JPS6119081B2 - - Google Patents
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- Publication number
- JPS6119081B2 JPS6119081B2 JP55180674A JP18067480A JPS6119081B2 JP S6119081 B2 JPS6119081 B2 JP S6119081B2 JP 55180674 A JP55180674 A JP 55180674A JP 18067480 A JP18067480 A JP 18067480A JP S6119081 B2 JPS6119081 B2 JP S6119081B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- tcnq
- radical
- conductive
- complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 229920000642 polymer Polymers 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- -1 ion radical salt Chemical class 0.000 claims description 18
- 229920001940 conductive polymer Polymers 0.000 claims description 15
- 239000003973 paint Substances 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 10
- 150000005837 radical ions Chemical class 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002861 polymer material Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 4
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical group N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims 1
- 230000005684 electric field Effects 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 230000006399 behavior Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- HOQAPVYOGBLGOC-UHFFFAOYSA-N 1-ethyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CC HOQAPVYOGBLGOC-UHFFFAOYSA-N 0.000 description 1
- RTQPKEOYPPMVGQ-UHFFFAOYSA-N 1-methylquinolin-1-ium Chemical compound C1=CC=C2[N+](C)=CC=CC2=C1 RTQPKEOYPPMVGQ-UHFFFAOYSA-N 0.000 description 1
- CRTKBIFIDSNKCN-UHFFFAOYSA-N 1-propylpyridin-1-ium Chemical compound CCC[N+]1=CC=CC=C1 CRTKBIFIDSNKCN-UHFFFAOYSA-N 0.000 description 1
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- CPYFLMXPZMBECD-UHFFFAOYSA-N 3-acetyl-1,8-dihydroxy-2-methylphenanthrene-9,10-dione Chemical compound C12=CC=CC(O)=C2C(=O)C(=O)C2=C1C=C(C(=O)C)C(C)=C2O CPYFLMXPZMBECD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-O acridine;hydron Chemical compound C1=CC=CC2=CC3=CC=CC=C3[NH+]=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-O 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000755 effect on ion Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- 230000005676 thermoelectric effect Effects 0.000 description 1
Landscapes
- Details Of Resistors (AREA)
- Non-Adjustable Resistors (AREA)
- Conductive Materials (AREA)
Description
【発明の詳細な説明】
本発明は、導電性電荷移動錯体を高分子マトリ
クス中に含有させた導電性高分子材料の電極部構
造に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrode part structure of a conductive polymer material containing a conductive charge transfer complex in a polymer matrix.
従来、導電性をもつ高分子組成物として、金属
やカーボンラツク、グラフアイトを高分子中に分
散した導電性複合材料のほかに、有機半導体であ
る電荷移動錯体を高分子中に分散した組成物も多
く提案されている。これは、成形性、可撓性等に
優れた高分子半導体材料を目ざしたものであり、
電子伝導性高分子を提供するものである。 Conventionally, conductive polymer compositions include conductive composite materials in which metals, carbon lacquer, and graphite are dispersed in polymers, as well as compositions in which charge transfer complexes, which are organic semiconductors, are dispersed in polymers. Many have also been proposed. This is aimed at creating a polymeric semiconductor material with excellent moldability, flexibility, etc.
The present invention provides an electronically conductive polymer.
この電荷移動錯体は、ほとんどすべて結晶粉体
であるが、高分子マトリクス中において、そのマ
トリクスが極性高分子である場合には一部溶解さ
れ、分子散性を示すことにその特徴がある。この
電荷移動錯体の電子伝導は、その錯体を形成して
いるラジカルイオンの電子の授受によつて電子伝
導されるものであり、その電荷輸送は、バンド伝
導よりホツピング伝導によるものが多いとされて
いる。 This charge transfer complex is almost entirely a crystalline powder, but is characterized by being partially dissolved in a polymer matrix when the matrix is a polar polymer and exhibiting molecular dispersion. Electron conduction in this charge transfer complex is carried out by the exchange of electrons between the radical ions forming the complex, and it is said that the charge transport is more likely to be due to hopping conduction than band conduction. There is.
