JPH0556367B2 - - Google Patents
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- Publication number
- JPH0556367B2 JPH0556367B2 JP60000115A JP11585A JPH0556367B2 JP H0556367 B2 JPH0556367 B2 JP H0556367B2 JP 60000115 A JP60000115 A JP 60000115A JP 11585 A JP11585 A JP 11585A JP H0556367 B2 JPH0556367 B2 JP H0556367B2
- Authority
- JP
- Japan
- Prior art keywords
- oxidizing agent
- thermoplastic resin
- composite
- membered heterocyclic
- heterocyclic compound
- 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 - Lifetime
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Conductive Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、導電性複合体の製造方法に関する。
詳しくは、熱可塑性樹脂と複素５員環式化合物重
合体からなる導電性樹脂複合体の製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing a conductive composite.
Specifically, the present invention relates to a method for producing a conductive resin composite comprising a thermoplastic resin and a five-membered heterocyclic compound polymer.
複素５員環式化合物が、酸化剤によつて不溶不
融の重合体を生成することはすでに良く知られて
いる。例えば、ピロール及びその誘導体は、無機
酸、塩化鉄、ベンゾキノン、オゾンなどによつて
酸化され、ピロール黒、ピロール赤などの重合体
になる（Advances in Heterocycbc
Chemistry、vol15、67ページ、（1973年））。同様
の反応でフランやチオフエン及びそれらの誘導体
なども重合体となる。
It is already well known that five-membered heterocyclic compounds form insoluble and infusible polymers by oxidizing agents. For example, pyrrole and its derivatives are oxidized by inorganic acids, iron chloride, benzoquinone, ozone, etc., resulting in polymers such as pyrrole black and pyrrole red (Advances in Heterocycbc
Chemistry, vol 15, page 67, (1973)). Furan, thiophene, and their derivatives also become polymers through similar reactions.
一方、適当な電解質の存在下における電解重合
によつて膜状のフラン、ピロール、チオフエンの
重合体が得られる（例えば、J.C.S.Chemical
Communication、1979、635ページ、Japan
Journal of Applied Physics vol21（1982年）
L562ページなど）。 On the other hand, membrane-like furan, pyrrole, and thiophene polymers can be obtained by electropolymerization in the presence of an appropriate electrolyte (for example, JCS Chemical
Communication, 1979, 635 pages, Japan
Journal of Applied Physics vol21 (1982)
page L562, etc.).
さらには、他の樹脂との複合体を電解重合で得
る方法の一例がPolymer Preprints Japan vol33
（1984年）844ページに挙げられている。 Furthermore, an example of a method for obtaining a composite with other resins by electropolymerization is Polymer Preprints Japan vol33
(1984) on page 844.
上記の従来の方法では、酸化剤によつて得られ
る重合体は不溶不融であり、所望の形状の成形物
とすることは困難である。また、電解重合では特
定の形態のフイルム状重合体しか得られず、しか
も、安価な電解質及び設備を必要とする。
In the above-mentioned conventional methods, the polymer obtained by the oxidizing agent is insoluble and infusible, and it is difficult to mold it into a desired shape. In addition, electrolytic polymerization can only produce a specific form of film-like polymer, and requires inexpensive electrolytes and equipment.
本発明者らは、これらの問題を解決する方法に
ついて鋭意検討した結果、特定の重合法により熱
可塑性樹脂と複素五員環式化合物重合体の複合樹
脂とすることで、成形可能でしかも導電性の良い
樹脂複合体が得られることを見い出し、本発明を
完成した。 As a result of intensive research into ways to solve these problems, the inventors of the present invention found that by using a specific polymerization method to create a composite resin of a thermoplastic resin and a five-membered heterocyclic compound polymer, it was possible to create a composite resin that is moldable and conductive. They discovered that a resin composite with good properties could be obtained, and completed the present invention.
即ち、本発明は、酸化剤を含浸させた熱可塑性
樹脂粒子に酸素及び複素５員環式化合物を含有す
るガスを接触せしることを特徴とする導電性樹脂
複合体の製造方法である。
That is, the present invention is a method for producing a conductive resin composite, characterized in that thermoplastic resin particles impregnated with an oxidizing agent are brought into contact with a gas containing oxygen and a five-membered heterocyclic compound.
