JPH06256516A - Production of electrically conductive polymer - Google Patents
Production of electrically conductive polymerInfo
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- JPH06256516A JPH06256516A JP7302193A JP7302193A JPH06256516A JP H06256516 A JPH06256516 A JP H06256516A JP 7302193 A JP7302193 A JP 7302193A JP 7302193 A JP7302193 A JP 7302193A JP H06256516 A JPH06256516 A JP H06256516A
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Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は、極めて安定で、水に対
して高い溶解度を有する新規導電性重合体の製造方法に
関する。さらに詳しくは、本発明は、電気、電子工業の
分野において、加工性に関して要求度の高い電極、セン
サー、エレクトロニクス表示素子、非線形光学素子、光
電変換素子、帯電防止剤他、各種導電材料あるいは光学
材料として用いるのに特に適した新規水溶性導電性重合
体の製造方法に関するものである。FIELD OF THE INVENTION The present invention relates to a method for producing a novel conductive polymer which is extremely stable and has a high solubility in water. More specifically, the present invention is, in the fields of electrical and electronic industries, electrodes, sensors, electronic display elements, non-linear optical elements, photoelectric conversion elements, antistatic agents, and other various conductive materials or optical materials that are highly required for workability. The present invention relates to a method for producing a novel water-soluble conductive polymer, which is particularly suitable for use as.
【０００２】[0002]
【従来の技術】π電子共役系の発達したポリマーは、導
電性のみならず金属／半導体転移における状態変化など
の特異な物性のために工業的に注目され、多くの用途を
目指した研究がなされてきた。中でも、ブレンステッド
酸基をポリマー主鎖に直接、またはスペーサーを介して
間接的に共有結合させることにより得られる水溶性自己
ドープ型共役系ポリマーは、外来ドーパントの寄与なし
に長期間にわたって安定な導電状態を示す点で特に注目
されてきた。2. Description of the Related Art Polymers having a developed π-electron conjugated system have attracted industrial attention because of their unique physical properties such as state change at the metal / semiconductor transition, and research aimed at many applications has been made. Came. Among them, a water-soluble self-doped conjugated polymer obtained by directly or covalently bonding a Bronsted acid group to a polymer main chain or indirectly through a spacer is a stable conductive material for a long period of time without contribution of an exogenous dopant. Particular attention has been given to indicating the condition.
【０００３】具体的な先行例として、例えばＦ．Ｗｕｄ
ｌらやＥ．Ｅ．Ｈａｖｉｎｇａらのアルカンスルホン酸
基を有するポリチオフェン誘導体（Ｊｏｕｒｎａｌ ｏ
ｆＡｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔ
ｙ誌、１０９巻１８５８頁、１９８７年；Ｐｏｌｙｍｅ
ｒ Ｂｕｌｌｅｔｉｎ誌、１８巻２７７頁、１９８７
年）、Ａｌｄｉｓｓｉのポリチオフェン誘導体やポリピ
ロール誘導体（米国特許４８８０５０８号）、ポリアニ
リンの芳香環に置換基としてカルボン酸基を共有結合さ
せた重合体（特許公表公報平１−５００８３５号）、ピ
ロールのＮ位にプロパンスルホン酸基が置換した重合体
（Ｊｏｕｒｎａｌ ｏｆ Ｃｈｅｍｉｃａｌ Ｓｏｃｉ
ｅｔｙ，Ｃｈｅｍｉｃａｌ Ｃｏｍｍｕｎｉｃａｔｉｏ
ｎ誌、６２１頁、１９８７年）、Ｎ位にプロパンスルホ
ン酸基が置換したポリアニリン重合体（Ｊｏｕｒｎａｌ
ｏｆ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ， Ｃｈｅ
ｍｉｃａｌ Ｃｏｍｍｕｎｉｃａｔｉｏｎ誌、１８０
頁、１９９０年；Ｓｙｎｔｈｅｔｉｃ Ｍｅｔａｌｓ
誌、３１巻３６９頁、１９８９年）、芳香環に直接スル
ホン酸基が置換したポリアニリン誘導体（Ｊｏｕｒｎａ
ｌ ｏｆ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏ
ｃｉｅｔｙ誌，１１２巻２８００頁、１９９０年）など
がこれまで製造法と共に開示されている。As a concrete precedent, for example, F.I. Wud
L et al. E. Havinga et al., Polythiophene Derivatives Having Alkanesulfonic Acid Group (Journal o
fAmerican Chemical Societ
Y, 109, 1858, 1987; Polymer
Bulletin, 18: 277, 1987
), A polythiophene derivative of Aldissi or a polypyrrole derivative (US Pat. No. 4,880,508), a polymer in which a carboxylic acid group is covalently bonded to the aromatic ring of polyaniline as a substituent (Patent Publication No. 1-500835), and the N-position of pyrrole. A polymer in which a propanesulfonic acid group is substituted (Journal of Chemical Soci
ety, Chemical Communicatio
n, p. 621, 1987), polyaniline polymer having a propanesulfonic acid group substituted at the N position (Journal).
of Chemical Society, Che
medical Communication, 180
P., 1990; Synthetic Metals
, Vol. 31, pp. 369, 1989), polyaniline derivatives in which an aromatic ring is directly substituted with a sulfonic acid group (Journa).
l of American Chemical So
Ciety magazine, Vol. 112, p. 2800, 1990) and the like have been disclosed so far together with the manufacturing method.
【０００４】一方、二環式系導電性重合体、例えばイソ
チアナフテン構造を有する重合体は、Ｊｏｕｒｎａｌ
ｏｆ Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ誌，４９
巻，３３８２頁、１９８４年；等に製造法と共に開示さ
れており、エネルギーギャップ（Ｅｇ）が１．１ｅＶと
極めて小さく、安定な導電状態を示すことが知られてい
る。しかしながらポリイソチアナフテンは不溶不融であ
り成形加工性が極めて悪い。そのため、アルキル基ある
いはアルコキシ基を導入することにより、有機溶媒に可
溶とする方法が特開平２−２４２８１６号等に開示され
ている。On the other hand, a bicyclic conductive polymer, for example, a polymer having an isothianaphthene structure is a Journal.
of Organic Chemistry, 49
Vol., P. 3382, 1984; and the like, together with the manufacturing method, it is known that the energy gap (Eg) is extremely small at 1.1 eV and a stable conductive state is exhibited. However, polyisothianaphthene is insoluble and infusible and has extremely poor moldability. Therefore, a method of introducing an alkyl group or an alkoxy group to make it soluble in an organic solvent is disclosed in JP-A-2-242816.
【０００５】また繰り返し構造単位のイソチアナフテニ
レン骨格に電子吸引性基や電子供与性基を導入すると、
半導体としての電子状態に影響を与えることをＢｒｅｄ
ａｓらは計算結果によって報告している（Ｊｏｕｒｎａ
ｌ ｏｆ ＣｈｅｍｉｃａｌＰｈｙｓｉｃｓ誌，８５巻
（８），４６７３頁、１９８６年）。また関連する例と
しては、ハロゲンを置換基とする重合体（特開昭６３−
３０７６０４号）や、電子吸引性基を置換基とする重合
体を列挙した公報（特開平２−２５２７２７号）もある
が、何れも本発明に関する重合体についての特性に関し
なんら記載されておらず、その製造方法についても具体
的な開示はない。When an electron withdrawing group or an electron donating group is introduced into the isothianaphthenylene skeleton of the repeating structural unit,
Bred to affect the electronic state as a semiconductor
as et al. reported on the calculation results (Journa
l of Chemical Physics, Vol. 85 (8), p. 4673, 1986). As a related example, a polymer having halogen as a substituent (Japanese Patent Laid-Open No. 63-
No. 307604) and Japanese Patent Laid-Open No. 252727/1990, which lists polymers having an electron-withdrawing group as a substituent, but none of them describes the properties of the polymer of the present invention. There is no specific disclosure about the manufacturing method.
【０００６】一方、１，３−ジヒドロイソチアナフテニ
レン構造を有する重合体からポリイソチアナフテンを製
造する方法としては、電気化学的な酸化的脱水素反応に
よる方法（特開昭６３−３０７６０４号）、塩化スルフ
リルとの気相反応による酸化的反応（Ｓｙｎｔｈｅｔｉ
ｃ Ｍｅｔａｌｓ誌、３１巻３９５頁１９８９年）及び
Ｎ−クロルサクシンイミド（ＮＣＳ）との反応（Ｓｙｎ
ｔｈｅｔｉｃ Ｍｅｔａｌｓ誌、４７巻３６７頁１９９
２年）による製造法がこれまでに知られている。これら
の先行技術には、ポリ（１，３−ジヒドロイソチアナフ
テニレン）が有機溶媒に可溶な重合物であるとの利点を
活かして、不溶不融のポリイソチアナフテンフィルム等
の成形体製造法が記載されている。On the other hand, as a method for producing polyisothianaphthene from a polymer having a 1,3-dihydroisothianaphthenylene structure, a method by an electrochemical oxidative dehydrogenation reaction (Japanese Patent Laid-Open No. 63-307604). ), An oxidative reaction by a gas phase reaction with sulfuryl chloride (Syntheti)
c Metals, 31: 395, 1989) and reaction with N-chlorsuccinimide (NCS) (Syn).
thetical Metals, 47, 367, 199.
The manufacturing method according to (2 years) is known so far. These prior arts take advantage of the fact that poly (1,3-dihydroisothianaphthenylene) is a polymer that is soluble in an organic solvent, making use of an insoluble and infusible polyisothianaphthene film molded article. The manufacturing method is described.
【０００７】しかしながら、製造されたポリイソチアナ
フテンが不溶不融であるために、加工性が制限される欠
点があった。また、高分子反応においてポリイソチアナ
フテンが不溶不融であるために発煙硫酸等のスルホン化
剤を作用しても、それだけでは反応は内部まで充分進行
せず、水溶性のπ電子共役系重合体を製造することはで
きなかった。However, since the produced polyisothianaphthene is insoluble and infusible, there is a drawback that the processability is limited. In addition, since polyisothianaphthene is insoluble and infusible in the polymer reaction, even if a sulfonating agent such as fuming sulfuric acid acts, the reaction does not proceed sufficiently to the inside and the water-soluble π-electron conjugated system It was not possible to produce a coalesce.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、１，３−ジ
ヒドロイソチアナフテニレン構造を含む重合体からスル
ホン化剤を作用させることにより、スルホン酸基が置換
したイソチアナフテニレン構造を含む水溶性の導電性重
合体を簡便に提供するものである。SUMMARY OF THE INVENTION The present invention comprises an isothianaphthenylene structure substituted with a sulfonic acid group by reacting a sulfonating agent from a polymer containing a 1,3-dihydroisothianaphthenylene structure. A water-soluble conductive polymer is simply provided.
