JPS61283656A - Electrically conductive resin composition - Google Patents
Electrically conductive resin compositionInfo
- Publication number
- JPS61283656A JPS61283656A JP12434785A JP12434785A JPS61283656A JP S61283656 A JPS61283656 A JP S61283656A JP 12434785 A JP12434785 A JP 12434785A JP 12434785 A JP12434785 A JP 12434785A JP S61283656 A JPS61283656 A JP S61283656A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- membered heterocyclic
- ferromagnetic
- polymer
- iron
- 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】
〔産業上の利用分野〕
本発明は導電性でしかも強磁性を有する樹脂組成物に関
する。詳しくは特定の粒子を樹脂中に分散してなる樹脂
組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition that is electrically conductive and ferromagnetic. Specifically, the present invention relates to a resin composition in which specific particles are dispersed in a resin.
静電気帯電防止あるいは電磁波シールド性を有する導電
性の樹脂組成物が開発されている。このために従来アル
ミニウム、ステンレス鋼などの金属の粉末あるいは繊維
、炭素粉末、炭素繊維などを樹脂中に添加混合すること
が行われている。Conductive resin compositions that have antistatic or electromagnetic shielding properties have been developed. For this purpose, powders or fibers of metals such as aluminum and stainless steel, carbon powders, carbon fibers, etc. have been conventionally added and mixed into the resin.
上述の従来の方法では導電性を付与するという目的はあ
る程度達成されるものの、金属の粉末や金属あるいは炭
素繊維を添加する方法では添加物が高価である上に樹脂
との混合および得られた組成物の成形加工が困難である
などの問題がある。Although the above-mentioned conventional methods achieve the purpose of imparting conductivity to some extent, the methods of adding metal powder, metal, or carbon fiber require expensive additives and are difficult to mix with resin and the resulting composition. There are problems such as difficulty in molding and processing objects.
また、炭素の粉末を添加する方法は添加物が比較的安価
であるが樹脂との混合が困難であり均一に分散し難いと
い５間頂かあり１強磁性の性質を付与することはできな
い。又、マグヘマイトのような強磁性の粒子を樹脂中に
分散せしめることで強磁性の樹脂組成物とすることはで
きるが導電性はほとんど期待できない。Further, in the method of adding carbon powder, although the additive is relatively inexpensive, it is difficult to mix with the resin, and it is difficult to disperse uniformly, and it is impossible to impart ferromagnetic properties due to the presence of 5-magnetic peaks. Furthermore, although a ferromagnetic resin composition can be obtained by dispersing ferromagnetic particles such as maghemite in a resin, it is hardly expected to have electrical conductivity.
本発明者らは上記問題を解決した導電性でしかも強磁性
を有する樹脂組成物について鋭意探索し。The present inventors have earnestly searched for a conductive and ferromagnetic resin composition that solves the above problems.
本発明を完成した。The invention has been completed.
すなわち１本発明は酸化剤を含浸せしめた強磁性酸化物
粒子と複素５員環式化合物を接触して得た複素５員環式
化合物の重合体を含有する粒子な貢脂中に分散してなる
導電性樹脂組成物である。That is, 1. the present invention involves dispersing in particles containing a polymer of a five-membered heterocyclic compound obtained by contacting ferromagnetic oxide particles impregnated with an oxidizing agent and a five-membered heterocyclic compound. This is a conductive resin composition.
本発明において用いられる強磁性酸化物としては、マグ
ネタイト、マグネタイトなどの鉄の酸化物を始めとして
、フェライト構造を有する鉄と他の金属との酸化物が例
示できる。また市販の磁性材料用のものがそのまま使用
でき、粒子の形状としても特に制限はないが、好ましく
は球状ないし針状の粒子、即ちアスペクト比が１〜１０
０のものが使用できる。粒子の大きさとしては、長袖が
０．１〜１０００μｍ程度のものが好ましい。Examples of the ferromagnetic oxide used in the present invention include magnetite, iron oxides such as magnetite, and oxides of iron and other metals having a ferrite structure. Also, commercially available magnetic materials can be used as is, and there are no particular restrictions on the shape of the particles, but preferably spherical or acicular particles, that is, with an aspect ratio of 1 to 10.
