JPS59135208A - Production of electroconductive composition - Google Patents
Production of electroconductive compositionInfo
- Publication number
- JPS59135208A JPS59135208A JP13683182A JP13683182A JPS59135208A JP S59135208 A JPS59135208 A JP S59135208A JP 13683182 A JP13683182 A JP 13683182A JP 13683182 A JP13683182 A JP 13683182A JP S59135208 A JPS59135208 A JP S59135208A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- temperature
- double bond
- cyano group
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】
本発明は導電性組成物の製造法に関する。炭素系の導電
性組成物は種々の方法で製造できるが、気相熱分解が最
も重要な方法の一つと考えられ、これまでに数多くの具
体策が提案されできた。メタン、プロパン、プロピレン
、ベンゼン、アセチレンなどの化合物を高温で熱分解す
るのもその一つであるが、反応温度は一般に高く通常９
００℃以上２５００℃を要し、エネルギー多消費型であ
る。しかもこの範囲中でも低温の領域では、導電性の高
い生成物は得られにくい。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing an electrically conductive composition. Although carbon-based conductive compositions can be produced by various methods, gas phase pyrolysis is considered to be one of the most important methods, and many specific methods have been proposed so far. One example is the thermal decomposition of compounds such as methane, propane, propylene, benzene, and acetylene at high temperatures, but the reaction temperature is generally high and usually 9
It requires a temperature of 00°C or more to 2500°C and is energy consuming. Moreover, within this range, it is difficult to obtain a highly conductive product in the low temperature region.
本発明においてシアン基と二重結合を持つ化合物の低温
反応によっても充分高い導電性を有する組成物の得られ
る方法が提案される。本発明の目的はすでに述べたよう
に導電性組成物の製造にあるが、単独使用以外にも他の
耐熱性材料たとえば炭素、セラミック、金属などの被服
層として利用する事も可能である。In the present invention, a method is proposed in which a composition having sufficiently high conductivity can be obtained even by low-temperature reaction of a compound having a cyan group and a double bond. As mentioned above, the purpose of the present invention is to produce a conductive composition, but in addition to being used alone, it can also be used as a coating layer for other heat-resistant materials such as carbon, ceramics, metals, etc.
なお本発明にａ３ける導電性組成物とは金属４Ｋ ７％
の高い電気伝導度を示す組成物は勿論の事、半導体領域
の電気伝導度をしつ組成物をも倉／、 ’−Ｃ−ｕｓろ
。In addition, the conductive composition in a3 of the present invention is metal 4K 7%
In addition to compositions that exhibit high electrical conductivity in semiconductor regions, we also provide compositions that exhibit high electrical conductivity in semiconductor regions.
以上に本発明の方法を詳細に述ノ＼る。本発明σ）要旨
はシアノ基と二重結合を持つ化合物を５００・・・３２
００ ℃のン晶１肛（゛反応させる１Ｎ（こある。The method of the present invention is described above in detail. The gist of the present invention σ) is that a compound having a cyano group and a double bond is
00℃ 1N (1N)
本発明の方法におい−Ｃ使用されるシアノ基と一二Φ結
合を含む化合物の具体例（３１、アクリロニｌ−，ＩＪ
ル、メタクＩＪ ｌ］二１〜リル、ｊ用〜ラシアノ−［
−チレン、りＩＪ ［”ｉアクリＬ」二１〜リル、およ
びその把のシアツリと一一Φ結合を持つ炭化水素であり
、これらｆｉｔ Ｅｌ’独−（用いてもよいが、２種以
上混合しＣもよく、さらにイの他の脂肪ｈχ炭化水素、
脂環族炭化水素、Ｚ杏族炭化水素、不飽和炭化水素など
と混合しく−用い−（も、Ｊ： Ｉｔ）。反応に際して
窒素、ヘリウム、ノ′ルゴン、水素等の反応雰叶気中Ｃ
不活性ガスてパ通常３−４０９８、好ましくは１０ ３
０ ％σ） ｌ’ａ ｌｕ ｉこ希釈し−Ｃおく１１が
出来る。Specific examples of compounds containing a cyano group and a 12Φ bond (31, acryloni l-, IJ
Ru, Metak IJ l] 21~Ril, j for~Raciano-[
-tyrene, ri IJ ["iacryl"] is a hydrocarbon having 21~lyl, and its bulk, 11 Φ bond, C is also good, and other fatty hχ hydrocarbons of A,
Used in combination with alicyclic hydrocarbons, Z apricot group hydrocarbons, unsaturated hydrocarbons, etc. (J: It). During the reaction, C in the reaction atmosphere of nitrogen, helium, norgon, hydrogen, etc.