【０００９】[0009]
【課題を解決するための手段】即ち、本発明は一般式
（Ｉ）That is, the present invention has the general formula (I)
【化５】 （式中、Ｒ1 及びＲ2 はそれぞれ独立にＨ、または炭素
数１〜２０の直鎖状もしくは分岐状のアルキル基または
アルコキシ基、ハロゲン、ニトロ基、１級、２級または
３級アミノ基、トリハロメチル基、フェニル基、置換フ
ェニル基を表す。Ｒ1 、Ｒ2 のアルキル基またはアルコ
キシ基には、カルボニル、エーテル、アミド結合を任意
に含んでも良い。）で表される化学構造を含む重合体
に、スルホン化剤を作用させることにより、下記一般式
（II）[Chemical 5] (In the formula, R 1 and R 2 are each independently H, or a linear or branched alkyl group or alkoxy group having 1 to 20 carbon atoms, halogen, nitro group, primary, secondary or tertiary amino group. , A trihalomethyl group, a phenyl group, and a substituted phenyl group. The alkyl group or alkoxy group of R 1 and R 2 may include a carbonyl, ether, or amide bond. By reacting the polymer with a sulfonating agent, the following general formula (II)
【化６】 （式中、Ｒ1 、Ｒ2 は前記と同じであり、ＭはＨ+ もし
くはＮａ+ 、Ｌｉ+ 、Ｋ+ 等のアルカリ金属イオンまた
はアンモニウムイオンもしくはアルキル置換した第４級
アンモニウムイオン等のカチオンを表す。ｍは０．２〜
２の範囲である。）で表される化学構造を含む重合体を
製造することを特徴とする導電性重合体の製造方法に関
する。[Chemical 6] (In the formula, R 1 and R 2 are the same as above, and M is an alkali metal ion such as H + or Na + , Li + , K + or a cation such as an ammonium ion or an alkyl-substituted quaternary ammonium ion. Represents, m is 0.2 to
The range is 2. The present invention relates to a method for producing a conductive polymer, which comprises producing a polymer having a chemical structure represented by
【００１０】また一般式（Ｉ）The general formula (I)
【化７】 （式中、Ｒ1 、Ｒ2 は前記と同じ）で表される化学構造
を含む重合体または該重合体と他の樹脂との複合物成形
体にスルホン化剤を作用させることにより、一般式（I
I）[Chemical 7] (Wherein R 1 and R 2 are the same as above), a sulfonating agent is applied to a polymer having a chemical structure represented by the chemical structure or a composite molded product of the polymer and another resin to give a compound of the general formula (I
I)
【化８】 （式中、Ｒ1 、Ｒ2 、Ｍ及びｍは前記と同じ）で表され
る化学構造を含む重合体または該重合体と他の樹脂との
複合物成形体を製造することを特徴とする導電性重合体
成形物の製造方法に関する。[Chemical 8] (Wherein R 1 , R 2 , M and m are the same as described above), or a polymer molded article containing the polymer having a chemical structure represented by the formula The present invention relates to a method for producing a conductive polymer molded product.
【００１１】本発明の製造方法は、前述したように例え
ば、公知のポリ（１，３−ジヒドロイソチアナフテニレ
ン）構造を含む重合体にスルホン化剤または酸化剤の存
在下スルホン化剤を反応させることにより、実用的な水
溶性導電性重合体を提供することにある。このスルホン
化剤を用いる製造方法は、主鎖がπ電子非共役系の重合
物を酸化的脱水素反応とスルホン化置換反応の２つの反
応を起こさせることによって、水溶性導電性重合体を与
える新規な製造法である。In the production method of the present invention, as described above, for example, a polymer containing a known poly (1,3-dihydroisothianaphthenylene) structure is reacted with a sulfonating agent in the presence of a sulfonating agent or an oxidizing agent. By doing so, it is intended to provide a practical water-soluble conductive polymer. This production method using a sulfonating agent gives a water-soluble conductive polymer by causing two reactions, a oxidative dehydrogenation reaction and a sulfonation substitution reaction, of a polymer whose main chain is a π-electron non-conjugated system. It is a new manufacturing method.
【００１２】従って、前躯体からの成形及び従来困難で
あった他の樹脂との複合化を可能にする。Therefore, the molding from the precursor and the compounding with other resins, which has been difficult in the past, are possible.
【００１３】一般式（Ｉ）で表される重合体として、例
えばＲ1 ＝Ｒ2 ＝Ｈのポリ（１，３−ジヒドロイソチア
ナフテニレン）は、公知の方法、例えばＡ．Ｊ．Ｈｅｅ
ｇｅｒらによる特開昭６１−１７５８１号に記載の方法
で容易に製造することができる。As the polymer represented by the general formula (I), for example, poly (1,3-dihydroisothianaphthenylene) having R 1 ═R 2 ═H can be prepared by a known method such as A. J. Hee
It can be easily produced by the method described in JP-A-61-17581 by Ger et al.
【００１４】一般式（Ｉ）に表される置換基Ｒ1 及びＲ
2 は、スルホン化反応及び酸化的脱水素反応を阻害しな
い置換基であれば何でもよく、例えばそれぞれ独立に
Ｈ、または直鎖状もしくは分岐状の炭素数１〜２０のア
ルキル基またはアルコキシ基、ハロゲン、ニトロ基、脂
肪族あるいは芳香族などで置換された１級、２級または
３級アミノ基、トリクロロメチル等のトリハロメチル
基、フェニル基、置換フェニル基等から選ばれる。上記
炭素数１〜２０のアルキル基またはアルコキシ基の鎖中
には、カルボニル、エーテル、アミド結合を含有しても
良い。Substituents R 1 and R represented by the general formula (I)
2 may be any substituent as long as it does not inhibit the sulfonation reaction and the oxidative dehydrogenation reaction, for example, each independently H, or a linear or branched alkyl group or alkoxy group having 1 to 20 carbon atoms, a halogen atom. , A nitro group, an aliphatic or aromatic substituted primary, secondary or tertiary amino group, a trihalomethyl group such as trichloromethyl, a phenyl group, a substituted phenyl group and the like. A carbonyl, ether, or amide bond may be contained in the chain of the alkyl group or alkoxy group having 1 to 20 carbon atoms.
【００１５】ここでＲ1 及びＲ2 として有用な例として
は、水素、アルキル基、アルコキシ基が挙げられる。こ
れらの置換基を更に詳しく例示すれば、アルキル基とし
てはメチル、エチル、イソプロピル、ブチル、ペンチ
ル、ヘキシル、オクチル、ドデシル、メトキシエチル、
エトキシエチル、アセトニル、フェナシルなど、アルコ
キシ基としてはメトキシ、エトキシ、プロポキシ、イソ
プロポキシ、オクチルオキシ、ドデシルオキシなどの基
が挙げられる。Examples of useful R 1 and R 2 include hydrogen, an alkyl group and an alkoxy group. Illustrating these substituents in more detail, examples of the alkyl group include methyl, ethyl, isopropyl, butyl, pentyl, hexyl, octyl, dodecyl, methoxyethyl,
Examples of the alkoxy group such as ethoxyethyl, acetonyl, and phenacyl include groups such as methoxy, ethoxy, propoxy, isopropoxy, octyloxy, dodecyloxy.
【００１６】またＲ1 及びＲ2 として上記以外に置換基
の例としてメチルアミノ、エチルアミノ、ジフェニルア
ミノ、アニリノなどのアミノ基、トリフルオロメチル
基、フェニル基、トシル基、キシリル基、アセトアミド
基などのアシルアミド基等が挙げられる。Examples of substituents other than the above as R 1 and R 2 include amino groups such as methylamino, ethylamino, diphenylamino and anilino, trifluoromethyl group, phenyl group, tosyl group, xylyl group and acetamide group. And the like.
【００１７】一般式（Ｉ）で表される化学構造を含む前
躯体ポリマーは、１０００以上の分子量を示す高分子で
ある。The precursor polymer containing the chemical structure represented by formula (I) is a polymer having a molecular weight of 1000 or more.
【００１８】一般式（Ｉ）で表される重合体をスルホン
化剤を、スルホン化剤の種類によって、好ましくは酸化
剤の共存下に反応させることによって、一般式（II）で
表される化学構造を含む重合体が製造される。By reacting the polymer represented by the general formula (I) with a sulfonating agent depending on the kind of the sulfonating agent, preferably in the presence of an oxidizing agent, the chemical formula represented by the general formula (II) A polymer containing the structure is produced.
【００１９】具体的には、一般式（Ｉ）で表される重合
物に対して、酸化能を有するスルホン化剤または酸化剤
と併用してこれを用いた場合、同一反応液中でスルホン
化置換反応及び酸化的脱水素反応が起こり、一般式（I
I）で表される化学構造を含む重合体が得られる。Specifically, when the polymer represented by the general formula (I) is used in combination with a sulfonating agent having an oxidizing ability or an oxidizing agent, it is sulfonated in the same reaction solution. Substitution reaction and oxidative dehydrogenation reaction occur, and the general formula (I
A polymer containing the chemical structure represented by I) is obtained.
【００２０】この製造方法において用いられるスルホン
化剤としては、一般に硫酸、発煙硫酸、三酸化硫黄、ク
ロロ硫酸、フルオロ硫酸、アミド硫酸等が挙げられ、中
でも発煙硫酸、三酸化硫黄が好ましい。また複数のスル
ホン化剤を混合して用いても良い。The sulfonating agent used in this production method generally includes sulfuric acid, fuming sulfuric acid, sulfur trioxide, chlorosulfuric acid, fluorosulfuric acid, amidosulfuric acid and the like, among which fuming sulfuric acid and sulfur trioxide are preferred. Further, a plurality of sulfonating agents may be mixed and used.
【００２１】スルホン化剤の使用量は、一般式（Ｉ）で
表される化学構造を含む重合体やスルホン化剤の種類に
よって異なるので一概には決められないが、一般には重
合体中に含まれる一般式（Ｉ）で表される化学構造１等
量に対し１．１倍等量から２０倍等量の範囲で用いるの
が望ましい。The amount of the sulfonating agent used depends on the type of the polymer having the chemical structure represented by the general formula (I) and the type of the sulfonating agent, and therefore cannot be unconditionally determined, but it is generally contained in the polymer. It is desirable to use in the range of 1.1 times equivalent to 20 times equivalent to 1 equivalent of the chemical structure represented by the general formula (I).
【００２２】また、前記スルホン化剤は他の酸化剤また
は酸化的脱水素剤、例えばオゾン、パーオキサイド、過
酸、２，３−ジクロロ−５，６−ジシアノ−１，４−ベ
ンゾキノン、テトラクロロ−１，２−ベンゾキノン、テ
トラクロロ−１，４−ベンゾキノン、テトラシアノ−
１，４−ベンゾキノン等のキノン類、ヨウ素、臭素等の
ハロゲン類、無水塩化アルミニウム／塩化第一銅、無水
塩化第二鉄及びバナジウム系、マンガン系、ニッケル系
などの金属錯体触媒を用いた酸素酸化剤等及びこれらの
組み合わせ等が挙げられるが、特に限定されるものでは
ない。The sulfonating agent may be another oxidizing agent or oxidative dehydrogenating agent such as ozone, peroxide, peracid, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetrachloro. -1,2-benzoquinone, tetrachloro-1,4-benzoquinone, tetracyano-
Oxygen using metal complex catalysts such as quinones such as 1,4-benzoquinone, halogens such as iodine and bromine, anhydrous aluminum chloride / cuprous chloride, anhydrous ferric chloride and vanadium-based, manganese-based, nickel-based, etc. Examples thereof include oxidizing agents and the like, and combinations thereof, but are not particularly limited.