0 can be used. The particle size is preferably about 0.1 to 1000 μm for long sleeves.
本発明においては上記強磁性酸化物粒子上に複素５員環
式化合物が重合されるが、この際に使用する酸化剤とし
ては、無機酸、金属化合物が有効であり、硫酸、塩酸、
硝酸、クロルスルホン酸などの無機酸、或は金属化合物
としては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。In the present invention, a five-membered heterocyclic compound is polymerized on the ferromagnetic oxide particles. Inorganic acids and metal compounds are effective as oxidizing agents used at this time, such as sulfuric acid, hydrochloric acid,
Inorganic acids such as nitric acid and chlorosulfonic acid, or metal compounds such as aluminum, tin, titanium, zirconium, chromium, manganese, iron, copper, and molybdenum, which are known as Lewis acids.
タンクステン、ルテニウム、パラジウム、白金等の金属
の塩化物、硫酸塩、硝酸塩アセチルアセトナート化合物
などが具体例として挙げられ、その他の酸化剤としてベ
ンゾキノン、ジアゾニウム塩などの有機化合物も使用可
能であり、これらの酸化剤は１種又は２種以上混合して
用いることも可能であり特に鉄、チタンの塩化物、硫酸
塩及び過硫酸のアルカリ金属塩或はアンモニウム塩が好
ましく使用できる。Specific examples include chlorides, sulfates, and nitrate acetylacetonate compounds of metals such as tanksten, ruthenium, palladium, and platinum, and organic compounds such as benzoquinone and diazonium salts can also be used as other oxidizing agents. These oxidizing agents may be used alone or in combination of two or more, and particularly preferred are iron and titanium chlorides, sulfates, and alkali metal salts or ammonium salts of persulfuric acid.
これらの酸化剤を含浸せしめる方法としては酸化剤と強
磁性酸化物粒子を共粉砕する方法、酸化剤を溶解した溶
液中に強磁性酸化物粒子を分散混合し次いでろ過、ある
いは溶媒を蒸発除去する方法、又は酸化剤の蒸気下に強
磁性酸化物粒子を分散し酸化剤を吸着せしめる方法など
が挙げられる。Methods for impregnating these oxidizing agents include co-pulverizing the oxidizing agent and ferromagnetic oxide particles, dispersing and mixing ferromagnetic oxide particles in a solution containing the oxidizing agent, and then filtering or removing the solvent by evaporation. or a method in which ferromagnetic oxide particles are dispersed under the vapor of an oxidizing agent to adsorb the oxidizing agent.
酸化剤と強磁性酸化物粒子との量比については特に制限
はないがｏ 、ｏｏｉ〜１．Ｏ重量比好ましくは０．０
１−０．２ 重量比である。There are no particular restrictions on the ratio of the oxidizing agent to the ferromagnetic oxide particles, but the ratio is between o, ooi and 1. O weight ratio preferably 0.0
1-0.2 weight ratio.
本発明において使用する複素５員環式化合物としてはピ
ロール、フラン、チオフェン及びそれらの誘導体が挙げ
られ中でもピロール、Ｎ−アルキルピロール、Ｎ−アリ
ールピロール、３及び／又は４位にアルキル基、ハロゲ
ン原子の置換した置換ピロールなどのピロール誘導体が
反応性の点から有利である。Examples of the five-membered heterocyclic compound used in the present invention include pyrrole, furan, thiophene, and derivatives thereof, including pyrrole, N-alkylpyrrole, N-arylpyrrole, an alkyl group at the 3 and/or 4 position, and a halogen atom. Pyrrole derivatives such as substituted pyrrole are advantageous from the viewpoint of reactivity.
酸化剤を含浸させた強磁性酸化物粒子と複素５員環式化
合物との接触方法としては、酸化剤を含浸させた強磁性
酸化物粒子を気相あるいは液相の複素５員環式化合物と
接触する方法が挙げられ。As a method of contacting ferromagnetic oxide particles impregnated with an oxidizing agent and a five-membered heterocyclic compound, the ferromagnetic oxide particles impregnated with an oxidizing agent are brought into contact with a five-membered heterocyclic compound in a gas phase or a liquid phase. There are ways to contact them.