ここで、前記のように、電荷移動錯体が高分子
マトリクスに一部溶解された場合には、そのラジ
カルイオンは、電子の授受のみならず、イオン的
挙動を併発し、直流電界による分極現象、いいか
えれば、直流電界による電流の経時変化を生じ、
電子伝導性材料としてはきわめて不都合な欠点と
なる。この分極現象を７，７，８，８−テトラシ
アノキノジメタン（以下TCNQと略す）を電子受
容体とするTCNQ錯体を用いて以下に説明する。 Here, as mentioned above, when the charge transfer complex is partially dissolved in the polymer matrix, the radical ions not only give and receive electrons but also exhibit ionic behavior, such as polarization phenomenon caused by a DC electric field, In other words, the DC electric field causes a change in current over time,
This is a very inconvenient drawback for an electronically conductive material. This polarization phenomenon will be explained below using a TCNQ complex having 7,7,8,8-tetracyanoquinodimethane (hereinafter abbreviated as TCNQ) as an electron acceptor.
TCNQは陰イオンラジカルTCNQ・となつて
D+（TCNQ）・あるいはD+（TCNQ）2・を形成し
ているため、直流電界により、陽極側にクーロン
力を受けとることになる。そのため、電極間に均
一に分散していたTCNQ・は電界印加の時間が増
すと共に陽極側に移動し、第１図のように、曲線
Ｃで示すTCNQ・の濃度は陰極近傍において低下
することになる。そのため曲線ρで示す抵抗率は
陰極近傍において上昇し、その部分に印加される
電圧が増す。それによつてされに陰極近傍部の比
抵抗の上昇がますます加速され、大きな比抵抗の
経時変化が起こることになる。 TCNQ becomes anion radical TCNQ・
Since it forms D + (TCNQ) or D + (TCNQ) 2 , the anode side receives Coulomb force due to the DC electric field. Therefore, TCNQ・, which was uniformly dispersed between the electrodes, moves toward the anode as the electric field application time increases, and as shown in Figure 1, the concentration of TCNQ・ shown by curve C decreases near the cathode. Become. Therefore, the resistivity shown by the curve ρ increases near the cathode, and the voltage applied to that portion increases. As a result, the rise in resistivity in the vicinity of the cathode is further accelerated, resulting in a large change in resistivity over time.
そこで本発明は、このような電荷移動錯体を分
散した高分子組成物の電極部構造を改良し、導電
性高分子組成物を用いたデバイスの経時安定性を
向上するものである。 Therefore, the present invention aims to improve the electrode structure of a polymer composition in which such a charge transfer complex is dispersed, thereby improving the stability over time of a device using a conductive polymer composition.
すなわち本発明は、電荷移動錯体を含む導電性
高分子組成物に対して前記錯体の少なくとも一成
分を含む電極を設けるものである。この構成によ
れば、TCNQ錯体を含む高分子組成物の第１図の
ような特性は大きく改善され、組成物各部の比抵
抗は一様になる。 That is, the present invention provides a conductive polymer composition containing a charge transfer complex with an electrode containing at least one component of the complex. According to this configuration, the characteristics as shown in FIG. 1 of the polymer composition containing the TCNQ complex are greatly improved, and the resistivity of each part of the composition becomes uniform.
本発明に用いる導電性高分子組成物とは、サー
スタ特性、熱電効果、光導電性、放射線誘起伝
導、磁気抵抗効果等外的作用因子により導電特性
を変化するような半導体材料や導体材料を指す。
導電性高分子材料に用いる高分子マトリクスとし
ては、汎用高分子材料を用いることができ、含有
させる電荷移動錯体の溶解度の高い高分子ほど、
先に述べたイオン伝導性の影響が大きく現れ、ポ
リエチレンやポリプロピレンのような無極性高分
子は、溶解度がほとんどなく、イオン伝導性の影
響が少ない。 The conductive polymer composition used in the present invention refers to semiconductor materials and conductor materials whose conductive properties change depending on external factors such as surster characteristics, thermoelectric effect, photoconductivity, radiation-induced conduction, and magnetoresistive effect. .