【００２３】これらを用いるときは、反応温度の低下、
反応時間の短縮、収率の向上などが期待できるので、酸
化力の弱いスルホン化剤を使用するときに有用である。When these are used, the reaction temperature is lowered,
Since it is expected to shorten the reaction time and improve the yield, it is useful when a sulfonating agent having a weak oxidizing power is used.
【００２４】本製造法に用いられる一般式（Ｉ）で表さ
れる化学構造を含む重合体の濃度は、その重合体の種類
や反応スケールまたは他の溶媒の種類によって異なる
が、一般には１０-2〜１０ｋｇ／リットルの範囲が望ま
しい。The concentration of the polymer containing the chemical structure represented by the general formula (I) used in the present production method varies depending on the type of the polymer, the reaction scale or the type of other solvent, but is generally 10 −. The range of 2 to 10 kg / liter is desirable.
【００２５】また反応温度は、それぞれの反応方法によ
って定められるもので、特に限定できるものではない
が、一般には−８０℃から２５０℃の温度範囲が望まし
く、特に−３０℃〜１５０℃の温度範囲で行われること
が望ましい。反応時間は、反応方法及び反応温度、反応
圧力あるいは重合体の化学構造等によって異なるので一
概には規定できないが、通常は０．０１時間から２４０
時間が望ましい。反応圧力は、常圧で行われることが好
ましいが、１０-5気圧から１００気圧下で行うことがで
きる。The reaction temperature is determined according to each reaction method and is not particularly limited, but generally a temperature range of -80 ° C to 250 ° C is desirable, and a temperature range of -30 ° C to 150 ° C is particularly preferable. It is desirable to be done in. The reaction time varies depending on the reaction method, the reaction temperature, the reaction pressure, the chemical structure of the polymer and the like, and therefore cannot be specified unconditionally.
Time is desirable. The reaction pressure is preferably atmospheric pressure, but may be under 10 −5 to 100 atm.
【００２６】スルホン化反応および酸化的脱水素反応は
全体をスルホン化および酸化的脱水素する時は、スルホ
ン化剤または反応溶媒を用いて溶解した溶液反応である
ことが必要であり、表面だけで良いときは気相、無溶
媒、または貪溶媒中で行うことができる。必要に応じて
本発明の製造法で用いられる反応溶媒は、反応温度や反
応時間、または用いられるスルホン化剤や重合体の化学
構造によって異なるので一概には規定できないが、重合
物及びスルホン化剤を溶解し、かつ酸化的脱水素反応や
スルホン化置換反応を阻害しないならば、どのような溶
媒であっても良い。例えば、具体的には水、硫酸、発煙
硫酸、ギ酸、酢酸、プロピオン酸、無水酢酸、あるいは
テトラヒドロフラン、ジオキサン、ジエチルエーテル等
のエーテル類、ジメチルホルムアミド、アセトニトリ
ル、ベンゾニトリル、Ｎ−メチルピロリドン（ＮＭ
Ｐ）、ジメチルスルホキシド（ＤＭＳＯ）等の極性溶
媒、酢酸エチル、酢酸ブチル等のエステル類、クロロホ
ルム、塩化メチレン等の非芳香族性の塩素系溶媒等が用
いられる。更にはこれらの混合溶媒を用いることもでき
る。When the entire sulfonation reaction and oxidative dehydrogenation reaction are sulfonation and oxidative dehydrogenation, it is necessary that the reaction is a solution reaction using a sulfonating agent or a reaction solvent. When it is good, it can be carried out in a gas phase, without solvent, or in a phagous solvent. The reaction solvent used in the production method of the present invention, if necessary, cannot be unconditionally specified because it varies depending on the reaction temperature, the reaction time, or the chemical structure of the sulfonating agent or polymer used, but the polymer and the sulfonating agent are not specified. Any solvent may be used as long as it dissolves and does not inhibit the oxidative dehydrogenation reaction or the sulfonation substitution reaction. For example, specifically, water, sulfuric acid, fuming sulfuric acid, formic acid, acetic acid, propionic acid, acetic anhydride, or ethers such as tetrahydrofuran, dioxane, diethyl ether, dimethylformamide, acetonitrile, benzonitrile, N-methylpyrrolidone (NM
P), polar solvents such as dimethylsulfoxide (DMSO), esters such as ethyl acetate and butyl acetate, non-aromatic chlorine solvents such as chloroform and methylene chloride, and the like are used. Furthermore, these mixed solvents can also be used.
【００２７】スルホン化反応の副反応として公知のスル
ホン結合を有する不溶性のポリマー（副生成物）の生成
を抑制するため、反応を阻害しない範囲で公知のスルホ
ン抑制剤、例えば脂肪酸、有機過酸、酸無水物、ピリジ
ン、酢酸またはケトン等を０．０１〜５０重量％添加し
ても良い。In order to suppress the formation of an insoluble polymer having a sulfone bond (a by-product) known as a side reaction of a sulfonation reaction, a known sulfone inhibitor such as a fatty acid or an organic peracid in a range that does not inhibit the reaction. You may add 0.01-50 weight% of acid anhydrides, pyridine, acetic acid, a ketone, etc.
【００２８】上述の製造方法により得られた一般式（I
I）で表される化学構造を含む重合体は、水に対して高
い溶解性を示し、限外濾過、透析及び／またはイオン交
換操作によって単離精製することができる。更に一般式
（II）で表される重合体が反応溶媒から析出物として得
られる場合には、濾過、再沈殿及び／または溶媒分別法
等によって単離精製を行うことができる。The general formula (I
The polymer containing the chemical structure represented by I) has high solubility in water and can be isolated and purified by ultrafiltration, dialysis and / or ion exchange operations. Further, when the polymer represented by the general formula (II) is obtained as a precipitate from the reaction solvent, it can be isolated and purified by filtration, reprecipitation and / or a solvent fractionation method.
【００２９】本発明の製造法で製造される一般式（II）
に表される化学構造を含む重合体において、式中スルホ
ン酸基の置換率を示すｍは０．２から２の範囲であり、
特に０．４から１．３の範囲が好ましい。The general formula (II) produced by the production method of the present invention
In the polymer having the chemical structure represented by the formula, m showing the substitution rate of the sulfonic acid group in the formula is in the range of 0.2 to 2,
Particularly, the range of 0.4 to 1.3 is preferable.
【００３０】ＭはＨ+ 、Ｎａ+ 、Ｌｉ+ ，Ｋ+ 等のアル
カリ金属イオンや、ＮＨ4 +、Ｎ（ＣＨ3 ）4 +、Ｎ（Ｃ6
Ｈ5 ）4 +、ＰＨ4 +、Ｐ（ＣＨ3 ）4 +、Ｐ（Ｃ6 Ｈ
5 ）4 +、ＡｓＨ4 +、Ａｓ（ＣＨ3 ）4 +，Ａｓ（Ｃ6 Ｈ
5 ）4 +等のＶｂ族元素のアルキル置換、またはアリール
置換型カチオンが用いられる。特定カチオンに変換する
には、通常のイオン交換樹脂でイオン交換することによ
り任意のカチオンに変換することができる。M is an alkali metal ion such as H + , Na + , Li + , K + , NH 4 + , N (CH 3 ) 4 + , N (C 6
H 5 ) 4 + , PH 4 + , P (CH 3 ) 4 + , P (C 6 H
5 ) 4 + , AsH 4 + , As (CH 3 ) 4 + , As (C 6 H
5 ) An alkyl-substituted or aryl-substituted cation of a Vb group element such as 4 + is used. In order to convert it into a specific cation, it can be converted into an arbitrary cation by performing ion exchange with an ordinary ion exchange resin.
【００３１】一般式（II）の式中ＭがＨ+ の場合、水溶
液中では外来のドーパントがなくても自己ドーピング状
態を示し、特に高濃度ではゲル状態を示すこともあるな
ど、Ｍを変えることにより種々の溶媒に対する溶解性や
溶媒親和性を変えることができる。When M is H + in the formula of the general formula (II), it shows a self-doping state even in the absence of an exogenous dopant in an aqueous solution, and may show a gel state especially at a high concentration. As a result, the solubility and solvent affinity for various solvents can be changed.
【００３２】また成形体であってその表面が一般式（I
I）で表される化学構造を含む重合体成形体または他の
樹脂との複合体となっている表面が導電性成形体は、一
般式（Ｉ）の１，３−ジヒドロイソチアナフテニレン構
造を含む重合体の成形体または該重合体と他の樹脂との
複合体からなる成形体から製造することができる。A molded product whose surface has the general formula (I
The surface of the polymer molded body containing the chemical structure represented by I) or a complex with another resin having a conductive surface has a 1,3-dihydroisothianaphthenylene structure of the general formula (I). It can be manufactured from a molded product of a polymer containing the above or a molded product of a composite of the polymer and another resin.
【００３３】この場合、一般式（Ｉ）の化学構造を含む
重合体の成形体または該重合体と他の樹脂との複合体を
スルホン化剤とまたは酸化剤の共存下、液固反応もしく
は気固反応で反応させる。即ち、一般式（Ｉ）の構造を
含む重合体が有機溶媒に可溶な化合物であっても、一般
式（Ｉ）で表される化学構造を含む重合物成形体または
該重合体と他の樹脂との複合体成形体を成形体の形状を
崩さず、一般式（II）で表される化学構造を表面に有す
る重合体を表面に有する成形体の製造ができる。In this case, a molded product of a polymer containing the chemical structure of the general formula (I) or a composite of the polymer and another resin is subjected to a liquid-solid reaction or gas in the presence of a sulfonating agent or an oxidizing agent. React with solid reaction. That is, even if the polymer containing the structure of the general formula (I) is a compound soluble in an organic solvent, a polymer molded product containing the chemical structure represented by the general formula (I) or the polymer and other It is possible to produce a molded product having a polymer having the chemical structure represented by the general formula (II) on the surface thereof, without destroying the shape of the molded product of the composite molded product with a resin.
【００３４】一般式（II）で表される化学構造を含む重
合物からなる種々の成形体は、一般式（Ｉ）の構造を含
む重合体の有機溶媒に対する溶解性の利点を活かして、
同様にフィルム（例えばスピンキャスト法）、線状成形
物、あるいは棒状、板状、シート状、その他の固体の成
形体を一般の高分子工業で行われる成形、製膜方法で容
易に製造することができる。Various molded articles made of a polymer having a chemical structure represented by the general formula (II) take advantage of the solubility of the polymer having the structure of the general formula (I) in an organic solvent.