具体的には、酸化剤を含浸せしめた強磁性酸化物粒子を
流動床あるいは固定床式反応器に入れ複素５員環式化合
物の蒸気を、必要に応じ窒素、ヘリウム、アルゴン、酸
素などの気体で希釈して、導入する方法あるいは、複素
５員環式化合物を溶解した溶液中に酸化剤を含浸せしめ
た強磁性酸化物粒子を分散攪拌処理することでスラリー
状態で反応する方法が例示される。Specifically, ferromagnetic oxide particles impregnated with an oxidizing agent are placed in a fluidized bed or fixed bed reactor, and the vapor of the 5-membered heterocyclic compound is mixed with a gas such as nitrogen, helium, argon, or oxygen as necessary. Examples include a method of diluting and introducing the compound, or a method of reacting in a slurry state by dispersing and stirring ferromagnetic oxide particles impregnated with an oxidizing agent in a solution containing a five-membered heterocyclic compound. .
本発明においては上述のような方法で得られた複素５員
環式化合物の重合体を含有する粒子を樹′脂と混合する
ことで導電性でしかも強磁性の樹脂組成物が得られる。In the present invention, an electrically conductive and ferromagnetic resin composition can be obtained by mixing particles containing a polymer of a five-membered heterocyclic compound obtained by the method described above with a resin.
ここで樹脂としては特に制限はなく、ポリエチレン、ポ
リプロピレン４ポリスチレン、ポリ塩化ビニル、ポリメ
タクリル酸メチル、ポリカーボネート、ポリフェニレン
オキサイド、ポリアミド。The resin is not particularly limited, and includes polyethylene, polypropylene 4 polystyrene, polyvinyl chloride, polymethyl methacrylate, polycarbonate, polyphenylene oxide, and polyamide.
ポリエステルなどの熱可塑性樹脂をはじめあらゆる樹脂
を用いることが可能であり、ポリイミド。It is possible to use any resin, including thermoplastic resins such as polyester, and polyimide.
フ＝ノール樹脂などの熱硬化性の樹脂であっても溶剤に
可溶または熱可塑性を有するプレポリマーの状態で混合
することで本発明の導電性の樹脂組成物とすることがで
きる。Even thermosetting resins such as phenol resins can be mixed in the form of prepolymers that are soluble in solvents or have thermoplasticity to form the conductive resin composition of the present invention.
上述の樹脂と複素５員環式化合物重合体含有粒子の混合
方法については特に制限はなく、樹脂が熱可塑性であれ
ばヘンシールミキサーなどで混合した後、押出機などで
造粒混合する方法あるいはロールなどを用いて混合する
ことができる。There is no particular restriction on the method of mixing the above-mentioned resin and the particles containing the five-membered heterocyclic compound polymer.If the resin is thermoplastic, it may be mixed in a Henshil mixer or the like, and then granulated and mixed in an extruder or the like; Mixing can be performed using a roll or the like.
熱硬化性の樹脂の場合には比較的高粘度の溶液あるいは
溶融状態で混合し、成形物とした後硬化する方法が採用
できる。In the case of thermosetting resins, a method can be adopted in which the resins are mixed in a relatively high viscosity solution or molten state, formed into a molded product, and then cured.
本発明の組成物は元の樹脂に比較して物性が劣ることも
なく、樹脂への分散が良好であるため。This is because the composition of the present invention does not have inferior physical properties compared to the original resin and is well dispersed in the resin.
導電性が高く、しかも強磁性であるというすぐれた機能
を有しており、電磁７−ルド材料などの用途が期待でき
、工業的に極めて価値がある。It has excellent functions of being highly conductive and ferromagnetic, and can be expected to be used as an electromagnetic 7-wire material, making it extremely valuable industrially.
以下、実施例を挙げ本発明をさらに説明する。 The present invention will be further explained below with reference to Examples.