Inert gas usually 3-4098, preferably 10 3
0% σ) l'a lu i This dilution yields -C and 11.
これらのカス状の川ｊ ）ｌ’ｌはし５００・−３２０
０℃、（１′よい（ｔよ６００へ一２０００℃、さらに
（ｆ、ｉ Ｌ ＜は７００−１り００”Ｃの温度で反応
させる。反応４ｉ種々のメカニズムで進行すると考λら
れる。たとえは、先ずニー重Ｗｉ合が間き、ついでジノ
′］阜の閉環による環化が起り、ざらに反応渦電の−１
，＝ Ｗｒとどもに脱水素環化その他の反１，６が複雑
に起（″、す、さらに高温（はグツフッ・イト化が進む
と考えらねる。これ以外にもイＡンヤ）他のラジカルへ
の開裂を粁るメカニズムも考えられる。反応生成物（よ
反応条件ＩＪ−ｔ）よるが、種々の構造の混？ｊし／：
、複雑な組成物と考えられる。These scum-like rivers j)l'l chopsticks 500・-320
The reaction is carried out at a temperature of 0°C, (1' good (t = 600 - 2000°C, and (f, i L < 700 - 100"C. Reaction 4i is thought to proceed by various mechanisms. First, there is a knee-heavy combination, and then cyclization occurs due to the ring closure of Dino′], and roughly -1 of the reaction eddy current occurs.
, = Dehydrocyclization and other anti-1,6 reactions occur in a complex manner with Wr ('', I don't think that even higher temperatures (higher temperature) will lead to further cyclization. In addition to this, there are other reactions. A mechanism that prevents cleavage into radicals is also considered.Depending on the reaction products (and reaction conditions), various structures may be mixed:
, considered a complex composition.
反応時間は条ｆ４ ＋、二もよるか、７００’Ｃ稈庶で
（まε）０秒程度（゛十分て・ある６、これ以−１−の
時間Ｃ′も勿論よく、またこれ以下の時間で１）イれな
りに効果はある。。The reaction time depends on the conditions f4+ and 2, or about 0 seconds at 700'C (or ε). 1) It will have a certain effect over time. .
本発明の１ノ法（こよれば低温の段階で窒素を含む新規
な化合物がまず生成する。反ｉ、ｉ＝、温度が−１−る
と窒素の含有率は低下しいわゆるグツフッ・（ｌ−構造
Ｉこ近づくと考えられる。この場合従来の気相熱分解ｊ
大木の製造払に比べると、反応速度が人さいので低温反
１・ｉｓ ｊ〕１−７１１ Ｉｔヒで、省丁ネル−（“
−の硯魚からみ−（もされめて高い価値がある。Method No. 1 of the present invention (according to which a new compound containing nitrogen is first formed at a low temperature stage. When the temperature is −1−, the nitrogen content decreases, and the so-called gutsufu (l -Structure I is considered to approach.In this case, conventional gas phase pyrolysis j
Compared to the production of large trees, the reaction speed is slow, so the low-temperature reaction 1-is j] 1-711 It is low-temperature reaction.
- from the inkstone fish - (also highly valued.