Similarly, a film (for example, a spin cast method), a linear molded product, or a rod-shaped, plate-shaped, sheet-shaped, or other solid molded product can be easily manufactured by a molding or film-forming method performed in a general polymer industry. You can
【００３５】一般式（Ｉ）で表される化学構造を含む重
合物と他の樹脂との複合体は一般式（Ｉ）の構造を含む
重合体の有機溶媒に対する溶解性の利点を生かして複合
化する。この際、溶媒が共通または混合可能な樹脂なら
何でもよく、例えば低密度ポリエチレン、ポリ塩化ビニ
ル、ポリスチレン、ポリメチルメタクリレート（ＰＭＭ
Ａ）、ポリアクリロニトリル等を用い、溶液状態におい
て他の樹脂と溶解もしくは混合し、その溶液から任意組
成比を有する成形体を形成することもできる。通常使用
する樹脂の割合は、本重合体に対し１０〜５００％の範
囲が好ましい。また、このとき用いられる溶媒として
は、トリクロロエチレン、ジクロロメタン、クロロホル
ム、四塩化炭素等のハロゲン化炭化水素系溶媒、ベンゼ
ン、トルエン、キシレン、クロロベンゼン、ジクロロベ
ンゼン等の芳香族系溶媒、テトラヒドロフラン（ＴＨ
Ｆ）、ジオキサン等のエーテル系溶媒、ジメチルスルホ
キシド（ＤＭＳＯ）、ジメチルホルムアミド（ＤＭ
Ｆ）、Ｎ−メチル−２−ピロリドン（ＮＭＰ）等の極性
溶媒、酢酸メチル、酢酸エチル等のエステル系溶媒な
ど、双方の化合物を溶解もしくは高い親和性を示すもの
であれば何でも良い。二成分以上の混合溶媒系でも良
い。A composite of a polymer containing the chemical structure represented by the general formula (I) and another resin is a composite compound by taking advantage of the solubility of the polymer containing the structure of the general formula (I) in an organic solvent. Turn into. At this time, any resin may be used as long as it has a common solvent or can be mixed, for example, low density polyethylene, polyvinyl chloride, polystyrene, polymethylmethacrylate (PMM).
A), polyacrylonitrile or the like may be used to dissolve or mix with other resin in a solution state to form a molded product having an arbitrary composition ratio from the solution. The ratio of the resin usually used is preferably in the range of 10 to 500% with respect to the present polymer. The solvent used at this time includes halogenated hydrocarbon solvents such as trichloroethylene, dichloromethane, chloroform and carbon tetrachloride, aromatic solvents such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, and tetrahydrofuran (TH
F), ether solvents such as dioxane, dimethyl sulfoxide (DMSO), dimethylformamide (DM
F), polar solvents such as N-methyl-2-pyrrolidone (NMP), ester solvents such as methyl acetate and ethyl acetate, and the like, as long as they dissolve both compounds or exhibit high affinity. A mixed solvent system of two or more components may also be used.
【００３６】このようにして製造された成形体、特に樹
脂表面に存在する一般式（Ｉ）はスルホン化剤の作用に
より一般式（II）式で表される化学構造を含む重合体に
変換され、無色から黒青色になる。この方法により形成
した成形体は極めて安定な導電状態を維持する。The molded product thus produced, particularly the general formula (I) present on the surface of the resin, is converted into a polymer having the chemical structure represented by the general formula (II) by the action of the sulfonating agent. , Colorless to black blue. The molded body formed by this method maintains an extremely stable conductive state.
【００３７】本発明の一般式（II）で表される化学構造
を含む水溶性導電性重合体は、公知の水溶性導電性重合
体、例えばポリチオフェン誘導体（特開平２−２４２８
１６号）と比較すると、半導体としてのエネルギーギャ
ップが約１．１ｅＶと小さく、低いドーピングレベルで
高い導電性を示し、その導電状態が極めて安定に得られ
るという特徴を持つ。そのため、特にドーピング時には
可視光の吸光度が小さくなるため、安定性に優れた透明
導電体としても期待できる。The water-soluble conductive polymer having a chemical structure represented by the general formula (II) of the present invention is a known water-soluble conductive polymer such as a polythiophene derivative (JP-A-2-2428).
16), the energy gap as a semiconductor is as small as about 1.1 eV, the semiconductor exhibits high conductivity at a low doping level, and its conductive state is extremely stable. Therefore, since the absorbance of visible light becomes small especially during doping, it can be expected as a transparent conductor having excellent stability.
【００３８】[0038]
【作用】本発明においては、一般式（Ｉ）で表される二
環複素環式の重合体にスルホン化剤を作用させて、一般
式（II）で表される化学構造を含む新規な水溶性導電性
重合体が得られたことに基づくものであり、スルホン化
剤の種類によっては好ましくは他の酸化的脱水素剤の共
存下にスルホン化置換反応と酸化的な脱水素反応を同時
に行わせる特殊な反応によって初めて得られたものであ
る。In the present invention, a sulfonating agent is allowed to act on the bicyclic heterocyclic polymer represented by the general formula (I) to give a novel water-soluble compound containing the chemical structure represented by the general formula (II). It is based on the fact that a conductive polymer is obtained, and depending on the type of the sulfonating agent, preferably the sulfonation substitution reaction and the oxidative dehydrogenation reaction are simultaneously carried out in the presence of another oxidative dehydrogenating agent. It was obtained for the first time by a special reaction.
【００３９】[0039]
【実施例】以下、実施例によって、本発明を更に詳しく
説明する。しかし、本発明の技術的範囲をこれらの実施
例によって限定されるものでない。 （実施例１） 一般式（II）で表される重合体の製造方法＜Ｒ1 ＝Ｒ2
＝Ｈ、Ｍ＝Ｎａ+ ＞ 室温下、ポリ（１，３−ジヒドロイソチアナフテニレ
ン）５００ｍｇに発煙硫酸（２０％ ＳＯ3 ）４ｍｌを
撹拌しながら加えた。直ちに反応液は濃青色を呈した。
室温下３日撹拌した後、反応混合物を１００ｍｌの０．
１Ｎ ＮａＯＨ／メタノール中に投入し、沈降した重合
物を遠心分離した。重合物を水１００ｍｌに溶解し透析
膜を通して不純物の硫酸ナトリウムを除去した。水溶液
から水を留去し、真空乾燥してＮａ型の濃青色ポリマー
１７２ｍｇを得た（収率３４％）。得られたポリマーの
紫外可視スペクトルを図１に示す。ＧＰＣにより測定し
た分子量分布を図２に示す。赤外線吸収スペクトルを図
３に示す。 元素分析値（％）［Ｃ8 Ｈ3 Ｓ2 Ｏ3 Ｎａ］ 理論値：Ｃ；４１．０２％，Ｈ；１．２９％，Ｓ；２
７．３８％，Ｎａ；９．８２％ 実測値：Ｃ；４１．４７％，Ｈ；１．４１％，Ｓ；２
７．８１％，Ｎａ；９．５８％The present invention will be described in more detail with reference to the following examples. However, the technical scope of the present invention is not limited by these examples. (Example 1) Method for producing polymer represented by general formula (II) <R 1 = R 2
= H, M = Na + > At room temperature, 4 ml of fuming sulfuric acid (20% SO 3 ) was added to 500 mg of poly (1,3-dihydroisothianaphthenylene) with stirring. Immediately, the reaction solution turned deep blue.
After stirring at room temperature for 3 days, the reaction mixture was added with 100 ml of 0.1.
It was put into 1N NaOH / methanol, and the precipitated polymer was centrifuged. The polymer was dissolved in 100 ml of water and the impurity sodium sulfate was removed through a dialysis membrane. Water was distilled off from the aqueous solution and vacuum drying was performed to obtain 172 mg of a Na-type dark blue polymer (yield 34%). The UV-visible spectrum of the obtained polymer is shown in FIG. The molecular weight distribution measured by GPC is shown in FIG. The infrared absorption spectrum is shown in FIG. Elemental analysis value (%) [C 8 H 3 S 2 O 3 Na] Theoretical value: C; 41.02%, H; 1.29%, S; 2
7.38%, Na; 9.82% Found: C; 41.47%, H; 1.41%, S; 2
7.81%, Na; 9.58%
【００４０】（実施例２） 一般式（II）で表される重合体の製造方法＜Ｒ1 ＝Ｒ2
＝Ｈ、Ｍ＝Ｈ+ ＞ 実施例１と同様の方法で製造した反応混合物２００ｍｇ
を約５００ｍｌの水に溶解し、塩酸でｐＨを１．９に調
整し限外濾過によって精製、濃縮した後、溶媒留去、真
空乾燥により黒色ポリマー１５０ｍｇを得た。得られた
ポリマーの水溶液の紫外可視スペクトルを図４に示す。
次にＮａＯＨを加えｐＨ８付近に調整すると、溶液中の
ポリマーは図１に示される紫外可視スペクトルに戻っ
た。本製造法で得られた重合物の電導度を四端子法で測
定した結果、１Ｓ／ｃｍであった。Example 2 Method for producing polymer represented by general formula (II) <R 1 = R 2
= H, M = H + > 200 mg of reaction mixture prepared in the same manner as in Example 1
Was dissolved in about 500 ml of water, the pH was adjusted to 1.9 with hydrochloric acid, purified and concentrated by ultrafiltration, the solvent was distilled off and vacuum dried to obtain 150 mg of a black polymer. The UV-visible spectrum of the aqueous solution of the obtained polymer is shown in FIG.
Next, NaOH was added to adjust the pH to around 8, and the polymer in the solution returned to the UV-visible spectrum shown in FIG. The electric conductivity of the polymer obtained by this production method was measured by the four-terminal method, and it was 1 S / cm.
【００４１】（実施例３） 一般式（II）で表される重合体の製造方法＜Ｒ1 ＝Ｒ2
＝Ｈ、Ｍ＝Ｌｉ+ ＞ 実施例２と同様の方法で製造した黒色ポリマー６００ｍ
ｇを水１５０ｍｌに溶解し、Ｌｉ型のイオン交換樹脂
（アンバーライトＩＲ−１２０Ｂ）でイオン交換処理す
ることによってＬｉ型重合物水溶液を得た。水を蒸発さ
せると濃青色ポリマー６０５ｍｇを得た。得られたポリ
マーの紫外可視スペクトルは実施例１で得られたものと
同等であり、赤外線吸収スペクトルは図５に示した。 元素分析値（％）［Ｃ8 Ｈ3 Ｓ2 Ｏ3 Ｌｉ］ 理論値：Ｃ；４４．０４％，Ｈ；１．３９％，Ｓ；２
９．３９％，Ｌｉ；３．１８％ 実測値：Ｃ；４４．５９％，Ｈ；１．６２％，Ｓ；２
８．９６％，Ｌｉ；２．９０％(Example 3) Method for producing polymer represented by general formula (II) <R 1 = R 2
= H, M = Li + > 600 m of black polymer produced by the same method as in Example 2
g was dissolved in 150 ml of water and subjected to an ion exchange treatment with a Li type ion exchange resin (Amberlite IR-120B) to obtain a Li type polymer aqueous solution. Evaporation of water gave 605 mg of a dark blue polymer. The UV-visible spectrum of the obtained polymer is equivalent to that obtained in Example 1, and the infrared absorption spectrum is shown in FIG. Elemental analysis value (%) [C 8 H 3 S 2 O 3 Li] Theoretical value: C; 44.04%, H; 1.39%, S; 2
9.39%, Li; 3.18% Found: C; 44.59%, H; 1.62%, S; 2
8.96%, Li; 2.90%
【００４２】（実施例４） 一般式（II）で表される重合体の製造方法＜Ｒ1 ＝Ｒ2
＝Ｈ、Ｍ＝Ｎａ+ ＞ 室温下、ポリ（１，３−ジヒドロイソチアナフテニレ
ン）５００ｍｇを１ｍｌの過酢酸溶液（新実験化学講座
１７巻 酸化と還元Ｉ−２ ７４１頁 に記載の方法
で調製した。）に５℃以下で溶かした。更に５℃以下に
冷却しながら発煙硫酸（２０％ ＳＯ3 ）２ｍｌを撹拌
しながら加えた。直ちに反応液は濃青色を呈した。室温
下１日撹拌した後、反応混合物を１００ｍｌの０．１Ｎ
ＮａＯＨ／メタノールに投入し、沈降した重合物を遠
心分離した。重合物を水１００ｍｌに溶解し、透析膜を
通して不純物の硫酸ナトリウムを除去した。水溶液から
水を留去し、真空乾燥してＮａ型の濃青色ポリマー１９
５ｍｇを得た。得られたポリマーの紫外可視スペクトル
と赤外線吸収スペクトルは、実施例１で得られたものと
同様であった。Example 4 Production Method of Polymer Represented by General Formula (II) <R 1 = R 2
= H, M = Na + > At room temperature, 500 mg of poly (1,3-dihydroisothianaphthenylene) in 1 ml of peracetic acid solution (New Experimental Chemistry Lecture, Volume 17, Oxidation and Reduction I-2, page 741) Was prepared) and melted at 5 ° C or lower. Further, 2 ml of fuming sulfuric acid (20% SO 3 ) was added with stirring while cooling to 5 ° C or lower. Immediately, the reaction solution turned deep blue. After stirring at room temperature for 1 day, the reaction mixture was added to 100 ml of 0.1N.
