明の導電性ポリアニリン溶液は、界面
活性剤構造を有する導電性ポリアニリンの溶液である。
そして、本発明では、上記界面活性剤構造を形成するた
めの界面活性剤として、分子構造中に、アルキレンエー
テルの繰り返し構造を有するものを使用することが最大
の特徴である。The conductive polyaniline solution of the present invention is a conductive polyaniline solution having a surfactant structure.
In the present invention, the greatest feature is that a surfactant having a repeating structure of alkylene ether in the molecular structure is used as the surfactant for forming the surfactant structure.
【００１２】上記界面活性剤構造を有する導電性ポリア
ニリンは、例えば、上記特定の界面活性剤の存在下に、
水相、有機相もしくは水相と有機相の混合相において、
アニリンまたはアニリン誘導体を化学酸化剤によって酸
化重合するか、もしくは水相、有機相もしくは水相と有
機相の混合相において、上記特定の界面活性剤と、アニ
リンまたはアニリン誘導体とを反応させて両親媒性構造
のアニリンモノマーを得た後、化学酸化剤によって酸化
重合することにより作製することができる。The conductive polyaniline having the above surfactant structure can be prepared, for example, in the presence of the above specific surfactant,
In an aqueous phase, an organic phase or a mixed phase of an aqueous phase and an organic phase,
Oxidative polymerization of aniline or an aniline derivative with a chemical oxidant, or reaction of the above-mentioned specific surfactant with aniline or an aniline derivative in an aqueous phase, an organic phase, or a mixed phase of an aqueous phase and an organic phase to produce an amphiphilic After obtaining an aniline monomer having a polar structure, it can be produced by oxidative polymerization with a chemical oxidant.
【００１３】また、上記界面活性剤構造を有する導電性
ポリアニリンは、アニリンまたはアニリン誘導体と、上
記特定の界面活性剤とを反応させて塩を合成した後、化
学酸化剤によって酸化重合するか、もしくは電解酸化重
合を行うことにより、上記特定の界面活性剤をドーピン
グ現象により取り込んだ導電性ポリアニリンを作製する
こともできる。The conductive polyaniline having the above surfactant structure is prepared by reacting aniline or an aniline derivative with the above specific surfactant to synthesize a salt, and then oxidatively polymerized by a chemical oxidant, or By conducting electrolytic oxidation polymerization, it is also possible to produce a conductive polyaniline incorporating the above-mentioned specific surfactant by a doping phenomenon.
【００１４】さらに、上記界面活性剤構造を有する導電
性ポリアニリンは、上記特定の界面活性剤を、硝酸と塩
酸によってニトロ化し、還元した後、化学酸化剤によっ
て酸化重合することにより、上記特定の界面活性剤をド
ーピング現象により取り込んだ導電性ポリアニリンを作
製することもできる。Further, the conductive polyaniline having the above-mentioned surfactant structure is obtained by nitrating the above-mentioned particular surfactant with nitric acid and hydrochloric acid, reducing the same, and then oxidatively polymerizing it with a chemical oxidant to give the above-mentioned particular interface. It is also possible to produce a conductive polyaniline incorporating an activator by a doping phenomenon.
【００１５】上記特定の界面活性剤としては、分子構造
中に、アルキレンエーテルの繰り返し構造を有するもの
を用いる必要がある。上記アルキレンエーテルの繰り返
し構造としては、特に限定はないが、例えば、下記の一
般式（１）で表されるアルキレンエーテルの繰り返し構
造があげられる。As the above-mentioned specific surfactant, it is necessary to use one having a repeating structure of alkylene ether in the molecular structure. The repeating structure of the alkylene ether is not particularly limited, and examples thereof include the repeating structure of the alkylene ether represented by the following general formula (1).
【００１６】[0016]
【化１】 [Chemical 1]
【００１７】上記一般式（１）において、繰り返し数ｍ
は２〜３０の範囲内が好ましく、特に好ましくはｍ＝６
〜１０の範囲内である。すなわち、繰り返し数ｍが２未
満であると、アルキレン鎖の親油性が小さすぎるため、
メチルエチルケトンやトルエン等の汎用の有機溶剤に対
する溶解性の向上効果が小さく、逆に繰り返し数ｍが３
０を超えると、アルキレン鎖が長鎖になりドーピングの
効力が下がり、導電性が劣る傾向がみられるからであ
る。In the above general formula (1), the number of repetitions m
Is preferably in the range of 2 to 30, and particularly preferably m = 6.