本発明において使用する酸化剤としては、無機
酸、金属塩が有効であり、硫酸、塩酸、硝酸、ク
ロルスルホン酸などの無機酸、ルイス酸として知
られるアルミニウム、錫、チタン、ジルコニウ
ム、クロム、、マンガン、鉄、銅、モリブデン、
タングステン、ルラニウム、パラジウム、白金な
どの塩化物、硫酸塩、アセチルアセトナート化合
物などの金属化合物が具体例として挙げられ、ベ
ンゾキノン、ジアゾニウム塩などの有機化合物も
利用可能である。中でも金属の塩化物が好ましく
使用できる。 As the oxidizing agent used in the present invention, inorganic acids and metal salts are effective, including inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and chlorosulfonic acid, aluminum, tin, titanium, zirconium, chromium, which are known as Lewis acids, manganese, iron, copper, molybdenum,
Specific examples include metal compounds such as chlorides, sulfates, and acetylacetonate compounds of tungsten, luranium, palladium, and platinum, and organic compounds such as benzoquinone and diazonium salts can also be used. Among them, metal chlorides can be preferably used.
本発明において用いられる熱可塑性樹脂として
は、ポリエチレン、ポリプロピレン、ポリ塩化ビ
ニル、ポリスチレン、スチレン−アクリロニトリ
ル共重合体、ポリカーボネート、ポリエステル、
ポリイソプレン、エチレン−プロピレンラバーな
ど市場で入手できるものが利用でき、形状は酸化
剤を含浸させた後、複素５員環式化合物と接触す
る際に適当な形状のものであれば良く、ペレツ
ト、パウダー、ビーズ等どのような形状であつて
も良い。 Thermoplastic resins used in the present invention include polyethylene, polypropylene, polyvinyl chloride, polystyrene, styrene-acrylonitrile copolymer, polycarbonate, polyester,
Commercially available rubber such as polyisoprene and ethylene-propylene rubber can be used, and any shape suitable for contacting the five-membered heterocyclic compound after being impregnated with an oxidizing agent may be used. It may be in any shape such as powder or beads.
本発明においては、上記樹脂粒子に前述の酸化
剤が含浸させられるわけであるが、この含浸の方
法については特に制限はない。通常は酸化剤を溶
媒に溶解した溶液に、上記の熱可塑性樹脂粒子を
分散させて行う。好ましい条件としては、熱可塑
性樹脂に浸透しやすい溶媒を用いることができ
る。又、結晶性の熱可塑性樹脂の場合には、樹脂
を高温で溶解する溶媒を選択し、高温で酸化剤と
均一溶液となし、次いで冷却した後、内部まで酸
化剤を含んだ固化した樹脂を過などによつて分
離して、酸化剤を含浸させた熱可塑性樹脂とする
こともできる。あるいは、酸化剤の溶媒に熱可塑
性樹脂を分散後、過もしくは溶媒の留去によつ
ても酸化剤を含浸した熱可塑性樹脂粒子が得られ
る。又、酸化剤と熱可塑性樹脂を共粉砕したり、
或は熱可塑性樹脂と酸化剤を共に溶解するような
溶媒を用いて、両者を混合後、両者に対して貧溶
媒中で析出、分離するなどしても、酸化剤を含浸
した熱可塑性樹脂粒子が得られる。酸化剤を熱可
塑性樹脂に含浸させる比については特に制限はな
いが好ましくは0.01〜0.5重量比程度である。 In the present invention, the resin particles are impregnated with the oxidizing agent described above, but there are no particular restrictions on the impregnation method. Usually, the above-mentioned thermoplastic resin particles are dispersed in a solution in which an oxidizing agent is dissolved in a solvent. As preferable conditions, a solvent that easily permeates into the thermoplastic resin can be used. In addition, in the case of crystalline thermoplastic resin, select a solvent that dissolves the resin at high temperature, form a homogeneous solution with the oxidizing agent at high temperature, and then cool the solidified resin containing the oxidizing agent to the inside. It is also possible to obtain a thermoplastic resin impregnated with an oxidizing agent by separating it by filtration or the like. Alternatively, thermoplastic resin particles impregnated with an oxidizing agent can also be obtained by dispersing the thermoplastic resin in a solvent for the oxidizing agent and then removing the solvent by distillation. In addition, by co-pulverizing the oxidizing agent and thermoplastic resin,
Alternatively, thermoplastic resin particles impregnated with an oxidizing agent can be obtained by mixing the thermoplastic resin and the oxidizing agent using a solvent that dissolves both, and then precipitating and separating them in a poor solvent for both. is obtained. There is no particular restriction on the ratio of the oxidizing agent to be impregnated into the thermoplastic resin, but the ratio by weight is preferably about 0.01 to 0.5.
本発明において用いる複素五員環式化合物とし
ては、ピロール、フラン、チオフエン、セレノフ
エン、テルロフエン及びそれらの誘導体が挙げら
れる。 Examples of the five-membered heterocyclic compound used in the present invention include pyrrole, furan, thiophene, selenophene, tellurophene, and derivatives thereof.