It was poured into NaOH / methanol and the precipitated polymer was centrifuged. The polymer was dissolved in 100 ml of water and the impurity sodium sulfate was removed through a dialysis membrane. Water was distilled off from the aqueous solution and dried in vacuum to obtain a Na-type dark blue polymer 19
5 mg was obtained. The UV-visible spectrum and infrared absorption spectrum of the obtained polymer were the same as those obtained in Example 1.
【００４３】（実施例５） 一般式（II）で表される重合体の製造方法＜Ｒ1 ＝Ｈ、
Ｒ2 ＝Ｏ（ＣＨ2 ）9ＣＨ3 、Ｍ＝Ｎａ+ ＞ 特開平２−２４２８１６号公報に記載の方法で製造した
ポリ（５−デシルオキシ−１，３−ジヒドロイソチアナ
フテニレン）５００ｍｇを撹拌しながら、発煙硫酸（２
０％ ＳＯ3 ）４．０ｍｌをゆっくりと加えた。直ちに
反応液は濃青色を呈した。反応混合物を１００ｍｌの
０．５Ｎ ＮａＯＨ／メタノールに沈降させ、遠心分離
により分離した。固体を水１００ｍｌに溶かし、透析に
より過剰の硫酸ナトリウムを除去した後、溶媒留去、真
空乾燥して黒色ポリマー１２０ｍｇを得た。得られたポ
リマーの紫外可視スペクトルは、実施例１で得られたも
のと同様であった。(Example 5) Process for producing polymer represented by general formula (II) <R 1 = H,
Stirring R 2 = O (CH 2) 9 CH 3, M = Na +> Patent poly prepared by the method described in 2-242816 JP (5-decyloxy-1,3-dihydro isothianaphthenylene) 500 mg While fuming sulfuric acid (2
4.0 ml of 0% SO 3 ) was added slowly. Immediately, the reaction solution turned deep blue. The reaction mixture was precipitated in 100 ml of 0.5 N NaOH / methanol and separated by centrifugation. The solid was dissolved in 100 ml of water, the excess sodium sulfate was removed by dialysis, the solvent was distilled off, and the residue was vacuum dried to obtain 120 mg of a black polymer. The UV-visible spectrum of the obtained polymer was similar to that obtained in Example 1.
【００４４】（実施例６） 一般式（II）で表される重合体の製造方法＜Ｒ1 ＝Ｒ2
＝Ｈ、Ｍ＝Ｎａ+ ＞ 室温下、ポリ（１，３−ジヒドロイソチアナフテニレ
ン）５００ｍｇを１ｍｌの氷酢酸に溶かした液に発煙硫
酸（２０％ ＳＯ3 含有）４ｍｌを撹拌しながら加え
た。ただちに反応液は濃青色を呈した。室温下３日撹拌
した後、反応混合物を１００ｍｌの０．１Ｎ ＮａＯＨ
／メタノール中に投入し、沈降した重合物を遠心分離し
た。重合物を水１００ｍｌに溶解し透析膜を通して不純
物の硫酸ナトリウムを除去した。水溶液から水を留去し
真空乾燥してＮａ型の濃青色ポリマー２０１ｍｇを得
た。得られたポリマーの紫外可視スペクトルと赤外線吸
収スペクトルは、実施例１で得られたものと同様であっ
た。(Example 6) Process for producing polymer represented by general formula (II) <R 1 = R 2
= H, M = Na + > At room temperature, 4 ml of fuming sulfuric acid (containing 20% SO 3 ) was added to a liquid obtained by dissolving 500 mg of poly (1,3-dihydroisothianaphthenylene) in 1 ml of glacial acetic acid while stirring. . Immediately, the reaction solution became deep blue. After stirring at room temperature for 3 days, the reaction mixture was added to 100 ml of 0.1N NaOH.
/ Powder in methanol and the precipitated polymer was centrifuged. The polymer was dissolved in 100 ml of water and the impurity sodium sulfate was removed through a dialysis membrane. Water was distilled off from the aqueous solution and vacuum drying was performed to obtain 201 mg of a Na-type dark blue polymer. The UV-visible spectrum and infrared absorption spectrum of the obtained polymer were the same as those obtained in Example 1.
【００４５】（実施例７） 一般式（II）で表される重合体＜Ｒ1 ＝Ｒ2 ＝Ｈ、Ｍ＝
Ｈ+ ＞を含む導電性樹脂成形体の製造方法 １００ｍｌのナスフラスコにトリクロロエチレンを１０
ｍｌとり、これに加温しながら低密度ポリエチレン９０
０ｍｇとポリ（１，３−ジヒドロイソチアナフテニレ
ン）１００ｍｇを溶解させた。この混合溶液を並ガラス
基板（６ｃｍ角）上にスピンコートで成膜し減圧乾燥し
て透明フィルムを作製した。次にフィルムを剥離した
後、室温下発煙硫酸（２０％ ＳＯ3 ）４ｍｌ中に投入
し、３日間放置した。フィルムは白色透明から淡黒灰色
に変わった。フィルムを水洗し風乾した結果、しなやか
な複合フィルムを合成した。得られた複合ポリマーの紫
外可視スペクトルを図６に示した。複合フィルムの電気
伝導度を四端子法で測定した結果、３Ｘ１０-2Ｓ／ｃｍ
であった。Example 7 Polymer represented by the general formula (II) <R 1 = R 2 = H, M =
Method for producing electrically conductive resin molded body containing H + >
Take 90 ml of low-density polyethylene 90 while heating.
0 mg and 100 mg of poly (1,3-dihydroisothianaphthenylene) were dissolved. This mixed solution was spin-coated on a normal glass substrate (6 cm square) and dried under reduced pressure to produce a transparent film. Next, after peeling off the film, it was put into 4 ml of fuming sulfuric acid (20% SO 3 ) at room temperature and left for 3 days. The film turned from white transparent to light black gray. As a result of washing the film with water and air-drying, a supple composite film was synthesized. The UV-visible spectrum of the obtained composite polymer is shown in FIG. The electric conductivity of the composite film was measured by the four-terminal method, and was 3 × 10 -2 S / cm.
Met.
【００４６】（実施例８） 一般式（II）で表される重合体＜Ｒ1 ＝Ｒ2 ＝Ｈ、Ｍ＝
Ｈ+ ＞を含む導電性樹脂成形体の製造方法 １００ｍｌのナスフラスコにＴＨＦを１５ｍｌとり、こ
れに加温しながらポリ塩化ビニル１ｇとポリ（１，３−
ジヒドロイソチアナフテニレン）５００ｍｇを溶かし
た。この混合溶液を並ガラス基板（６ｃｍ角）上にスピ
ンコートで成膜し減圧乾燥して白色のフィルムを作製し
た。剥離したフィルムを室温下、発煙硫酸（２０％ Ｓ
Ｏ3 ）４ｍｌ中に投入し、１０時間後取り出した。淡黒
灰色のフィルムを水洗し風乾した。得られた複合ポリマ
ーの紫外可視スペクトルを図７に示した。(Example 8) Polymer represented by the general formula (II) <R 1 = R 2 = H, M =
Method for producing conductive resin molded body containing H + > 15 ml of THF was placed in a 100 ml eggplant flask, and 1 g of polyvinyl chloride and poly (1,3-
500 mg of dihydroisothianaphthenylene) was dissolved. This mixed solution was spin-coated on a normal glass substrate (6 cm square) and dried under reduced pressure to produce a white film. The peeled film is treated with fuming sulfuric acid (20% S
It was put into 4 ml of O 3 ) and taken out after 10 hours. The light gray film was washed with water and air dried. The UV-visible spectrum of the obtained composite polymer is shown in FIG.
【００４７】（実施例９） 一般式（II）で表される重合体＜Ｒ1 ＝Ｒ2 ＝Ｈ、Ｍ＝
Ｈ+ ＞を含む導電性樹脂成形体の製造方法 １００ｍｌのナスフラスコにトリクロロエチレンを１０
ｍｌとり、これに加温しながら低密度ポリエチレン９０
０ｍｇとポリ（１，３−ジヒドロイソチアナフテニレ
ン）１００ｍｇを溶解させた。この混合溶液を並ガラス
基板（６ｃｍ角）上にスピンコートで成膜し減圧乾燥し
て透明フィルムを作製した。ガラス基板から剥離したフ
ィルム表面に水を噴霧した後、三酸化硫黄５００ｍｇの
入った密閉容器に４０℃で３０日間保存した。フィルム
は白色透明から淡黒灰色にかわった。フィルムを水洗し
風乾した結果、しなやかな複合フィルムを合成した。得
られた複合ポリマーの紫外可視スペクトルを図８に示し
た。(Example 9) Polymer represented by the general formula (II) <R 1 = R 2 = H, M =
Method for producing electrically conductive resin molded body containing H + >
Take 90 ml of low-density polyethylene 90 while heating.
0 mg and 100 mg of poly (1,3-dihydroisothianaphthenylene) were dissolved. This mixed solution was spin-coated on a normal glass substrate (6 cm square) and dried under reduced pressure to produce a transparent film. After water was sprayed on the surface of the film peeled from the glass substrate, the film was stored in a closed container containing 500 mg of sulfur trioxide at 40 ° C. for 30 days. The film changed from white transparent to light black gray. As a result of washing the film with water and air-drying, a supple composite film was synthesized. The UV-visible spectrum of the obtained composite polymer is shown in FIG.