Within the range of 10 to 10. That is, when the repeating number m is less than 2, the lipophilicity of the alkylene chain is too small,
The effect of improving solubility in general-purpose organic solvents such as methyl ethyl ketone and toluene is small, and conversely, the number of repetitions m is 3
This is because if it exceeds 0, the alkylene chain becomes a long chain, the effect of doping decreases, and the conductivity tends to deteriorate.
【００１８】また、上記一般式（１）において、ｎは１
〜５の範囲内が好ましく、特に好ましくはｎ＝２〜３の
範囲内である。In the above general formula (1), n is 1
It is preferably in the range of -5, and particularly preferably in the range of n = 2-3.
【００１９】上記特定の界面活性剤は、分子構造中に、
アルキレンエーテルの繰り返し構造とともに、スルホン
酸構造またはリン酸エステル構造を有するものが好まし
い。このように、スルホン酸構造またはリン酸エステル
構造を有するものであると、これらがポリアニリンのド
ーパントとしての役割を果たし、導電性がさらに良好と
なるとともに、メチルエチルケトン（ＭＥＫ）のような
ケトン系の有機溶剤、もしくはトルエンのような芳香族
系の有機溶剤に対する溶解性がより向上する。The above-mentioned specific surfactant has the following molecular structure:
Those having a sulfonic acid structure or a phosphoric acid ester structure together with a repeating structure of alkylene ether are preferable. As described above, when they have a sulfonic acid structure or a phosphoric acid ester structure, they function as a dopant of polyaniline, the conductivity is further improved, and a ketone-based organic compound such as methyl ethyl ketone (MEK) is used. The solubility in a solvent or an aromatic organic solvent such as toluene is further improved.
【００２０】本発明において、上記スルホン酸構造と
は、−ＳＯ3 Ｘ（Ｘ：Ｈ、Ｎａ、ＮＨ 4 等）で表される
基を有する構造部分を意味し、例えば、スルホン酸基、
スルホン酸ナトリウム、スルホン酸アンモニウム等があ
げられる。In the present invention, the sulfonic acid structure and
Is -SO3X (X: H, Na, NH FourEtc.)
Means a structural portion having a group, for example, a sulfonic acid group,
Sodium sulfonate, ammonium sulfonate, etc.
You can
【００２１】上記のような、分子構造中に、アルキレン
エーテルの繰り返し構造とともに、スルホン酸構造また
はリン酸エステル構造を有する界面活性剤としては、具
体的には、ポリオキシアルキレンアルキルエーテルリン
酸エステル、ポリオキシアルキレンアルキルフェニルエ
ーテルスルホン酸構造等があげられる。これらは単独で
もしくは２種以上併せて用いられる。Specific examples of the surfactant having a sulfonic acid structure or a phosphoric acid ester structure in the molecular structure as well as a repeating structure of alkylene ether include polyoxyalkylene alkyl ether phosphoric acid ester, Examples thereof include polyoxyalkylene alkylphenyl ether sulfonic acid structures. These may be used alone or in combination of two or more.
【００２２】上記特定の界面活性剤としては、具体的に
は、下記の式（２）または（３）で表されるポリオキシ
アルキレンアルキルエーテルリン酸エステル、下記の式
（４）で表されるポリオキシアルキレンアルキルフェニ
ルエーテルサルフェートアンモニウム塩等があげられ
る。Specific examples of the above-mentioned specific surface active agent include polyoxyalkylene alkyl ether phosphate represented by the following formula (2) or (3) and the following formula (4). Examples thereof include polyoxyalkylene alkylphenyl ether sulfate ammonium salt and the like.
【００２３】[0023]
【化２】 [Chemical 2]
【００２４】[0024]
【化３】 [Chemical 3]
【００２５】[0025]
【化４】 [Chemical 4]
【００２６】前記ポリアニリンの重合に用いる化学酸化
剤としては、特に限定はなく、例えば、過硫酸アンモニ
ウム、過酸化水素水、塩化第二鉄等があげられる。これ
らは単独でもしくは２種以上併せて用いられる。これら
のなかでも、過硫酸アンモニウムが好適に用いられる。The chemical oxidizing agent used for the polymerization of the polyaniline is not particularly limited, and examples thereof include ammonium persulfate, hydrogen peroxide solution, ferric chloride and the like. These may be used alone or in combination of two or more. Among these, ammonium persulfate is preferably used.