General-purpose polymer materials can be used as the polymer matrix used in the conductive polymer material, and the higher the solubility of the charge transfer complex contained in the polymer, the more
The effect of ion conductivity mentioned above is significant, and nonpolar polymers such as polyethylene and polypropylene have almost no solubility and therefore have little effect on ion conductivity.
一方、本発明に用いる電荷移動錯体は、それ自
体、半導性を示す材料であり、電子受容体と電子
供与体より構成され、イオンラジカルとなつて導
電キヤリヤーを輸送するサイトとなる。陰イオン
ラジカルを形成する分子としては、TCNQ、ジク
ロロジシアノキノン等のシアノキノンやテトラシ
アノエチレン、ハロキノン、ヨウ素等がある。ま
た陽イオンラジカルを形成する分子としては、テ
トラチオフルバレン、テトラチオテトラセン、テ
トラフエニルジチオピラニリデン等の含イオウ化
合物やエチカルカルバゾール、Ｎ，Ｎ−ジメチル
−Ｐ−フエニレンジアミン等の含窒素化合物等が
ある。これらの電荷移動錯体は高分子中におい
て、その含有量が溶解度までは分子分散され、そ
れ以上の含有量では粒子状態で分散される場合が
多く、それぞれの粒子が導電性結晶粒子としての
働きをする。 On the other hand, the charge transfer complex used in the present invention is itself a material exhibiting semiconductivity, and is composed of an electron acceptor and an electron donor, and becomes an ion radical and serves as a site for transporting a conductive carrier. Molecules that form anion radicals include cyanoquinones such as TCNQ and dichlorodicyanoquinone, tetracyanoethylene, haloquinone, and iodine. Molecules that form cation radicals include sulfur-containing compounds such as tetrathiofulvalene, tetrathiotetracene, and tetraphenyldithiopyranylidene, and ethylcarbazole and N,N-dimethyl-P-phenylenediamine. There are nitrogen compounds, etc. These charge transfer complexes are molecularly dispersed in polymers until their content reaches solubility, and when their content exceeds that level, they are often dispersed in the form of particles, with each particle acting as a conductive crystal particle. do.
次に、これらの挙動について、TCNQのナトリ
ウム塩Na（TCNQ）をポリウレタンとポリ塩化
ビニル混練体中に分散した組成物を例にとつて詳
細に述べる。 Next, these behaviors will be described in detail using, as an example, a composition in which the sodium salt of TCNQ (Na (TCNQ)) is dispersed in a kneaded body of polyurethane and polyvinyl chloride.
前記混練体のNa（TCNQ）含量と比低抗ρの
関係は第２図のようであり、Na（TCNQ）の高
分子マトリクスへの溶解度は約0.1重量％であ
る。Na（TCNQ）を加えない場合（ブランク）
に比べ、Na（TCNQ）含量0.05〜20重量％の領域
（MDCと呼ぶ）は、分子分散散されたキヤリヤサ
イトによる伝導領域であり、20重量％以上では粒
子分散したNa（TCNQ）同志の接触による電子
伝導の領域（GDCと呼ぶ）である。 The relationship between the Na(TCNQ) content and the specific resistance ρ of the kneaded body is as shown in FIG. 2, and the solubility of Na(TCNQ) in the polymer matrix is about 0.1% by weight. When Na (TCNQ) is not added (blank)
Compared to this, the region with a Na(TCNQ) content of 0.05 to 20% by weight (referred to as MDC) is a conduction region due to molecularly dispersed carrier sites; This is the region of electron conduction by contact (called GDC).
第３図はNa（TCNQ）を含む１mm厚のシート
状高分子組成物の試料に一対の電極を設け、60℃
において103V／cmの直流電圧を印加した場合の
抵抗率の経時変化を示す。曲線ａおよびｂはそれ
ぞれNa（TCNQ）含量0.5重量％および20重量％
の試料の特性を示す。この場合、電極は高分子組
成物に対して直接黒鉛電極を設けて構成した。 Figure 3 shows a sample of a 1 mm thick sheet-like polymer composition containing Na (TCNQ) with a pair of electrodes installed at 60°C.
The graph shows the change in resistivity over time when a DC voltage of 10 3 V/cm was applied. Curves a and b have Na(TCNQ) content of 0.5% and 20% by weight, respectively.