【００４８】[0048]
【発明の効果】本発明の製造法で製造された導電性重合
体は、水溶性であって、加工性の優れた高い導電性重合
体であり、そのため精密な加工の要求される電極、セン
サー、エレクトロニクス表示素子、非線形光学素子、光
学変換素子、帯電防止材など各種導電材料あるいは光学
材料として有用なものである。また、本発明に製造法の
特徴は原料に加工、成形性に優れた前躯体ポリマーを用
い、温和な条件で高い導電性を有する重合体及び樹脂成
形体、樹脂複合成形体を製造するのに特に有用である。The electroconductive polymer produced by the production method of the present invention is a water-soluble and highly electroconductive polymer having excellent processability, and therefore electrodes and sensors which require precise processing. , Electronic display elements, non-linear optical elements, optical conversion elements, antistatic materials, and other various conductive materials or optical materials. Further, the feature of the production method in the present invention is to process a raw material, to use a precursor polymer having excellent moldability, to produce a polymer and a resin molded article having high conductivity under mild conditions, and a resin composite molded article. Especially useful.
【図１】実施例１で得た重合体の紫外可視スペクトルで
ある。1 is an ultraviolet-visible spectrum of the polymer obtained in Example 1. FIG.
【図２】実施例１で得た重合体のゲルパーミエーション
クロマトグラフである。2 is a gel permeation chromatograph of the polymer obtained in Example 1. FIG.
【図３】実施例１で得た重合体の赤外線吸収スペクトル
である。FIG. 3 is an infrared absorption spectrum of the polymer obtained in Example 1.
【図４】実施例２で得た重合体の紫外可視スペクトルで
ある。4 is an ultraviolet-visible spectrum of the polymer obtained in Example 2. FIG.
【図５】実施例３で得た重合体の赤外線吸収スペクトル
である。5 is an infrared absorption spectrum of the polymer obtained in Example 3. FIG.
【図６】実施例７で得た重合体の紫外可視スペクトルで
ある。6 is an ultraviolet-visible spectrum of the polymer obtained in Example 7. FIG.
【図７】実施例８で得た重合体の紫外可視スペクトルで
ある。7 is an ultraviolet-visible spectrum of the polymer obtained in Example 8. FIG.
【図８】実施例９で得た重合体の紫外可視スペクトルで
ある。8 is an ultraviolet-visible spectrum of the polymer obtained in Example 9. FIG.
【手続補正書】[Procedure amendment]
【提出日】平成５年６月１０日[Submission date] June 10, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項２[Name of item to be corrected] Claim 2
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【化３】 （式中、Ｒ1 、Ｒ2 は前記と同じ）で表される化学構造
を含む重合体の成形体または該重合体と他の樹脂との複
合物成形体にスルホン化剤を作用させることにより、一
般式（II）[Chemical 3] (In the formula, R 1 and R 2 are the same as above) By acting a sulfonating agent on a molded product of a polymer having a chemical structure or a molded product of the polymer and another resin. , General formula (II)
【化４】 （式中、Ｒ1 、Ｒ2 、Ｍ及びｍは前記と同じ）で表され
る化学構造を含む重合体の成形体または該重合体と他の
樹脂との複合物成形体を製造することを特徴とする導電
性重合体成形物の製造方法。[Chemical 4] (Wherein R 1 , R 2 , M and m are the same as above) to produce a molded article of a polymer having a chemical structure or a composite molded article of the polymer and another resin. A method for producing a characteristic electrically conductive polymer molding.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１０】また一般式（Ｉ）The general formula (I)
【化７】 （式中、Ｒ1 、Ｒ2 は前記と同じ）で表される化学構造
を含む重合体の成形体または該重合体と他の樹脂との複
合物成形体にスルホン化剤を作用させることにより、一
般式（II）[Chemical 7] (In the formula, R 1 and R 2 are the same as above) By acting a sulfonating agent on a molded product of a polymer having a chemical structure or a molded product of the polymer and another resin. , General formula (II)
【化８】 （式中、Ｒ1 、Ｒ2 、Ｍ及びｍは前記と同じ）で表され
る化学構造を含む重合体の成形体または該重合体と他の
樹脂との複合物成形体を製造することを特徴とする導電
性重合体成形物の製造方法に関する。[Chemical 8] (Wherein R 1 , R 2 , M and m are the same as above) to produce a molded article of a polymer having a chemical structure or a composite molded article of the polymer and another resin. The present invention relates to a method for producing a characteristic electrically conductive polymer molded product.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２５[Name of item to be corrected] 0025
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２５】また反応温度は、それぞれの反応方法によ
って定められるもので、特に限定できるものではない
が、一般には−８０℃〜２５０℃の温度範囲が望まし
く、特に−３０℃〜１５０℃の温度範囲で行われること
が望ましい。反応時間は、反応方法及び反応温度、反応
圧力あるいは重合体の化学構造等によって異なるので一
概には規定できないが、通常は０．０１時間から２４０
時間が望ましい。反応圧力は、常圧で行われることが好
ましいが、１０-5気圧から１００気圧下で行うことがで
きる。The reaction temperature is determined according to each reaction method and is not particularly limited. However, a temperature range of -80 ° C to 250 ° C is generally desirable, and a temperature range of -30 ° C to 150 ° C is particularly preferable. It is desirable to be done in. The reaction time varies depending on the reaction method, the reaction temperature, the reaction pressure, the chemical structure of the polymer and the like, and therefore cannot be specified unconditionally, but is usually 0.01 hour to 240 hours.
Time is desirable. The reaction pressure is preferably atmospheric pressure, but may be under 10 −5 to 100 atm.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３２[Name of item to be corrected] 0032
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３２】また成形体であってその表面が一般式（I
I）で表される化学構造を含む重合体成形体または該重
合体と他の樹脂との複合体となっている表面が導電性の
成形体は、一般式（Ｉ）の１，３−ジヒドロイソチアナ
フテニレン構造を含む重合体の成形体または該重合体と
他の樹脂との複合体からなる成形体から製造することが
できる。A molded product whose surface has the general formula (I
Polymer molding containing the chemical structure represented by I) or the weight thereof
Combined with other surface has a complex conductive resin of <br/> moldings general formula (I) of 1,3-dihydro isothianaphthenylene molding of polymers containing oxyalkylene structure or It can be produced from a molded product composed of a composite of the polymer and another resin.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３９[Correction target item name] 0039
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３９】[0039]
【実施例】以下、実施例によって、本発明を更に詳しく
説明する。しかし、本発明の技術的範囲をこれらの実施
例によって限定されるものでない。 （実施例１） 一般式（II）で表される重合体の製造方法＜Ｒ1 ＝Ｒ2
＝Ｈ、Ｍ＝Ｎａ+ ＞ 室温下、ポリ（１，３−ジヒドロイソチアナフテニレ
ン）５００ｍｇに発煙硫酸（２０％ ＳＯ3 ）４ｍｌを
撹拌しながら加えた。直ちに反応液は濃青色を呈した。
室温下３日撹拌した後、反応混合物を１００ｍｌの０．
１Ｎ ＮａＯＨ／メタノール中に投入し、沈降した重合
物を遠心分離した。重合物を水１００ｍｌに溶解し透析
膜を通して不純物の硫酸ナトリウムを除去した。水溶液
から水を留去し、真空乾燥してＮａ型の濃青色ポリマー
１７２ｍｇを得た（収率３４％）。得られたポリマーの
可視近赤外スペクトルを図１に示す。ＧＰＣにより測定
した分子量分布を図２に示す。赤外線吸収スペクトルを
図３に示す。 元素分析値（％）［Ｃ8 Ｈ3 Ｓ2 Ｏ3 Ｎａ］ 理論値：Ｃ；４１．０２％，Ｈ；１．２９％，Ｓ；２
７．３８％，Ｎａ；９．８２％ 実測値：Ｃ；４１．４７％，Ｈ；１．４１％，Ｓ；２
７．８１％，Ｎａ；９．５８％The present invention will be described in more detail with reference to the following examples. However, the technical scope of the present invention is not limited by these examples. (Example 1) Method for producing polymer represented by general formula (II) <R 1 = R 2
= H, M = Na + > At room temperature, 4 ml of fuming sulfuric acid (20% SO 3 ) was added to 500 mg of poly (1,3-dihydroisothianaphthenylene) with stirring. Immediately, the reaction solution turned deep blue.
After stirring at room temperature for 3 days, the reaction mixture was added with 100 ml of 0.1.
It was put into 1N NaOH / methanol, and the precipitated polymer was centrifuged. The polymer was dissolved in 100 ml of water and the impurity sodium sulfate was removed through a dialysis membrane. Water was distilled off from the aqueous solution and vacuum drying was performed to obtain 172 mg of a Na-type dark blue polymer (yield 34%). The resulting polymer
The the visible near-infrared spectrum is shown in Figure 1. The molecular weight distribution measured by GPC is shown in FIG. The infrared absorption spectrum is shown in FIG. Elemental analysis value (%) [C 8 H 3 S 2 O 3 Na] Theoretical value: C; 41.02%, H; 1.29%, S; 2
7.38%, Na; 9.82% Found: C; 41.47%, H; 1.41%, S; 2
7.81%, Na; 9.58%
【手続補正６】[Procedure correction 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４０[Correction target item name] 0040
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４０】（実施例２） 一般式（II）で表される重合体の製造方法＜Ｒ1 ＝Ｒ2
＝Ｈ、Ｍ＝Ｈ+ ＞ 実施例１と同様の方法で製造した反応混合物２００ｍｇ
を約５００ｍｌの水に溶解し、塩酸でｐＨを１．９に調
整し限外濾過によって精製、濃縮した後、溶媒留去、真
空乾燥により黒色ポリマー１５０ｍｇを得た。得られた
ポリマーの水溶液の可視近赤外スペクトルを図４に示
す。次にＮａＯＨを加えｐＨ８付近に調整すると、溶液
中のポリマーは図１に示される可視近赤外スペクトルに
戻った。本製造法で得られた重合物の電導度を四端子法
で測定した結果、１Ｓ／ｃｍであった。Example 2 Method for producing polymer represented by general formula (II) <R 1 = R 2
= H, M = H + > 200 mg of reaction mixture prepared in the same manner as in Example 1
Was dissolved in about 500 ml of water, the pH was adjusted to 1.9 with hydrochloric acid, purified and concentrated by ultrafiltration, the solvent was distilled off and vacuum dried to obtain 150 mg of a black polymer. The the visible near-infrared spectrum of the aqueous solution of the resulting polymer is shown in FIG. Next, when adjusted to about pH8 added NaOH, the polymer in the solution was returned to the visible near-infrared spectrum Ru shown in Figure 1. The electric conductivity of the polymer obtained by this production method was measured by the four-terminal method, and it was 1 S / cm.