実施例１
〔重合体を含有する粒子の製造〕
マグヘマイト（戸田工業（株）製） １ ｋｇと塩化第
２鉄１０（ｌを共粉砕して酸化剤含浸マグヘマイト粒子
とした。この粒子を内径１０ＣＩｒＬの流動床反応装置
に入れ、ビロールの蒸気を空気に同伴させて、ビロール
として２００ｍ１／ｈで導入し、５時間反応した。ビロ
ール重合体０．０４ｋｇを含有する粒子を得た。Example 1 [Production of particles containing polymer] 1 kg of maghemite (manufactured by Toda Kogyo Co., Ltd.) and 10 (l) of ferric chloride were co-pulverized to obtain oxidizing agent-impregnated maghemite particles. The particles had an inner diameter of 10 CIrL. The mixture was placed in a fluidized bed reactor, and virol vapor was entrained in air, introduced as virol at a rate of 200 ml/h, and reacted for 5 hours.Particles containing 0.04 kg of virol polymer were obtained.
上記重合体を含有する粒子１ｋｌＪとプロピレンとエチ
レンのブロック共重合体（エチレン含１９ｗｔ％）１０
ｋｇを２５朋押出機（ＢＴ−２５プラスチツク工学研究
所＠）製）を用いて造粒し、得られた組成物を用いて厚
さ１朋の射出成形フートを作成し、物性を測定した。結
果を表に示す。1klJ of particles containing the above polymer and 10% block copolymer of propylene and ethylene (19wt% ethylene content)
kg was granulated using a 25 mm extruder (BT-25 manufactured by Plastics Engineering Research Institute @), and the resulting composition was used to create an injection molded foot with a thickness of 1 mm, and its physical properties were measured. The results are shown in the table.
なお、各物性の測定は下記によった。In addition, each physical property was measured as follows.
（１）メルトフローインデックスＭ丁： ＡＳＴＭ
Ｄ１２３８（条件２３０°Ｃ１荷重２．１６に！Ｆ）（
２）降伏応力 ：ＡＳＴＭ Ｄ６３８（２３°Ｃ
）（３）デーポン衝撃強度 ：ＪＩＳ Ｋ−６７１
８に準する（−１０°Ｃ１２３°Ｃ）
（４）アイジフト衝撃強度 ： ＡＳＴＭ Ｄ２５
６（−１０°Ｃ１２３°Ｃ）
（５）曲げ剛性率 ：ＡＳＴＭ Ｄ７４７（２３℃
）比較例１．参考例１
実施例１で用いたマグヘマイトのみを実施例１と同様の
条件で単に粉砕したものを用いた他は実施例１と同様に
造粒成形し、物性を測定した（比較例１）。又、参考の
ためブロック共重合体のみを造粒成形し、物性を測定し
た（参考例１）。これらの結果を表に示す。(1) Melt flow index M: ASTM
D1238 (condition 230°C1 load 2.16!F) (
2) Yield stress: ASTM D638 (23°C
) (3) Depon impact strength: JIS K-671
8 (-10°C123°C) (4) Eye lift impact strength: ASTM D25
6 (-10°C123°C) (5) Bending rigidity: ASTM D747 (23°C
) Comparative example 1. Reference Example 1 Pelletization was performed in the same manner as in Example 1, except that the maghemite used in Example 1 was simply ground under the same conditions as in Example 1, and the physical properties were measured (Comparative Example 1). For reference, only the block copolymer was granulated and its physical properties were measured (Reference Example 1). These results are shown in the table.
実施例２
ビロール５００−を、５１のシクロヘキサンに溶解した
溶液中に実施例１と同様に共粉砕して得た塩化第２鉄含
浸マグヘマイトを１０時間分散混合し、ろ過してシクロ
ヘキサン及び未反応のビロールを除去して乾燥して重合
体を含有する粒子を得た。このものは０．０６ ｋＰの
ビロールの重合体を含有していた。この重合体を含有す
る粒子を用い。Example 2 Ferric chloride-impregnated maghemite obtained by co-pulverizing Virol 500- in the same manner as in Example 1 was dispersed in a solution of 51 dissolved in cyclohexane for 10 hours, and filtered to remove cyclohexane and unreacted Virol was removed and dried to obtain polymer-containing particles. This contained a 0.06 kP virol polymer. using particles containing this polymer.
実施例１と同様に造粒成形し、物性を測定した。It was granulated and molded in the same manner as in Example 1, and its physical properties were measured.
結果を表に示す。The results are shown in the table.