【００２７】前記有機相に用いる有機溶剤としては、特
に限定はないが、メチルエチルケトン（ＭＥＫ）のよう
なケトン系溶剤や、トルエンのような芳香族系溶剤等の
汎用の有機溶剤を用いることができる。The organic solvent used in the organic phase is not particularly limited, but a general-purpose organic solvent such as a ketone solvent such as methyl ethyl ketone (MEK) or an aromatic solvent such as toluene can be used. .
【００２８】前記のようにして得られる、界面活性剤構
造を有する導電性ポリアニリンの数平均分子量（Ｍｎ）
は、５００〜１００，０００の範囲内が好ましく、特に
好ましくは１，０００〜２０，０００の範囲内である。The number average molecular weight (Mn) of the conductive polyaniline having a surfactant structure obtained as described above.
Is preferably in the range of 500 to 100,000, particularly preferably in the range of 1,000 to 20,000.
【００２９】このようにして得られる本発明の導電性ポ
リアニリン溶液は、例えば、ラングミュアーブロジェッ
ト（ＬＢ）膜形成手法やスピンコーティング法によっ
て、ポリアニリン薄膜とすることも可能である。また、
ミセル、ベシクル構造を形成する両親媒性物質（界面活
性剤）とともに、ミセル、共ベシクルを形成して、ポリ
アニリン複合体を形成することも可能である。The conductive polyaniline solution of the present invention thus obtained can be formed into a polyaniline thin film by, for example, a Langmuir-Blodgett (LB) film forming method or a spin coating method. Also,
It is also possible to form micelles and co-vesicles together with amphiphiles (surfactants) that form micelle and vesicle structures to form polyaniline complexes.
【００３０】本発明の導電性ポリアニリン溶液は、電
気、電子、材料等の諸分野において、高分子表面の金属
めっきや導電性化および各種絶縁材料の導電性化に特に
有用であり、例えば、電子写真感光体もしくは静電記録
誘電体等の像担持体上に形成された潜像を現像して顕像
化するための現像装置に用いられる現像剤担持体に用い
ることができる。また、静電気防止用のコーティング
剤、繊維の処理剤、自動車用燃料ホースの帯電防止材料
に用いることもできる。The electroconductive polyaniline solution of the present invention is particularly useful for metal plating and electroconductivity of polymer surfaces and electroconductivity of various insulating materials in various fields such as electricity, electrons and materials. It can be used as a developer carrier used in a developing device for developing and visualizing a latent image formed on an image carrier such as a photographic photoreceptor or an electrostatic recording dielectric. It can also be used as an antistatic coating agent, a fiber treatment agent, and an antistatic material for automobile fuel hoses.
【００３１】つぎに、実施例について比較例と併せて説
明する。Next, examples will be described together with comparative examples.
【００３２】[0032]
【実施例１】アニリン塩酸塩０．２モルの水溶液１００
ｍｌに、界面活性剤である前記式（４）で表されるポリ
オキシアルキレンアルキルフェニルエーテルサルフェー
トアンモニウム塩（第一工業製薬社製、ハイテノールＮ
Ｏ８）０．２モルを加えて加熱し、その溶液をさらに２
〜８℃に保って攪拌しながら、過硫酸化アンモニウム
０．２モルを加えて８時間反応を行った。当初、不均一
系であったものが反応が進行するにつれて、均一系とな
り、ポリアニリン特有の緑色の溶液が得られた。この得
られたポリアニリンは、メタノールを加えるとポリアニ
リンの沈殿が得られる。このポリアニリン溶液の電気抵
抗を、ＪＩＳ Ｋ ７１９４に準じて測定した結果、電
気抵抗は３５Ω・ｃｍであった。Example 1 Aqueous solution of 0.2 mol of aniline hydrochloride 100
In ml, a polyoxyalkylene alkyl phenyl ether sulfate ammonium salt represented by the above formula (4) which is a surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Hitenol N
O8) 0.2 mol was added and heated, and the solution was further added to 2
0.2 mol of ammonium persulfate was added to the reaction mixture while stirring at 8 ° C. for 8 hours. At first, the heterogeneous system became homogeneous as the reaction proceeded, and a green solution peculiar to polyaniline was obtained. With the obtained polyaniline, precipitation of polyaniline can be obtained by adding methanol. The electric resistance of this polyaniline solution was measured according to JIS K 7194, and as a result, the electric resistance was 35 Ω · cm.