The characteristics of the sample are shown below. In this case, the electrode was constructed by providing a graphite electrode directly to the polymer composition.
図からも明らかなように、前者の領域MDCで
は、曲線ａのように、直流電場による電流変化が
大きく、後者の領域GDCでは、曲線ｂのよう
に、比抵抗上昇は少ないが、ある時間を経た後に
生じてくるのが一般的である。ｂにおいて、電流
が初期に増加するのは、Na（TCNQ）粒子の電
界による配列が起こり、低抵抗化するためであ
り、これはマトリクスポリマーの硬度や粒子分散
状態を変えることによりなくすることができる。 As is clear from the figure, in the former region MDC, as shown by curve a, the current change due to the DC electric field is large, and in the latter region GDC, as shown in curve b, the increase in resistivity is small, but It usually occurs after a period of time. In b, the initial increase in current is due to alignment of Na(TCNQ) particles caused by the electric field, resulting in lower resistance, and this can be eliminated by changing the hardness of the matrix polymer and the state of particle dispersion. can.
一方、曲線ＡおよびＢは、前記ａおよびｂに対
応応する試料に対しては、Na（TCNQ）を50重
量％含有するカーボンペイント電極を設けた場合
の特性を示す。 On the other hand, curves A and B show the characteristics when a carbon paint electrode containing 50% by weight of Na (TCNQ) was provided for the samples corresponding to a and b above.
第３図において、ａの変化がｂより大きいの
は、（Na）TCNQ含量がｂより少ないためで、電
界により移動したイオンラジカルが補給されず濃
度むらができ、高抵抗部ができやすいためであ
る。 In Figure 3, the reason why the change in a is larger than b is because the (Na)TCNQ content is lower than b, and the ion radicals moved by the electric field are not replenished, resulting in uneven concentration and the formation of high resistance areas. be.
本発明の構造では、この電極からラジカルイオ
ンが供給され、TCNQ濃度の欠乏層を生じないた
め、高抵抗化は生じない。この電極内では、ラジ
カルイオンと同極性の電極近接部でTCNQ濃度の
低下は起こるが、電極の比低抗は低いため、それ
によるその抵抗上昇はデバイスの抵抗にほとんど
影響を与えないオーダーである。それ故、本発明
によつて抵抗経時変化がきわめて改善されたデバ
イスを提供することになる。 In the structure of the present invention, radical ions are supplied from this electrode and no TCNQ concentration depletion layer is generated, so that high resistance does not occur. Within this electrode, a decrease in TCNQ concentration occurs near the electrode with the same polarity as the radical ion, but since the specific resistance of the electrode is low, the resulting increase in resistance is of an order that has little effect on the resistance of the device. . Therefore, the present invention provides a device with significantly improved resistance change over time.
本発明に用いる導電性高分子組成物のマトリク
ス高分子としては、汎用の高分子を用いることが
できるが、添加するイオンラジカル塩の溶解度の
小さい程、イオン伝導の挙動は小さい。しかし、
いくらこの挙動の小さいマトリクス高分子におい
ても、長期間にわたる高温かつ強電界の下では、
この挙動は促進され、実際の抵抗値を変化させる
ことになる。それ故本発明は、このようなデバイ
スにおいて長寿命化、高信頼性の上で非常に重要
なものである。 A general-purpose polymer can be used as the matrix polymer of the conductive polymer composition used in the present invention, but the lower the solubility of the ion radical salt added, the lower the ionic conduction behavior. but,
No matter how small this behavior is for matrix polymers, under long-term high temperatures and strong electric fields,
This behavior is accelerated and results in a change in the actual resistance value. Therefore, the present invention is very important for extending the lifespan and high reliability of such devices.