本発明のジノ法−（得られる導電性組成物を他の祠１１
の表…１被覆層として用いる際の基盤としては、６英、
ガーノス、窒化ボウ索、窒化ケイ素、サファイア、シリ
ゴＪン等の無機質の÷オ料、アルミニウム、ス）ンレス
、銅その他の金属材料、グラノアイト、炭素繊維等の炭
素（Ａ利等が用いられる。基盤としＣ丁ピタキシＸフル
重合に用いられる結晶性基盤さらにグラフＡエピタキシ
ャルに用いられる基盤も勿論用いる事が出きる。Zino method of the present invention (the conductive composition obtained is transferred to another shrine 11)
Table...1 As a base when used as a coating layer, 6-E,
Inorganic materials such as garnos, nitride, silicon nitride, sapphire, silicone, aluminum, stainless steel, copper and other metal materials, granoite, carbon fiber such as carbon fiber, etc. are used. It is of course possible to use the crystalline substrate used in the full polymerization of Toshi C-cho Pitaxy X, as well as the substrate used in the Graph A epitaxial process.
本発明は触ＩＪを使用しない熱段応を典型的実施態様と
しているが、触媒を用いる方法もまたＩｔ１能である。Although the present invention typically embodies a thermal stage reaction without the use of a catalytic IJ, catalytic processes are also possible.
触媒とし−Ｃはアルミプ、鉄、」パル１〜、ニラクル、
ハノジウム、舌の小金属、これらの合金、酸化物、炭化
物その他の化合物が用いられる。As a catalyst - C is aluminum, iron, Pal 1~, Niracle,
Hanodium, small metals, alloys thereof, oxides, carbides and other compounds are used.
触媒を用いる事により反応の温度をさらに低十さＵる８
１１か出来る。ざらにプラズマ重合の手ｄ１を（ｊｆ用
（Ｊる事も出来る。By using a catalyst, the temperature of the reaction can be further lowered8.
I can do 11. Roughly plasma polymerization hand d1 (for jf (J) can also be used.
本発明にＪ、り得られる導電１コ［組成物は一般には基
盤上に１４石物として□て得られるが、繊維状また（よ
り、０繊帷状の生成物ム勿論本発明の範囲に包含される
。。Although the conductive composition obtained according to the present invention is generally obtained as a 14-layer material on a substrate, fibrous or even fibrous products are of course within the scope of the present invention. Included.
本発明により得られる導電Ｍ ｌｌ（−１成物の電気電
５ｊＪ度はドーピングおよびインターツル−シフｊンの
Ｊｌン人（ごより白土さμ冑る１、１ヘ−バントとしＵ
ｆｊ−トン索、Ｙ’ｍフッ化ヒ素、−′塩化アンツー
しンｉ１３よひ（の他の公知の化合物が用いられ得る、
。The electrical conductivity of the conductive material obtained according to the present invention is 5JJ, which is 1,1 and 1% as compared with doping and interspersion.
Other known compounds can be used, such as fj-ton, Y'm arsenic fluoride, and anzushin chloride.
.
以上に実施例により本発明の方法を詳細に説明づる。The method of the present invention will be explained in detail using Examples above.
実施例１
内（−１￥１５ｍｍの石英製の反応鴛（こ反応の基盤ど
して石英板を入れ、電気炉を用いｌ’ ６００ ’Ｃに
加熱づる。ここに窒素カスをキー１７すＡ７−どじ、こ
れにアクリロニ１〜リル、メタクリ１」二１ヘリル、ツ
ー１〜ノシアノ−［−１−レン、メタン、ゾ［−１ビ１
ノン、アレブレン、（）−＝ヘノ゛タン、ベンぜン、？
ｔｌ−二トリル、シ十Ｆレントリノ′ミン、２−ビニル
ピリジン、ｄ３よびクロルアクリロニトリルをそ４′１
ぞれ別に２０容早％含む原料ガスを１００ ｍｌ／’ｍ
ｉｎの速用て・２時間供給した。反発後基盤である石英
ｊｋを取り出し反応生成物を肉眼で観察した。アクリロ
ニトリル、メタクリロニトリル、テトラシアノエチレン
、Ｊ３よびクロロアクリロニトリルでは金属光沢を持つ
反応物が基盤上に生成していたが、これ以外の原料では
表面被覆層の生成はなかった。Example 1 Insert a quartz plate (-1 yen 15 mm) into a quartz plate as a base for this reaction, and heat it to l'600'C using an electric furnace. -Doji, this includes acryloni 1~lyl, methacrylic 1''21heryl, two 1~nocyano-[-1-lene, methane, zo[-1bi1
Non, alebren, ()-=henotane, benzene, ?