【００３３】そして、上記ポリアニリン溶液に、メチル
エチルケトン（ＭＥＫ）を加えて上澄みを分離させたと
ころ、ポリアニリンとＭＥＫとが相溶し、均一溶液とな
った。また、上記ポリアニリン溶液に、トルエンを加え
て上澄みを分離させたところ、ポリアニリンとトルエン
とが相溶し、均一溶液となった。Then, methyl ethyl ketone (MEK) was added to the polyaniline solution to separate the supernatant, and polyaniline and MEK were compatible with each other to form a uniform solution. Further, when toluene was added to the above polyaniline solution to separate the supernatant, polyaniline and toluene were compatible with each other to form a uniform solution.
【００３４】さらに、上記上澄みをガラス板上に塗布
し、乾燥させて、厚み２０μｍの塗膜を作製した。そし
て、２５℃×５０％ＲＨの環境下において、１０Ｖの電
圧を印加した時の膜の電気抵抗を、ＪＩＳ Ｋ ７１９
４に準じて測定した結果、電気抵抗は４９Ω・ｃｍであ
った。Further, the above supernatant was applied on a glass plate and dried to prepare a coating film having a thickness of 20 μm. Then, the electrical resistance of the film when a voltage of 10 V was applied in an environment of 25 ° C. × 50% RH was measured according to JIS K 719.
As a result of measurement according to 4, the electric resistance was 49 Ω · cm.
【００３５】[0035]
【実施例２】アニリン塩酸塩０．２モルの水溶液１００
ｍｌに、界面活性剤である前記式（２）で表されるポリ
オキシアルキレンアルキルエーテルリン酸エステル（第
一工業製薬社製、プライサーフ２１５Ｃ）０．２モルを
加えて加熱し、その溶液をさらに２〜８℃に保って攪拌
しながら過硫酸化アンモニウム０．２モルを加えて２０
時間反応を行った。当初、不均一系であったものが反応
が進行するにつれて、均一系となり、ポリアニリン特有
の緑色の溶液が得られた。この得られたポリアニリン
は、メタノールを加えるとポリアニリンの沈殿が得られ
る。このポリアニリン溶液の電気抵抗を、ＪＩＳ Ｋ
７１９４に準じて測定した結果、電気抵抗は５２００Ω
・ｃｍであった。Example 2 Aqueous solution of 0.2 mol of aniline hydrochloride 100
0.2 ml of a polyoxyalkylene alkyl ether phosphate represented by the above formula (2) which is a surfactant (Prysurf 215C, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was added to ml and the solution was heated, Further, 0.2 mol of ammonium persulfate is added with stirring at 2 to 8 ° C.
The reaction was carried out over time. At first, the heterogeneous system became homogeneous as the reaction proceeded, and a green solution peculiar to polyaniline was obtained. With the obtained polyaniline, precipitation of polyaniline can be obtained by adding methanol. The electrical resistance of this polyaniline solution was measured according to JIS K
As a result of measurement according to 7194, electric resistance is 5200Ω
・ It was cm.
【００３６】そして、上記ポリアニリン溶液に、メチル
エチルケトン（ＭＥＫ）を加えて上澄みを分離させたと
ころ、ポリアニリンとＭＥＫとが相溶し、均一溶液とな
った。また、上記ポリアニリン溶液に、トルエンを加え
て上澄みを分離させたところ、ポリアニリンとトルエン
とが相溶し、均一溶液となった。Then, methyl ethyl ketone (MEK) was added to the polyaniline solution to separate the supernatant, and polyaniline and MEK were compatible with each other to form a uniform solution. Further, when toluene was added to the above polyaniline solution to separate the supernatant, polyaniline and toluene were compatible with each other to form a uniform solution.
【００３７】さらに、上記上澄みをガラス板上に塗布
し、乾燥させて、厚み２０μｍの塗膜を作製した。そし
て、２５℃×５０％ＲＨの環境下において、１０Ｖの電
圧を印加した時の膜の電気抵抗を、ＪＩＳ Ｋ ７１９
４に準じて測定した結果、電気抵抗は６１Ω・ｃｍであ
った。Further, the above supernatant was applied on a glass plate and dried to prepare a coating film having a thickness of 20 μm. Then, the electrical resistance of the film when a voltage of 10 V was applied in an environment of 25 ° C. × 50% RH was measured according to JIS K 719.