これらの化合物の蒸気と酸素の混合ガス、或い
はさらに不活性ガスで希釈した混合ガスは上述し
た酸化剤を含浸した熱可塑性樹脂と接触させるこ
とにより導電性樹脂複合体を形成する。この接触
処理は、実質的に液状媒体の存在しない条件下で
行なわれる。即ち、適当な容器に上記の酸化剤を
含浸させた熱可塑性樹脂粒子を入れ、そこに複素
五員環式化合物と酸素を含むガスを流通せしめる
方法、或いは、流動床式や固定床式反応器に上記
の酸化剤を含浸した熱可塑性樹脂粒子を入れ、そ
こに複素五員環式化合物と酸素を含むガスを流通
し接触処理を行う方法などがある。特に均一に接
触処理を行う方法としては流動床式反応器を用い
るのが良好である。 A mixed gas of the vapor of these compounds and oxygen, or a mixed gas further diluted with an inert gas, is brought into contact with the thermoplastic resin impregnated with the above-mentioned oxidizing agent to form a conductive resin composite. This contacting treatment is carried out under conditions substantially free of liquid media. That is, a method in which thermoplastic resin particles impregnated with the above-mentioned oxidizing agent are placed in a suitable container and a gas containing a five-membered heterocyclic compound and oxygen is caused to flow therein, or a fluidized bed type or fixed bed type reactor is used. There is a method in which thermoplastic resin particles impregnated with the above-mentioned oxidizing agent are placed in a container, and a gas containing a five-membered heterocyclic compound and oxygen is passed therethrough for contact treatment. In particular, as a method for uniformly carrying out the contact treatment, it is preferable to use a fluidized bed reactor.
反応温度に関しては特に制限はなく、室温でも
充分反応が進行する。反応時間についても特に制
限はないが、良好な導電性を得るためには、複素
５員環式化合物の重合体が、複合体中に熱可塑性
樹脂に対して0.1〜２重量比程度まで含まれるよ
う混合ガスを流通せしめるのが望ましい。 There is no particular restriction on the reaction temperature, and the reaction proceeds satisfactorily even at room temperature. There is no particular restriction on the reaction time, but in order to obtain good conductivity, the polymer of the 5-membered heterocyclic compound is included in the composite at a weight ratio of about 0.1 to 2 to the thermoplastic resin. It is desirable to allow a mixed gas to flow.
上述の方法で得られた導電性複合樹脂は、必要
に応じて酸化剤を除去する操作が行なわれるが酸
化剤としてルイス酸を用いた場合には、ドーパン
トとして導電性を向上させる効果があるために酸
化剤の除去は特に行なわず、単に未反応の複素五
員環式化合物の除去だけで充分である。 The conductive composite resin obtained by the above method is subjected to an operation to remove the oxidizing agent if necessary, but when a Lewis acid is used as the oxidizing agent, it has the effect of improving conductivity as a dopant. The oxidizing agent is not particularly removed, and it is sufficient to simply remove the unreacted five-membered heterocyclic compound.
本発明の方法を実施することによつて比較的多
量の複素５員環式化合物重合体を均一に分散した
成形可能な複合体が得られしかも機構は不明であ
るが酸素によつては複合体の導電性が大幅に高め
られるため、高導電性の樹脂複合体が容易に得ら
れるものと推定される。
By carrying out the method of the present invention, a moldable composite in which a comparatively large amount of a five-membered heterocyclic compound polymer is uniformly dispersed can be obtained. It is presumed that a highly conductive resin composite can be easily obtained because the conductivity of the resin is significantly increased.
本発明の方法を実施することによつて、成形可
能な導電性樹脂複合体を簡便に得ることができ工
業的に価値が高い。
By carrying out the method of the present invention, a moldable conductive resin composite can be easily obtained and is of high industrial value.
以下、実施例を挙げ、本発明をさらに説明す
る。
Hereinafter, the present invention will be further explained with reference to Examples.
実施例 １
塩化第二鉄１重量部に対してポリプロピレン４
重量部を共粉砕して得た酸化剤含浸樹脂1.0ｇを
ガラス管につめ、２mlのピロールを乾燥した空気
（20ml／min）とともに吹き込んだ、反応温度は
室温であり、所要時間は24時間であつた。乾燥
後、得られたポリピロール複合体は1.2ｇであり、
加熱圧縮した成形物の比抵抗は1.6×102Ωcmであ
つた。Example 1 1 part by weight of ferric chloride to 4 parts polypropylene
1.0 g of the oxidizing agent-impregnated resin obtained by co-pulverizing the parts by weight was packed in a glass tube, and 2 ml of pyrrole was blown in with dry air (20 ml/min). The reaction temperature was room temperature, and the reaction time was 24 hours. It was hot. After drying, the obtained polypyrrole composite weighs 1.2 g;
The specific resistance of the heated and compressed molded product was 1.6×10 2 Ωcm.