次に本発明に用いる電極としては導体粒子と高
分子結着材とからなる導電ペイントを母体とし、
このペイント中へ、前記導電性電荷移動錯体ある
いはその少なくとも一成分を添加したものを用い
る。この場合にも前記の低抵抗層の場合と同様に
この電極より電界によつてラジカルイオンが補給
され、TCNQ等ラジカルイオンの欠乏層を生じな
いため、高抵抗化は生じない。この電極内ではラ
ジカルイオンと同極性の電極近接部でラジカルイ
オンの濃度低下は起こるが、電極の比抵抗は低い
ためそれによる抵抗上昇はデバイスにほとんど影
響を与えないオーダーである。本発明に用いる前
記導電ペイントとは、銀ペイント、カーボンペイ
ント等の汎用塗料が便利である。この電極は、ま
た金属網中にこれらの錯体含有導電ペイントを塗
布することによつても得られるのは当然である。 Next, the electrode used in the present invention uses a conductive paint made of conductive particles and a polymer binder as a base,
The conductive charge transfer complex or at least one component thereof is added to this paint. In this case, as in the case of the low resistance layer described above, radical ions are replenished from this electrode by the electric field, and no layer deficient in radical ions such as TCNQ is created, so that no increase in resistance occurs. Within this electrode, the concentration of radical ions decreases near the electrode of the same polarity as the radical ions, but since the specific resistance of the electrode is low, the resulting increase in resistance is on the order of having almost no effect on the device. The conductive paint used in the present invention is conveniently a general-purpose paint such as silver paint or carbon paint. Naturally, this electrode can also be obtained by applying a conductive paint containing these complexes into a metal mesh.
電極にNa（TCNQ）を50重量％含有するカー
ボンペイント電極を用いて、第３図と同様に60℃
にて直流抵抗率ρの経時変化を観察したところ、
第３図とほぼ同一の結果を得た。 Using a carbon paint electrode containing 50% by weight of Na (TCNQ), the electrode was heated to 60°C in the same manner as shown in Figure 3.
When we observed the change in DC resistivity ρ over time, we found that
Almost the same results as in FIG. 3 were obtained.
次に本発明において錯体の一成分を電極あるい
は電極近傍に添加する場合、それが錯体成分中の
イオンラジカル成分あるいはそのイオンラジカル
の中性体であることが望ましい。この中性分子も
電界により電極反応して同様のイオンラジカルと
なつて移動をし、前記本発明のような挙動を示
す。 Next, in the present invention, when one component of the complex is added to the electrode or the vicinity of the electrode, it is desirable that it be an ion radical component in the complex component or a neutral form of the ion radical. These neutral molecules also react with the electrodes due to the electric field, become similar ion radicals, and move, exhibiting the same behavior as in the present invention.
具体例として、中性TCNQを10重量％添加した
銀ペイントを電極として用い、同様のNa
（TCNQ）含有のポリウレタン−ポリ塩化ビニル
組成物で実験したところ、やはり抵抗率の変化は
第３図と同様に、著しく抑制された。 As a specific example, a silver paint containing 10% by weight of neutral TCNQ was used as an electrode, and a similar Na
When an experiment was conducted using a polyurethane-polyvinyl chloride composition containing (TCNQ), the change in resistivity was also significantly suppressed, as in FIG. 3.
またさらに、プロピルピリジニウムTCNQ錯体
を45重量％含有させたアクリルゴム組成物（抵抗
率（20℃）106Ω・cm）にTCNQ10重量％含有の
カーボンペイント電極を用いた場合、アクリジニ
ウム（TCNQ）2を35重量％含有させたエチレン−
酢酸ビニル共重合体（抵抗率（20℃）104Ω・
cm）にメチルキノリニウム（TCNQ）2を20重量％
含有させた銀ペイント電極を用いた場合、のいず
れにおいても直流電界の常時印加に対して、同様
に著しく抵抗の経時変化率のきわめて小さい特性
を得ることができた。 Furthermore, when a carbon paint electrode containing 10% by weight of TCNQ is used in an acrylic rubber composition containing 45% by weight of propylpyridinium TCNQ complex (resistivity (20°C) 10 6 Ω・cm), acridinium (TCNQ) 2 Ethylene containing 35% by weight of
Vinyl acetate copolymer (resistivity (20℃) 10 4 Ω・
20% by weight of methylquinolinium (TCNQ) 2 in cm)
When silver paint electrodes containing silver paint were used, it was possible to obtain characteristics in which the rate of change in resistance over time was similarly extremely small even when a direct current electric field was constantly applied.