As a result of measurement according to 4, the electric resistance was 61 Ω · cm.
【００３８】[0038]
【比較例１】アニリン塩酸塩０．２モルの水溶液１００
ｍｌに、界面活性剤であるドデシル硫酸ナトリウム（Ｓ
ＤＳ）０．２モルを加えて加熱し、その溶液をさらに０
℃以下に保って攪拌しながら、過硫酸化アンモニウム
０．２５モルを加えて４時間反応を行った。当初、不均
一系であったものが反応が進行するにつれて、均一系と
なり、ポリアニリン特有の緑色の溶液が得られた。この
得られたポリアニリンは、メタノールを加えるとポリア
ニリンの沈殿が得られる。このポリアニリン溶液の電気
抵抗を、ＪＩＳ Ｋ ７１９４に準じて測定した結果、
電気抵抗は１１５Ω・ｃｍであった。Comparative Example 1 Aqueous solution of aniline hydrochloride 0.2 mol 100
Sodium dodecyl sulfate (S
DS) 0.2 mol was added and the solution was heated to 0
0.25 mol of ammonium persulfate was added with stirring at a temperature of not higher than 0 ° C. and the reaction was carried out for 4 hours. At first, the heterogeneous system became homogeneous as the reaction proceeded, and a green solution peculiar to polyaniline was obtained. With the obtained polyaniline, precipitation of polyaniline can be obtained by adding methanol. The electric resistance of this polyaniline solution was measured according to JIS K 7194,
The electric resistance was 115 Ω · cm.
【００３９】そして、上記ポリアニリン溶液に、メチル
エチルケトン（ＭＥＫ）を加えて上澄みを分離させたと
ころ、ポリアニリンとＭＥＫとの相溶性が悪く、均一な
溶液とならなかった。また、上記ポリアニリン溶液に、
トルエンを加えて上澄みを分離させたところ、ポリアニ
リンとトルエンとの相溶性が悪く、均一な溶液とならな
かった。Then, when methyl ethyl ketone (MEK) was added to the above polyaniline solution to separate the supernatant, the compatibility between polyaniline and MEK was poor, and a uniform solution was not obtained. Also, in the above polyaniline solution,
When toluene was added and the supernatant was separated, the compatibility between polyaniline and toluene was poor and a uniform solution was not obtained.
【００４０】さらに、上記上澄みをガラス板上に塗布
し、乾燥させて、厚み２０μｍの塗膜を作製した。そし
て、２５℃×５０％ＲＨの環境下において、１０Ｖの電
圧を印加した時の膜の電気抵抗を、ＪＩＳ Ｋ ７１９
４に準じて測定した結果、電気抵抗は７８００Ω・ｃｍ
であった。Further, the above supernatant was applied on a glass plate and dried to prepare a coating film having a thickness of 20 μm. Then, the electrical resistance of the film when a voltage of 10 V was applied in an environment of 25 ° C. × 50% RH was measured according to JIS K 719.
As a result of measuring according to 4, the electric resistance is 7800 Ω · cm.
Met.