実施例３．比較例２
マグヘマイトにかえてマグネタイト（和光紬薬（イ）製
を用いた他は実施例１（実施例３）、比較例１（比較例
２）と同様に造粒成形し、物性を測定した。結果を表に
示す。Example 3. Comparative Example 2 Granule molding was carried out in the same manner as in Example 1 (Example 3) and Comparative Example 1 (Comparative Example 2) except that magnetite (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) was used instead of maghemite, and the physical properties were measured. .The results are shown in the table.
実施例４
ビロールにかえてチオフェンを用いて得た重合体を含有
する粒子を用いた他は実施例１と同様に造粒成形し、物
性を測定した。結果を表に示す。Example 4 Particles were formed in the same manner as in Example 1, except that particles containing a polymer obtained by using thiophene instead of virol were used, and the physical properties were measured. The results are shown in the table.
なお１重合体を含有する粒子はチオフーン重合体をマグ
ヘマイ）ｌｋｌ？に対し０．０２ｋｇ含有していた。Particles containing one polymer are thiophene polymers (maghemai) lkl? It contained 0.02 kg.
Claims (1)
環式化合物を接触して得た複素５員環式化合物の重合体
を含有する粒子を樹脂中に分散してなる導電性樹脂組成
物。1. A conductive resin obtained by dispersing in a resin particles containing a polymer of a five-membered heterocyclic compound obtained by contacting ferromagnetic oxide particles impregnated with an oxidizing agent and a five-membered heterocyclic compound. Composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12434785A JPS61283656A (en) | 1985-06-10 | 1985-06-10 | Electrically conductive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12434785A JPS61283656A (en) | 1985-06-10 | 1985-06-10 | Electrically conductive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61283656A true JPS61283656A (en) | 1986-12-13 |
| JPH0443111B2 JPH0443111B2 (en) | 1992-07-15 |
Family
ID=14883115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12434785A Granted JPS61283656A (en) | 1985-06-10 | 1985-06-10 | Electrically conductive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61283656A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62116665A (en) * | 1985-11-18 | 1987-05-28 | Mitsui Toatsu Chem Inc | Electrically conductive resin composition |
| DE19631563A1 (en) * | 1996-07-26 | 1998-02-26 | Frank Dr Ing Lux | Pure or functionalised electroconductive polymer material |
| WO2003089515A1 (en) * | 2002-04-22 | 2003-10-30 | Konica Minolta Holdings, Inc. | Organic semiconductor composition, organic semiconductor element, and process for producing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59168010A (en) * | 1983-03-07 | 1984-09-21 | バスフ アクチエンゲゼルシヤフト | Manufacture of electroconductive powdery pyrrole polymer |
| JPS61250057A (en) * | 1985-04-30 | 1986-11-07 | Mitsui Toatsu Chem Inc | Conductive resin composition |
-
1985
- 1985-06-10 JP JP12434785A patent/JPS61283656A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59168010A (en) * | 1983-03-07 | 1984-09-21 | バスフ アクチエンゲゼルシヤフト | Manufacture of electroconductive powdery pyrrole polymer |
| JPS61250057A (en) * | 1985-04-30 | 1986-11-07 | Mitsui Toatsu Chem Inc | Conductive resin composition |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62116665A (en) * | 1985-11-18 | 1987-05-28 | Mitsui Toatsu Chem Inc | Electrically conductive resin composition |
| DE19631563A1 (en) * | 1996-07-26 | 1998-02-26 | Frank Dr Ing Lux | Pure or functionalised electroconductive polymer material |
| WO2003089515A1 (en) * | 2002-04-22 | 2003-10-30 | Konica Minolta Holdings, Inc. | Organic semiconductor composition, organic semiconductor element, and process for producing the same |
| JPWO2003089515A1 (en) * | 2002-04-22 | 2005-09-02 | コニカミノルタホールディングス株式会社 | Organic semiconductor composition, organic semiconductor element and method for producing the same |
| US7582897B2 (en) | 2002-04-22 | 2009-09-01 | Konica Minolta Holdings, Inc. | Organic semiconductor composition, organic semiconductor element, and their manufacturing method |
| JP4736324B2 (en) * | 2002-04-22 | 2011-07-27 | コニカミノルタホールディングス株式会社 | Semiconductor device and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0443111B2 (en) | 1992-07-15 |
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