tl-nitrile, cyF lentrinomine, 2-vinylpyridine, d3 and chloroacrylonitrile
100 ml/'m of raw material gas containing 20% by volume separately.
Ingredients were used immediately for 2 hours. After repulsion, the quartz JK substrate was taken out and the reaction products were observed with the naked eye. With acrylonitrile, methacrylonitrile, tetracyanoethylene, J3, and chloroacrylonitrile, a reaction product with metallic luster was formed on the substrate, but with the other raw materials, no surface coating layer was formed.
実施例２
アクリロニトリルをアルゴンを用いて５％に希釈し５０
ｍｌ／ｍｉｎの速度で６００，８００．１５００℃に
温度をあげた反応管に入れた石英板の上で反応させた。Example 2 Acrylonitrile was diluted to 5% with argon to 50%
The reaction was carried out on a quartz plate placed in a reaction tube heated to 600, 800, or 1500° C. at a rate of ml/min.
１時間の反応後基盤として用いた石英板を取り出し、基
盤上の生成物をとり元素分析を行なった。結果は次の通
りでああった。After one hour of reaction, the quartz plate used as a substrate was taken out, and the product on the substrate was taken for elemental analysis. The results were as follows.
焼成温度 原子比
°Ｃ炭素 窒素 水累
６００ ５．５ １．０ ０．６８００ ６
．８．１．ＯＯ，４
１５００８、，３１，００，１
反応温度が低い場合窒素を多量に含有する生成物が得ら
れる。反応生成物の電気伝導度を測定した結果は次の通
りであった。Firing temperature Atomic ratio °C Carbon Nitrogen Water 600 5.5 1.0 0.6800 6
．． 8.1. OO,4 15008,,31,00,1 If the reaction temperature is low, nitrogen-rich products are obtained. The results of measuring the electrical conductivity of the reaction product were as follows.
反応温度 電気伝導度
６００℃ ０．０２’ Ｓ／ｃｍ８００℃
８０ Ｓ／ｃｍ１５００’Ｃ９００Ｓ／ｃｍ
実施例３
内径２０ｃｍの反応管に醇化第１鉄を塗布した磁性のボ
ートを入れ１０００℃まで昇温しアクリロニトリルを１
５ ｃｍ／ｍｉｎの流速で２時間反応させた。反発後磁
性のボートを取り出し観察したところ長さ６ｍｍのウィ
スカーが密生していた。Reaction temperature Electric conductivity 600℃ 0.02' S/cm 800℃
80 S/cm1500'C900S/cm Example 3 A magnetic boat coated with ferrous chloride was placed in a reaction tube with an inner diameter of 20 cm, the temperature was raised to 1000°C, and acrylonitrile was added to the reaction tube for 1 hour.
The reaction was carried out for 2 hours at a flow rate of 5 cm/min. After the repulsion, the magnetic boat was taken out and observed, and it was found that whiskers 6 mm in length were growing densely.