【手続補正７】[Procedure Amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４１[Correction target item name] 0041
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４１】（実施例３） 一般式（II）で表される重合体の製造方法＜Ｒ1 ＝Ｒ2
＝Ｈ、Ｍ＝Ｌｉ+ ＞ 実施例２と同様の方法で製造した黒色ポリマー６００ｍ
ｇを水１５０ｍｌに溶解し、Ｌｉ型のイオン交換樹脂
（アンバーライトＩＲ−１２０Ｂ）でイオン交換処理す
ることによってＬｉ型重合物水溶液を得た。水を蒸発さ
せると濃青色ポリマー６０５ｍｇを得た。得られたポリ
マーの可視近赤外スペクトルは実施例１で得られたもの
と同等であり、赤外線吸収スペクトルは図５に示した。 元素分析値（％）［Ｃ8 Ｈ3 Ｓ2 Ｏ3 Ｌｉ］ 理論値：Ｃ；４４．０４％，Ｈ；１．３９％，Ｓ；２
９．３９％，Ｌｉ；３．１８％ 実測値：Ｃ；４４．５９％，Ｈ；１．６２％，Ｓ；２
８．９６％，Ｌｉ；２．９０％(Example 3) Method for producing polymer represented by general formula (II) <R 1 = R 2
= H, M = Li + > 600 m of black polymer produced by the same method as in Example 2
g was dissolved in 150 ml of water and subjected to an ion exchange treatment with a Li type ion exchange resin (Amberlite IR-120B) to obtain a Li type polymer aqueous solution. Evaporation of water gave 605 mg of a dark blue polymer. The visible near-infrared spectrum of the polymer obtained was comparable to those obtained in Example 1, infrared absorption spectrum shown in FIG. Elemental analysis value (%) [C 8 H 3 S 2 O 3 Li] Theoretical value: C; 44.04%, H; 1.39%, S; 2
9.39%, Li; 3.18% Found: C; 44.59%, H; 1.62%, S; 2
8.96%, Li; 2.90%
【手続補正８】[Procedure Amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４２[Correction target item name] 0042
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４２】（実施例４） 一般式（II）で表される重合体の製造方法＜Ｒ1 ＝Ｒ2
＝Ｈ、Ｍ＝Ｎａ+ ＞ 室温下、ポリ（１，３−ジヒドロイソチアナフテニレ
ン）５００ｍｇを１ｍｌの過酢酸溶液（新実験化学講座
１７巻 酸化と還元Ｉ−２ ７４１頁 に記載の方法
で調製した。）に５℃以下で溶かした。更に５℃以下に
冷却しながら発煙硫酸（２０％ ＳＯ3 ）２ｍｌを撹拌
しながら加えた。直ちに反応液は濃青色を呈した。室温
下１日撹拌した後、反応混合物を１００ｍｌの０．１Ｎ
ＮａＯＨ／メタノールに投入し、沈降した重合物を遠
心分離した。重合物を水１００ｍｌに溶解し、透析膜を
通して不純物の硫酸ナトリウムを除去した。水溶液から
水を留去し、真空乾燥してＮａ型の濃青色ポリマー１９
５ｍｇを得た。得られたポリマーの可視近赤外スペクト
ルと赤外線吸収スペクトルは、実施例１で得られたもの
と同様であった。Example 4 Production Method of Polymer Represented by General Formula (II) <R 1 = R 2
= H, M = Na + > At room temperature, 500 mg of poly (1,3-dihydroisothianaphthenylene) in 1 ml of peracetic acid solution (New Experimental Chemistry Lecture, Volume 17, Oxidation and Reduction I-2, page 741) Was prepared) and melted at 5 ° C or lower. Further, 2 ml of fuming sulfuric acid (20% SO 3 ) was added with stirring while cooling to 5 ° C or lower. Immediately, the reaction solution turned deep blue. After stirring at room temperature for 1 day, the reaction mixture was added to 100 ml of 0.1N.
It was poured into NaOH / methanol and the precipitated polymer was centrifuged. The polymer was dissolved in 100 ml of water and the impurity sodium sulfate was removed through a dialysis membrane. Water was distilled off from the aqueous solution and dried in vacuum to obtain a Na-type dark blue polymer 19
5 mg was obtained. It obtained the visible near-infrared spectrum <br/> Le and infrared absorption spectrum of the polymer was similar to that obtained in Example 1.
【手続補正９】[Procedure Amendment 9]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４３[Correction target item name] 0043
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４３】（実施例５） 一般式（II）で表される重合体の製造方法＜Ｒ1 ＝Ｈ、
Ｒ2 ＝Ｏ（ＣＨ2 ）9ＣＨ3 、Ｍ＝Ｎａ+ ＞ 特開平２−２４２８１６号公報に記載の方法に準じて製
造した５−デシルイソチアナフテンを特開昭６１−１７
５８１号公報に記載の方法に準じて製造したポリ（５−
デシルオキシ−１，３−ジヒドロイソチアナフテニレ
ン）５００ｍｇを撹拌しながら、発煙硫酸（２０％ Ｓ
Ｏ3 ）４．０ｍｌをゆっくりと加えた。直ちに反応液は
濃青色を呈した。反応混合物を１００ｍｌの０．５Ｎ
ＮａＯＨ／メタノールに沈降させ、遠心分離により分離
した。固体を水１００ｍｌに溶かし、透析により過剰の
硫酸ナトリウムを除去した後、溶媒留去、真空乾燥して
黒色ポリマー１２０ｍｇを得た。得られたポリマーの可
視近赤外スペクトルは、実施例１で得られたものと同様
であった。(Example 5) Process for producing polymer represented by general formula (II) <R 1 = H,
R 2 = O (CH 2) 9 CH 3, M = Na +> manufactured according to the method described in JP-A-2-242816
The produced 5-decylisothianaphthene is disclosed in JP-A-61-17.
Poly (5-) produced according to the method described in Japanese Patent No. 581
While stirring 500 mg of decyloxy-1,3-dihydroisothianaphthenylene, fuming sulfuric acid (20% S
O 3) 4.0ml was added slowly. Immediately, the reaction solution turned deep blue. 100 ml of 0.5N reaction mixture
It was precipitated in NaOH / methanol and separated by centrifugation. The solid was dissolved in 100 ml of water, the excess sodium sulfate was removed by dialysis, the solvent was distilled off, and the residue was vacuum dried to obtain 120 mg of a black polymer. The visible near-infrared spectrum of the obtained polymer was similar to that obtained in Example 1.
【手続補正１０】[Procedure Amendment 10]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４４[Correction target item name] 0044
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４４】（実施例６） 一般式（II）で表される重合体の製造方法＜Ｒ1 ＝Ｒ2
＝Ｈ、Ｍ＝Ｎａ+ ＞ 室温下、ポリ（１，３−ジヒドロイソチアナフテニレ
ン）５００ｍｇを１ｍｌの氷酢酸に溶かした液に発煙硫
酸（２０％ ＳＯ3 含有）４ｍｌを撹拌しながら加え
た。ただちに反応液は濃青色を呈した。室温下３日撹拌
した後、反応混合物を１００ｍｌの０．１Ｎ ＮａＯＨ
／メタノール中に投入し、沈降した重合物を遠心分離し
た。重合物を水１００ｍｌに溶解し透析膜を通して不純
物の硫酸ナトリウムを除去した。水溶液から水を留去し
真空乾燥してＮａ型の濃青色ポリマー２０１ｍｇを得
た。得られたポリマーの可視近赤外スペクトルと赤外線
吸収スペクトルは、実施例１で得られたものと同様であ
った。(Example 6) Process for producing polymer represented by general formula (II) <R 1 = R 2
= H, M = Na + > At room temperature, 4 ml of fuming sulfuric acid (containing 20% SO 3 ) was added to a liquid obtained by dissolving 500 mg of poly (1,3-dihydroisothianaphthenylene) in 1 ml of glacial acetic acid while stirring. . Immediately, the reaction solution became deep blue. After stirring at room temperature for 3 days, the reaction mixture was added to 100 ml of 0.1N NaOH.
/ Powder in methanol and the precipitated polymer was centrifuged. The polymer was dissolved in 100 ml of water and the impurity sodium sulfate was removed through a dialysis membrane. Water was distilled off from the aqueous solution and vacuum drying was performed to obtain 201 mg of a Na-type dark blue polymer. The visible near infrared spectrum and the infrared absorption spectrum of the obtained polymer were similar to those obtained in Example 1.
【手続補正１１】[Procedure Amendment 11]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４５[Name of item to be corrected] 0045
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４５】（実施例７） 一般式（II）で表される重合体＜Ｒ1 ＝Ｒ2 ＝Ｈ、Ｍ＝
Ｈ+ ＞を含む導電性樹脂成形体の製造方法 １００ｍｌのナスフラスコにトリクロロエチレンを１０
ｍｌとり、これに加温しながら低密度ポリエチレン９０
０ｍｇとポリ（１，３−ジヒドロイソチアナフテニレ
ン）１００ｍｇを溶解させた。この混合溶液を並ガラス
基板（６ｃｍ角）上にスピンコートで成膜し減圧乾燥し
て透明フィルムを作製した。次にフィルムを剥離した
後、室温下発煙硫酸（２０％ ＳＯ3 ）４ｍｌ中に投入
し、３日間放置した。フィルムは白色透明から淡黒灰色
に変わった。フィルムを水洗し風乾した結果、しなやか
な複合フィルムを合成した。得られた複合ポリマーの可
視近赤外スペクトルを図６に示した。複合フィルムの電
気伝導度を四端子法で測定した結果、３Ｘ１０-2Ｓ／ｃ
ｍであった。Example 7 Polymer represented by the general formula (II) <R 1 = R 2 = H, M =
Method for producing electrically conductive resin molded body containing H + >
Take 90 ml of low-density polyethylene 90 while heating.
0 mg and 100 mg of poly (1,3-dihydroisothianaphthenylene) were dissolved. This mixed solution was spin-coated on a normal glass substrate (6 cm square) and dried under reduced pressure to produce a transparent film. Next, after peeling off the film, it was put into 4 ml of fuming sulfuric acid (20% SO 3 ) at room temperature and left for 3 days. The film turned from white transparent to light black gray. As a result of washing the film with water and air-drying, a supple composite film was synthesized. The visible near-infrared spectrum of the obtained composite polymer is shown in FIG. The electric conductivity of the composite film was measured by the four-terminal method, and was 3X10 -2 S / c.
It was m.
【手続補正１２】[Procedure Amendment 12]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４６[Correction target item name] 0046
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４６】（実施例８） 一般式（II）で表される重合体＜Ｒ1 ＝Ｒ2 ＝Ｈ、Ｍ＝
Ｈ+ ＞を含む導電性樹脂成形体の製造方法 １００ｍｌのナスフラスコにＴＨＦを１５ｍｌとり、こ
れに加温しながらポリ塩化ビニル１ｇとポリ（１，３−
ジヒドロイソチアナフテニレン）５００ｍｇを溶かし
た。この混合溶液を並ガラス基板（６ｃｍ角）上にスピ
ンコートで成膜し減圧乾燥して白色のフィルムを作製し
た。剥離したフィルムを室温下、発煙硫酸（２０％ Ｓ
Ｏ3 ）４ｍｌ中に投入し、１０時間後取り出した。淡黒
灰色のフィルムを水洗し風乾した。得られた複合ポリマ
ーの可視近赤外スペクトルを図７に示した。(Example 8) Polymer represented by the general formula (II) <R 1 = R 2 = H, M =
Method for producing conductive resin molded body containing H + > 15 ml of THF was placed in a 100 ml eggplant flask, and 1 g of polyvinyl chloride and poly (1,3-
500 mg of dihydroisothianaphthenylene) was dissolved. This mixed solution was spin-coated on a normal glass substrate (6 cm square) and dried under reduced pressure to produce a white film. The peeled film is treated with fuming sulfuric acid (20% S
It was put into 4 ml of O 3 ) and taken out after 10 hours. The light gray film was washed with water and air dried. The the visible near-infrared spectrum of the resulting composite polymer shown in FIG.