【００４１】[0041]
【比較例２】特開２００１−２８８２６４号公報に準じ
て、ポリアニリン溶液を作製した。すなわち、フラスコ
内に、濃塩酸１０ｇ、ドデシルベンゼンスルホン酸（Ｄ
ＢＳＡ）５ｇおよび水４０ｇを入れて、水溶液を調製し
た。また、ビーカー内に入れたペルオキシ硫酸アンモニ
ウム（ＡＰＳ）５ｇを、水５０ｇに溶解して、酸化剤水
溶液を調製した。ついで、トルエン４０ｇとアニリン２
ｇから調製したアニリン溶液を、上記フラスコに加え、
フラスコ内の混合物を激しく攪拌して、エマルジョンを
形成した。そして、攪拌を停止してエマルジョンを静置
し、水相と非水相または油相に分離した後、非水相を水
相から分離した。つぎに、この分離した非水相に、攪拌
下、上記酸化剤水溶液を滴下し、反応混合物を攪拌して
さらにエマルジョンを形成した。室温で１〜２時間反応
させた。エマルジョンのｐＨを１以下に制御した。重合
後、攪拌を停止し静置すると、エマルジョンは下相と上
相に分離した。可溶性ポリアニリンを含有する上相は透
明性を示し、肉眼で、上相に固形沈殿は観察されなかっ
た。このポリアニリン溶液の上相の電気抵抗を、ＪＩＳ
Ｋ ７１９４に準じて測定した結果、電気抵抗は８７
Ω・ｃｍであった。Comparative Example 2 A polyaniline solution was prepared according to Japanese Patent Laid-Open No. 2001-288264. That is, 10 g of concentrated hydrochloric acid and dodecylbenzenesulfonic acid (D
An aqueous solution was prepared by adding 5 g of BSA) and 40 g of water. Further, 5 g of ammonium peroxysulfate (APS) placed in a beaker was dissolved in 50 g of water to prepare an oxidant aqueous solution. Next, 40 g of toluene and aniline 2
The aniline solution prepared from g was added to the flask,
The mixture in the flask was vigorously stirred to form an emulsion. Then, the stirring was stopped, the emulsion was allowed to stand, and the aqueous phase and the non-aqueous phase or the oil phase were separated, and then the non-aqueous phase was separated from the aqueous phase. Next, the above-mentioned aqueous oxidant solution was added dropwise to the separated non-aqueous phase with stirring, and the reaction mixture was stirred to further form an emulsion. The reaction was carried out at room temperature for 1 to 2 hours. The pH of the emulsion was controlled below 1. After the polymerization, stirring was stopped and the mixture was allowed to stand, whereby the emulsion separated into a lower phase and an upper phase. The upper phase containing soluble polyaniline showed transparency and no macroscopic solid precipitation was observed in the upper phase with the naked eye. The electrical resistance of the upper phase of this polyaniline solution was measured by JIS
As a result of measurement according to K 7194, the electric resistance is 87.
It was Ω · cm.
【００４２】〔まとめ〕上記の結果から、全実施例品
は、メチルエチルケトン（ＭＥＫ）やトルエンとの相溶
性が優れるとともに、水にも可溶であり、しかも導電性
に優れていることがわかる。[Summary] From the above results, it can be seen that all the products of Examples have excellent compatibility with methyl ethyl ketone (MEK) and toluene, as well as being soluble in water and excellent in conductivity.
【００４３】これに対して、比較例１品は、メチルエチ
ルケトン（ＭＥＫ）やトルエンとの相溶性がやや劣って
いた。比較例２品は、トルエンに対する溶解性は優れる
が、ＭＥＫに対する可溶性が悪いため、ＭＥＫ溶液とし
て使用することができない。On the other hand, the product of Comparative Example 1 was slightly inferior in compatibility with methyl ethyl ketone (MEK) and toluene. The product of Comparative Example 2 has excellent solubility in toluene but poor solubility in MEK, and therefore cannot be used as a MEK solution.
【００４４】[0044]
【発明の効果】以上のように、本発明の導電性ポリアニ
リン溶液は、界面活性剤構造を有する導電性ポリアニリ
ンの溶液であって、上記界面活性剤構造を形成するため
に用いられる界面活性剤が、分子構造中に、アルキレン
エーテルの繰り返し構造を有するものであるため、水に
可溶で、しかもメチルエチルケトン（ＭＥＫ）のような
ケトン系溶剤やトルエンのような芳香族系溶剤等の汎用
の有機溶剤にも可溶であり、導電性にも非常に優れてい
る。このように、本発明の導電性ポリアニリン溶液は、
少量の有機溶剤で溶解できるため、厚塗りが可能になる
とともに、ポリアニリン導電性薄膜を作製する際に有機
溶剤の乾燥時間が短縮できる等の利点もある。As described above, the conductive polyaniline solution of the present invention is a solution of a conductive polyaniline having a surfactant structure, and the surfactant used for forming the surfactant structure is Since it has a repeating structure of alkylene ether in its molecular structure, it is soluble in water and is a general-purpose organic solvent such as a ketone solvent such as methyl ethyl ketone (MEK) or an aromatic solvent such as toluene. It is also soluble in water and has excellent conductivity. Thus, the conductive polyaniline solution of the present invention,
Since it can be dissolved with a small amount of an organic solvent, it has the advantages of enabling thick coating and shortening the drying time of the organic solvent when producing a polyaniline conductive thin film.