特許出願人 工業技術院長 石板Ｍ−手 続 補
正 書 （方式）昭和５９年 ９月つ８日
特許庁長官 若 杉 和 夫 殿
１、事件の表示
昭和５７年特許願第１３６８３１号
″″′□
１
ｌ−−（−１，ｉ
明細書中「発明の名称」の欄
−６に
一）
・′、−＼ジ
：、（ｊｔ’、１Patent Applicant Director of the Agency of Industrial Science and Technology Slate M-Procedural Amendment (Method) September 8, 1981 Kazuo Wakasugi, Commissioner of the Patent Office 1, Indication of Case Patent Application No. 136831 of 1982''''□ 1 l--(-1, i "Title of the invention" column-6 in the specification) ・', -\di:, (jt', 1
Claims (1)
２０−０℃の温度で反応させる事を特徴とする導電性組
成物の製造方法。 （２、特許請求の範囲第１項の記載の方法において、シ
アノ基と二重結合を含む化合物が下記の一般式で示され
、かつその炭素数が６以下である事を特徴とする方法。 ここで、Ｘ、Ｙ、Ｚは 水素、ハロゲン、シアノ基、お
よびアルギル基から選ばれる原子団。 （３）’に’ｉ訂請求の範囲Ｍ２項記載の方法において
、シアノ基を含む化合物がアクリロニトリル、α−クロ
ルアクリロニトリルまたはβクロルアクリロニｉ〜リル
である事を特徴とする方法。[Scope of Claims] (1) A compound containing a cyan group and a double bond containing 500 to 3
A method for producing a conductive composition, characterized in that the reaction is carried out at a temperature of 20-0°C. (2. The method according to claim 1, wherein the compound containing a cyano group and a double bond is represented by the following general formula and has 6 or less carbon atoms. Here, X, Y, and Z are atomic groups selected from hydrogen, halogen, cyano group, and argyl group. , α-chloroacrylonitrile or β-chloroacryloni-lyl.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13683182A JPH0237926B2 (en) | 1982-08-07 | 1982-08-07 | DODENSEISOSEIBUTSUNOSEIZOHOHO |
| US06/520,197 US4673720A (en) | 1982-08-07 | 1983-08-04 | Electroconductive polymer and process for preparation thereof |
| US07/039,239 US4778625A (en) | 1982-08-07 | 1987-04-17 | Electroconductive polymer and process for preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13683182A JPH0237926B2 (en) | 1982-08-07 | 1982-08-07 | DODENSEISOSEIBUTSUNOSEIZOHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59135208A true JPS59135208A (en) | 1984-08-03 |
| JPH0237926B2 JPH0237926B2 (en) | 1990-08-28 |
Family
ID=15184518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13683182A Expired - Lifetime JPH0237926B2 (en) | 1982-08-07 | 1982-08-07 | DODENSEISOSEIBUTSUNOSEIZOHOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0237926B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2554456A1 (en) * | 1983-11-03 | 1985-05-10 | Gen Electric | SEMICONDUCTOR MATERIAL BASED ON GLASS TISSUE FIBERS AND PROCESS FOR PRODUCING THE SAME |
| US4886626A (en) * | 1987-05-19 | 1989-12-12 | Crest-Foam Corporation | Conductive polyurethane foam compositions containing tetralyanoethylene and method |
| US5028355A (en) * | 1987-05-19 | 1991-07-02 | Crest-Foam Corporation | Conductive polyurethane foam containing picric acid and analog thereof |
-
1982
- 1982-08-07 JP JP13683182A patent/JPH0237926B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2554456A1 (en) * | 1983-11-03 | 1985-05-10 | Gen Electric | SEMICONDUCTOR MATERIAL BASED ON GLASS TISSUE FIBERS AND PROCESS FOR PRODUCING THE SAME |
| US4886626A (en) * | 1987-05-19 | 1989-12-12 | Crest-Foam Corporation | Conductive polyurethane foam compositions containing tetralyanoethylene and method |
| US5028355A (en) * | 1987-05-19 | 1991-07-02 | Crest-Foam Corporation | Conductive polyurethane foam containing picric acid and analog thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0237926B2 (en) | 1990-08-28 |
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