【手続補正１３】[Procedure Amendment 13]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４７[Correction target item name] 0047
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４７】（実施例９） 一般式（II）で表される重合体＜Ｒ1 ＝Ｒ2 ＝Ｈ、Ｍ＝
Ｈ+ ＞を含む導電性樹脂成形体の製造方法 １００ｍｌのナスフラスコにトリクロロエチレンを１０
ｍｌとり、これに加温しながら低密度ポリエチレン９０
０ｍｇとポリ（１，３−ジヒドロイソチアナフテニレ
ン）１００ｍｇを溶解させた。この混合溶液を並ガラス
基板（６ｃｍ角）上にスピンコートで成膜し減圧乾燥し
て透明フィルムを作製した。ガラス基板から剥離したフ
ィルム表面に水を噴霧した後、三酸化硫黄５００ｍｇの
入った密閉容器に４０℃で３０日間保存した。フィルム
は白色透明から淡黒灰色にかわった。フィルムを水洗し
風乾した結果、しなやかな複合フィルムを合成した。得
られた複合ポリマーの可視近赤外スペクトルを図８に示
した。(Example 9) Polymer represented by the general formula (II) <R 1 = R 2 = H, M =
Method for producing electrically conductive resin molded body containing H + >
Take 90 ml of low-density polyethylene 90 while heating.
0 mg and 100 mg of poly (1,3-dihydroisothianaphthenylene) were dissolved. This mixed solution was spin-coated on a normal glass substrate (6 cm square) and dried under reduced pressure to produce a transparent film. After water was sprayed on the surface of the film peeled from the glass substrate, the film was stored in a closed container containing 500 mg of sulfur trioxide at 40 ° C. for 30 days. The film changed from white transparent to light black gray. As a result of washing the film with water and air-drying, a supple composite film was synthesized. The the visible near-infrared spectrum of the resulting composite polymer shown in FIG.
【手続補正１４】[Procedure Amendment 14]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】図面の簡単な説明[Name of item to be corrected] Brief description of the drawing
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図面の簡単な説明】[Brief description of drawings]
【図１】実施例１で得た重合体の可視近赤外スペクトル
である。1 is a the visible near-infrared spectrum of the polymer in Example 1.
【図２】実施例１で得た重合体のゲルパーミエーション
クロマトグラフである。2 is a gel permeation chromatograph of the polymer obtained in Example 1. FIG.
【図３】実施例１で得た重合体の赤外線吸収スペクトル
である。FIG. 3 is an infrared absorption spectrum of the polymer obtained in Example 1.
【図４】実施例２で得た重合体の可視近赤外スペクトル
である。4 is a the visible near-infrared spectrum of the polymer obtained in Example 2.
【図５】実施例３で得た重合体の赤外線吸収スペクトル
である。5 is an infrared absorption spectrum of the polymer obtained in Example 3. FIG.
【図６】実施例７で得た重合体の可視近赤外スペクトル
である。6 is a the visible near-infrared spectrum of the polymer in Example 7.
【図７】実施例８で得た重合体の可視近赤外スペクトル
である。7 is a the visible near-infrared spectrum of the polymer in Example 8.
【図８】実施例９で得た重合体の可視近赤外スペクトル
である。8 is a the visible near-infrared spectrum of the polymer in Example 9.
【手続補正１５】[Procedure Amendment 15]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】全図[Correction target item name] All drawings
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図１】 [Figure 1]
【図２】 [Fig. 2]
【図３】 [Figure 3]
【図４】 [Figure 4]
【図５】 [Figure 5]
【図６】 [Figure 6]
【図７】 [Figure 7]
【図８】 [Figure 8]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 池ノ上 芳章 東京都大田区多摩川２−24−25昭和電工株 式会社総合技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiaki Ikenoue 2-24-25 Tamagawa, Ota-ku, Tokyo Showa Denko K.K.
Claims (3)
数１〜２０の直鎖状もしくは分岐状のアルキル基または
アルコキシ基、ハロゲン、ニトロ基、１級、２級または
３級アミノ基、トリハロメチル基、フェニル基、置換フ
ェニル基を表す。Ｒ1 、Ｒ2 のアルキル基またはアルコ
キシ基には、カルボニル、エーテル、アミド結合を任意
に含んでも良い。）で表される化学構造を含む重合体に
スルホン化剤を作用させることにより、下記一般式（I
I） 【化２】 （式中、Ｒ1 、Ｒ2 は前記と同じであり、ＭはＨ+ もし
くはＮａ+ 、Ｌｉ+ 、Ｋ+ 等のアルカリ金属イオンまた
はアンモニウムイオンもしくはアルキル置換した第４級
アンモニウムイオン等のカチオンを表す。ｍは０．２〜
２の範囲である。）で表される化学構造を含む重合体を
製造することを特徴とする導電性重合体の製造方法。1. A compound represented by the general formula (I): (In the formula, R 1 and R 2 are each independently H, or a linear or branched alkyl group or alkoxy group having 1 to 20 carbon atoms, halogen, nitro group, primary, secondary or tertiary amino group. , A trihalomethyl group, a phenyl group, and a substituted phenyl group. The alkyl group or alkoxy group of R 1 and R 2 may include a carbonyl, ether, or amide bond. By reacting the polymer with a sulfonating agent, the following general formula (I
I) [Chemical 2] (In the formula, R 1 and R 2 are the same as described above, and M is an alkali metal ion such as H + or Na + , Li + , K + or a cation such as an ammonium ion or an alkyl-substituted quaternary ammonium ion. Represents, m is 0.2 to
The range is 2. The manufacturing method of the electroconductive polymer characterized by manufacturing the polymer containing the chemical structure represented by these.
を含む重合体または該重合体と他の樹脂との複合物成形
体にスルホン化剤を作用させることにより、一般式（I
I） 【化４】 （式中、Ｒ1 、Ｒ2 、Ｍ及びｍは前記と同じ）で表され
る化学構造を含む重合体または該重合体と他の樹脂との
複合物成形体を製造することを特徴とする導電性重合体
成形物の製造方法。2. A compound represented by the general formula (I): (Wherein R 1 and R 2 are the same as above), a sulfonating agent is applied to a polymer having a chemical structure represented by the chemical structure or a composite molded product of the polymer and another resin to give a compound of the general formula (I
I) [Chemical 4] (Wherein R 1 , R 2 , M and m are the same as described above), or a polymer molded article containing the polymer having a chemical structure represented by the formula A method for producing a conductive polymer molded article.
し、酸化剤の共存下に行う請求項１または２記載の導電
性重合体または導電性重合体成形物の製造方法。3. The method for producing a conductive polymer or a molded product of a conductive polymer according to claim 1 or 2, wherein the sulfonating agent is allowed to act on the polymer in the presence of an oxidizing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07302193A JP3149290B2 (en) | 1993-03-08 | 1993-03-08 | Method for producing conductive polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07302193A JP3149290B2 (en) | 1993-03-08 | 1993-03-08 | Method for producing conductive polymer |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000359053A Division JP3310267B2 (en) | 2000-11-27 | 2000-11-27 | Method for producing conductive polymer molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06256516A true JPH06256516A (en) | 1994-09-13 |
| JP3149290B2 JP3149290B2 (en) | 2001-03-26 |
Family
ID=13506270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07302193A Expired - Fee Related JP3149290B2 (en) | 1993-03-08 | 1993-03-08 | Method for producing conductive polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3149290B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6024895A (en) * | 1995-08-11 | 2000-02-15 | Mitsubishi Rayon Co., Ltd. | Cross-linkable, electrically conductive composition, electric conductor and process for forming the same |
| JP2009074092A (en) * | 2006-02-08 | 2009-04-09 | Showa Denko Kk | Antistatic agent, antistatic film and article coated with antistatic film |
| US7645400B2 (en) | 2002-11-01 | 2010-01-12 | Mitsubishi Rayon Co., Ltd. | Composition containing carbon nanotubes having a coating |
| US9627144B2 (en) | 2011-08-17 | 2017-04-18 | Mitsubishi Rayon Co., Ltd. | Solid electrolytic capacitor and method for manufacturing same |
| WO2018147318A1 (en) | 2017-02-10 | 2018-08-16 | 三菱ケミカル株式会社 | Conductive composition, method for producing conductive composition, and method for producing conductor |
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| WO2019198749A1 (en) | 2018-04-10 | 2019-10-17 | 三菱ケミカル株式会社 | Electrically conductive composition, electrically conductive film, and laminate |
| WO2020100791A1 (en) | 2018-11-15 | 2020-05-22 | 三菱ケミカル株式会社 | Conductive composition and method for manufacturing same, and conductor and method for manufacturing same |
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1993
- 1993-03-08 JP JP07302193A patent/JP3149290B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6024895A (en) * | 1995-08-11 | 2000-02-15 | Mitsubishi Rayon Co., Ltd. | Cross-linkable, electrically conductive composition, electric conductor and process for forming the same |
| US7645400B2 (en) | 2002-11-01 | 2010-01-12 | Mitsubishi Rayon Co., Ltd. | Composition containing carbon nanotubes having a coating |
| JP2009074092A (en) * | 2006-02-08 | 2009-04-09 | Showa Denko Kk | Antistatic agent, antistatic film and article coated with antistatic film |
| US9627144B2 (en) | 2011-08-17 | 2017-04-18 | Mitsubishi Rayon Co., Ltd. | Solid electrolytic capacitor and method for manufacturing same |
| US10096395B2 (en) | 2012-07-24 | 2018-10-09 | Mitsubishi Chemical Corporation | Conductor, conductive composition and laminate |
| US11145432B2 (en) | 2012-07-24 | 2021-10-12 | Mitsubishi Chemical Corporation | Conductor, conductive composition and laminate |
| WO2018147318A1 (en) | 2017-02-10 | 2018-08-16 | 三菱ケミカル株式会社 | Conductive composition, method for producing conductive composition, and method for producing conductor |
| WO2019146715A1 (en) | 2018-01-26 | 2019-08-01 | 三菱ケミカル株式会社 | Electroconductive composition and production method therefor, and water-soluble polymer and production method therefor |
| WO2019177096A1 (en) | 2018-03-15 | 2019-09-19 | 三菱ケミカル株式会社 | Conductive film, method for producing same, conductor, resist pattern formation method, and laminate |
| WO2019198749A1 (en) | 2018-04-10 | 2019-10-17 | 三菱ケミカル株式会社 | Electrically conductive composition, electrically conductive film, and laminate |
| WO2020100791A1 (en) | 2018-11-15 | 2020-05-22 | 三菱ケミカル株式会社 | Conductive composition and method for manufacturing same, and conductor and method for manufacturing same |
| WO2021153678A1 (en) | 2020-01-29 | 2021-08-05 | 三菱ケミカル株式会社 | Conductive composite, resist coating material, resist, and resist pattern formation method |
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|---|---|
| JP3149290B2 (en) | 2001-03-26 |
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