【００４５】また、上記界面活性剤構造を形成するため
に用いられる界面活性剤が、分子構造中に、スルホン酸
構造またはリン酸エステル構造を有するものであると、
これらがポリアニリンのドーパントとしての役割を果た
し、導電性がさらに良好となるとともに、メチルエチル
ケトン（ＭＥＫ）のようなケトン系の有機溶剤、もしく
はトルエンのような芳香族系の有機溶剤に対する溶解性
がより向上する。If the surfactant used for forming the above-mentioned surfactant structure has a sulfonic acid structure or a phosphoric acid ester structure in the molecular structure,
These serve as dopants for polyaniline, further improving conductivity, and further improving solubility in ketone-based organic solvents such as methyl ethyl ketone (MEK) or aromatic-based organic solvents such as toluene. To do.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 倉本 憲幸 山形県米沢市林泉寺２丁目７−１ Ｆターム(参考） 4J043 PA02 QB02 RA01 SB01 UA121 UB211 XA13 XA28 XA38 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Noriyuki Kuramoto 2-7-1, Rinsenji Temple, Yonezawa City, Yamagata Prefecture F-term (reference) 4J043 PA02 QB02 RA01 SB01 UA121 UB211 XA13 XA28 XA38
Claims (4)
リンの溶液であって、上記界面活性剤構造を形成するた
めに用いられる界面活性剤が、分子構造中に、アルキレ
ンエーテルの繰り返し構造を有するものであることを特
徴とする導電性ポリアニリン溶液。1. A solution of a conductive polyaniline having a surfactant structure, wherein the surfactant used for forming the surfactant structure has a repeating structure of alkylene ether in the molecular structure. A conductive polyaniline solution characterized by:
いられる界面活性剤が、分子構造中に、スルホン酸構造
またはリン酸エステル構造を有するものである請求項１
記載の導電性ポリアニリン溶液。2. The surfactant used for forming the surfactant structure has a sulfonic acid structure or a phosphoric acid ester structure in the molecular structure.
The conductive polyaniline solution described.
いられる界面活性剤が、ポリオキシアルキレンアルキル
エーテルリン酸エステル、またはポリオキシアルキレン
アルキルフェニルエーテルスルホン酸構造を有するもの
である請求項１または２記載の導電性ポリアニリン溶
液。3. The surfactant used for forming the surfactant structure has a polyoxyalkylene alkyl ether phosphate or a polyoxyalkylene alkyl phenyl ether sulfonic acid structure. 2. The conductive polyaniline solution according to 2.
電性ポリアニリン溶液の製法であって、上記界面活性剤
構造を有する導電性ポリアニリンを水溶液で合成した
後、ケトン系溶剤または芳香族系溶剤に転相することを
特徴とする導電性ポリアニリン溶液の製法。4. The method for producing the conductive polyaniline solution according to claim 1, wherein the conductive polyaniline having the surfactant structure is synthesized in an aqueous solution, and then a ketone solvent or an aroma is used. A method for producing a conductive polyaniline solution, which comprises subjecting a phase to a group-based solvent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060671A (en) * | 2003-07-31 | 2005-03-10 | Maruai:Kk | Method for producing polyaniline conductive ink |
| WO2005035626A1 (en) * | 2003-10-08 | 2005-04-21 | The Yokohama Rubber Co., Ltd. | Process for producing conductive polyaniline and organic polymer composition |
| US7351359B2 (en) | 2003-10-08 | 2008-04-01 | The Yokohama Rubber Co., Ltd. | Method for producing conductive polyaniline and organic polymer composition |
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|---|---|---|---|---|
| KR101813650B1 (en) | 2009-07-08 | 2017-12-29 | 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 | Electrically conductive polymer composition and method for producing same |
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2002
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060671A (en) * | 2003-07-31 | 2005-03-10 | Maruai:Kk | Method for producing polyaniline conductive ink |
| WO2005035626A1 (en) * | 2003-10-08 | 2005-04-21 | The Yokohama Rubber Co., Ltd. | Process for producing conductive polyaniline and organic polymer composition |
| US7351359B2 (en) | 2003-10-08 | 2008-04-01 | The Yokohama Rubber Co., Ltd. | Method for producing conductive polyaniline and organic polymer composition |
| US7497975B2 (en) | 2003-10-08 | 2009-03-03 | The Yokohama Rubber Co., Ltd. | Method for producing conductive polyaniline |
| US7875209B2 (en) | 2003-10-08 | 2011-01-25 | The Yokohama Rubber Co., Ltd. | Photovoltaic device comprising conductive polyaniline |
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