本発明は、以上のように、導電性電荷移動錯体
を含有させた導電性高分子組成物よりデバイスの
高寿命、高信頼性化を実現するものであり、工業
的価値は大なるものである。 As described above, the present invention realizes longer life and higher reliability of devices by using a conductive polymer composition containing a conductive charge transfer complex, and has great industrial value. .
第１図は導電性高分子材料を用いた装置の直流
電界印加後における比抵抗およびTCNQ濃度の分
布を示す図、第２図はTCNQを含む高分子組成物
のTCNQ含量と抵抗率と関係を示す図、第３図は
TCNQを含む高分子組成物を含む高分子組成物に
直流電圧を印加した場合の抵抗率の経時変化を示
す。
Figure 1 shows the distribution of specific resistance and TCNQ concentration after application of a DC electric field in a device using a conductive polymer material, and Figure 2 shows the relationship between the TCNQ content and resistivity of a polymer composition containing TCNQ. The diagram shown in Figure 3 is
Fig. 3 shows the change in resistivity over time when a direct current voltage is applied to a polymer composition containing a polymer composition containing TCNQ.
Claims (1)
含有させた導電性高分子組成物より少なくとも一
対の電極を取り出す装置において、前記の少なく
とも一方の電極中に前記錯体の少なくとも一成分
を含むことを特徴とする導電性高分子材料の電極
部。 ２ 電極が、導電性電荷移動錯体の少なくとも一
成分を含む銀ペイントあるいはカーボンペイント
である特許請求の範囲第１項記載の導電性高分子
材料の電極部。 ３ 錯体がイオンラジカル塩であり、前記錯体の
ラジカルイオンの極性と同極性の電極中に、前記
錯体のラジカルイオン成分が含有されている特許
請求の範囲第１項または第２項記載の導電性高分
子材料の電極部。 ４ イオンラジカル塩がシアノキノンアニオンラ
ジカルを陰イオンラジカルとする塩であり、前記
陰イオンラジカルあるいはその中性分子が陰極側
の電極に含有されている特許請求の範囲第３項記
載の導電性高分子材料の電極部。 ５ シアノキノンが７，７，８，８−テトラシア
ノキノジメタンである特許請求の範囲第４項記載
の導電性高分子材料の電極部。[Scope of Claims] 1. In an apparatus for extracting at least one pair of electrodes from a conductive polymer composition containing a conductive charge transfer complex in a polymer matrix, at least one of the complexes is contained in at least one of the electrodes. An electrode part made of a conductive polymer material characterized by containing a component. 2. The electrode portion of a conductive polymer material according to claim 1, wherein the electrode is silver paint or carbon paint containing at least one component of a conductive charge transfer complex. 3. The conductivity according to claim 1 or 2, wherein the complex is an ion radical salt, and the radical ion component of the complex is contained in an electrode having the same polarity as the radical ion of the complex. Electrode part made of polymer material. 4. The conductive polymer according to claim 3, wherein the ion radical salt is a salt having a cyanoquinone anion radical as an anion radical, and the anion radical or its neutral molecule is contained in the cathode side electrode. Electrode part of molecular material. 5. The electrode portion of a conductive polymer material according to claim 4, wherein the cyanoquinone is 7,7,8,8-tetracyanoquinodimethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55180674A JPS57103205A (en) | 1980-12-19 | 1980-12-19 | Electrode section made of conductive high polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55180674A JPS57103205A (en) | 1980-12-19 | 1980-12-19 | Electrode section made of conductive high polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57103205A JPS57103205A (en) | 1982-06-26 |
| JPS6119081B2 true JPS6119081B2 (en) | 1986-05-15 |
Family
ID=16087319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55180674A Granted JPS57103205A (en) | 1980-12-19 | 1980-12-19 | Electrode section made of conductive high polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57103205A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0477093U (en) * | 1990-11-16 | 1992-07-06 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007278867A (en) * | 2006-04-07 | 2007-10-25 | Ghitron Technology Co Ltd | Electrode structure of humidity sensing part |
-
1980
- 1980-12-19 JP JP55180674A patent/JPS57103205A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0477093U (en) * | 1990-11-16 | 1992-07-06 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57103205A (en) | 1982-06-26 |
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