比較例 １
実施例１において乾燥した空気の代りに窒素ガ
スを用いるほかは実施例１と同様の操作を行つた
ところ、得られたポリピロール複合体は1.15ｇで
あり、加熱圧縮した成形物の比抵抗は1.6×103Ω
cmであつた。Comparative Example 1 The same operation as in Example 1 was carried out except that nitrogen gas was used instead of dry air. Resistance is 1.6×10 3 Ω
It was cm.
実施例 ２
実施例１において乾燥した空気の代りに、酸素
を用いてるほかは実施例１と同様の操作を行つた
ところ、得られたポリピロール複合体は1.2ｇで
あり、加熱圧縮した成形物の比抵抗は7.0×10Ω
cmであつた。Example 2 The same operation as in Example 1 was carried out except that oxygen was used instead of the dry air in Example 1, and the obtained polypyrrole composite weighed 1.2 g, which was the same as that of a heated and compressed molded product. Specific resistance is 7.0×10Ω
It was cm.
実施例 ３
実施例１においてポリプロピレンの代りに、ア
クリルニトリル系共重合体″バレツクス″（商標、
ソハイオケミカル社製）を用いるほかは実施例１
と同様の操作を行つたところ、ポリピロール複合
体は1.25ｇであり、加熱圧縮した成形物の比抵抗
は5.0×103Ωcmであつた。Example 3 In Example 1, instead of polypropylene, acrylonitrile copolymer "Barex" (trademark) was used.
Example 1, except that the material (manufactured by Sohio Chemical Co., Ltd.) was used.
When the same operation as above was carried out, the weight of the polypyrrole composite was 1.25 g, and the specific resistance of the heated and compressed molded product was 5.0×10 3 Ωcm.
実施例 ４
実施例１において、ピロールをチオフエンに代
え、反応時間を240時間にするほかは実施例１と
同様の操作を行つたところ得られたポリチオフエ
ン複合体は1.1ｇであり、加熱圧縮した成形物の
比抵抗は4.5×105Ωcmであつた。Example 4 The same procedure as in Example 1 was carried out except that pyrrole was replaced with thiophene and the reaction time was changed to 240 hours. The specific resistance of the material was 4.5×10 5 Ωcm.
Claims (1)
及び複素５員環式化合物を含有するガスを接触せ
しめることを特徴とする導電性樹脂複合体の製造
方法。1. A method for producing a conductive resin composite, which comprises contacting thermoplastic resin particles impregnated with an oxidizing agent with a gas containing oxygen and a five-membered heterocyclic compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60000115A JPS61264053A (en) | 1985-01-07 | 1985-01-07 | Production of electrically-conductive resin composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60000115A JPS61264053A (en) | 1985-01-07 | 1985-01-07 | Production of electrically-conductive resin composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61264053A JPS61264053A (en) | 1986-11-21 |
| JPH0556367B2 true JPH0556367B2 (en) | 1993-08-19 |
Family
ID=11465051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60000115A Granted JPS61264053A (en) | 1985-01-07 | 1985-01-07 | Production of electrically-conductive resin composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61264053A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6284115A (en) * | 1985-10-09 | 1987-04-17 | Mitsubishi Chem Ind Ltd | conductive material |
| JPH0819222B2 (en) * | 1987-04-14 | 1996-02-28 | 凸版印刷株式会社 | Method for producing conductive polymer |
| JPH07103297B2 (en) * | 1989-11-27 | 1995-11-08 | アキレス株式会社 | Conductive composite |
| JPH0616948A (en) * | 1992-04-16 | 1994-01-25 | Mearthane Prod Corp | Conductive and semiconductive polymer materials |
| US6111051A (en) | 1998-08-07 | 2000-08-29 | Mearthane Products Corporation | Preparation of conductive polyurethanes using a conductive quasi-solution |
| US5639847A (en) * | 1995-05-25 | 1997-06-17 | Mearthane Products Corp. | Preparation of conductive polyurethanes using a conductive quasi-solution |
| US6451438B1 (en) | 2000-11-30 | 2002-09-17 | Mearthane Products Corporation | Copolymerization of reactive silicone and urethane precursors for use in conductive, soft urethane rollers |
| US8222341B2 (en) | 2009-03-17 | 2012-07-17 | Mearthane Products Corporation | Semi-conductive silicone polymers |
-
1985
- 1985-01-07 JP JP60000115A patent/JPS61264053A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61264053A (en) | 1986-11-21 |
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