JPH0717838B2 - Composite organic dielectric - Google Patents
Composite organic dielectricInfo
- Publication number
- JPH0717838B2 JPH0717838B2 JP12929686A JP12929686A JPH0717838B2 JP H0717838 B2 JPH0717838 B2 JP H0717838B2 JP 12929686 A JP12929686 A JP 12929686A JP 12929686 A JP12929686 A JP 12929686A JP H0717838 B2 JPH0717838 B2 JP H0717838B2
- Authority
- JP
- Japan
- Prior art keywords
- organic
- dielectric
- polymer
- conjugated
- organic 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 - Fee Related
Links
Landscapes
- 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、誘電率の良好な新規な複合有機誘電体に関す
る。TECHNICAL FIELD The present invention relates to a novel composite organic dielectric having a good dielectric constant.
従来、高分子化合物の誘電率を高める方法として、チタ
ン酸バリウム等の高誘電率のセラミック誘電体を添加し
て、該高分子化合物よりも高い誘電率を有する組成物を
得る方法は知られている（特開昭53−88198、同53−138
448、同58−166609、同60−107204号等）。Conventionally, as a method of increasing the dielectric constant of a polymer compound, a method of adding a ceramic dielectric having a high dielectric constant such as barium titanate to obtain a composition having a dielectric constant higher than that of the polymer compound is known. (Japanese Patent Laid-Open Nos. 53-88198 and 53-138)
448, 58-166609, 60-107204, etc.).
一方、軽量化や賦形性の面で有利な有機化合物誘電体、
例えば、テトラシアノキノジメタン錯塩を添加する方法
も知られている（特開昭51−62840、同57−40807、同57
−16415、同57−187356号等）。On the other hand, organic compound dielectrics that are advantageous in terms of weight reduction and shapeability,
For example, a method of adding a tetracyanoquinodimethane complex salt is also known (JP-A-51-62840, JP-A-57-40807, and JP-A-57-40807).
-16415, 57-187356, etc.).
しかしながら、これら従来の誘電体組成物で用いる誘電
体は、一般に微粒子であるため二次凝集を起こしやすい
ほか、そもそも高分子化合物との相溶性が悪いため、得
られる誘電体組成物は、構成成分の誘電体粒子が本来有
する誘電特性を十分発揮し得ていない。However, since the dielectrics used in these conventional dielectric compositions are generally fine particles, secondary aggregation is likely to occur, and since the compatibility with polymer compounds is poor in the first place, the resulting dielectric composition has The dielectric properties originally possessed by the above dielectric particles cannot be sufficiently exhibited.
本発明は、有機化合物誘電体が高分子化合物中へ相溶性
がよく、かつ均一に混和して有機化合物誘電体が本来有
する誘電特性を十分ひき出すべく、両者間に有機共役系
高分子を存在させることにより、この目的を達成して為
されたものである。The present invention has an organic conjugated polymer between the organic compound dielectric and the organic compound dielectric so that the organic compound dielectric has a good compatibility with the polymer compound and is mixed uniformly to bring out the dielectric properties originally possessed by the organic compound dielectric. By doing so, it was achieved to achieve this purpose.
即ち、本発明は、「非共役系有機高分子と有機化合物誘
電体粒子との間に有機共役系高分子が少なくとも部分的
に存在している構成からなることを特徴とする複合有機
誘電体」である。That is, the present invention is a "composite organic dielectric characterized in that the organic conjugated polymer is at least partially present between the non-conjugated organic polymer and the organic compound dielectric particles". Is.
本発明の複合誘電体は、有機化合物誘電体が二次凝集少
なく均一に分散しているため、良好な誘電特性を発揮す
る。これにより、一般コンデンサー用のほか光起電力の
太陽電池用など広い範囲の応用が期待される。The composite dielectric of the present invention exhibits good dielectric properties because the organic compound dielectric is uniformly dispersed with little secondary aggregation. As a result, it is expected to be applied in a wide range of applications such as general capacitors as well as photovoltaic solar cells.
本発明で使用する非共役系有機高分子は、ポリオレフィ
ン（エチレン重合体、プロピレン重合体、ポリ−４−メ
チルペンテン−１、ポリブデン−１等の単独または共重
合体でワックスも含まれる）、熱可塑性ポリエステル
（ポリエチレンテレフタレート、ポリブチレンテレフタ
レート等、低分子量物も含む）、ポリカーボネート、ポ
リスチレン、ポリアクリロニトリル、ポリスチレン、ハ
ロカーボン重合体（ポリフッ化ビニル、ポリ塩化ビニ
ル、ポリ塩化ビニリデン）、ポリメチルメタクリレート
などの熱可塑性高分子のほか、エポキシ樹脂、不飽和ポ
リエステルなどの熱硬化性高分子が挙げられる。これら
は２種以上併用してもよい。The non-conjugated organic polymer used in the present invention is a polyolefin (a homopolymer or a copolymer of ethylene polymer, propylene polymer, poly-4-methylpentene-1, polybutene-1, etc., including wax), heat Plastic polyester (including low molecular weight materials such as polyethylene terephthalate, polybutylene terephthalate, etc.), polycarbonate, polystyrene, polyacrylonitrile, polystyrene, halocarbon polymer (polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride), polymethyl methacrylate, etc. In addition to thermoplastic polymers, thermosetting polymers such as epoxy resins and unsaturated polyesters may be mentioned. You may use these 2 or more types together.
分散性、相溶性のほか、接着性、帯電性、着色性などの
他の機能をも要求される場合は、各種のグラフトまたは
ブロック共重合体を用いることも構わない。特に色素等
の特徴を同時に期待する場合は、光透過性の高い高分子
が選ばれる。また、後に架橋させることもできる。In addition to dispersibility and compatibility, various other functions such as adhesiveness, chargeability, and colorability are required, and various graft or block copolymers may be used. In particular, when characteristics such as a dye are also expected at the same time, a polymer having high light transmittance is selected. It can also be crosslinked later.
次に、本発明で使用する有機化合物誘電体は粒子状のも
のである。大きさは用途によって異なるが最終的に上記
高分子と複合化するため、あまり大きくない方が良い。
好ましくは20μ以下、さらに好ましくは10μ以下、特に
好ましくは５μ以下である。具体的な例としては、例え
ば誘電性有機顔料がある。これには銅フタロシアニンの
ような金属フタロシアニン、無金属フタロシアニン等の
シアン顔料；クロロダイアンブルーのようなアゾ顔料；
あるいはクリプトシアニン、シアニンのようなシアニン
顔料などがある。特に安定性の点からフタロシアニン顔
料が好ましい。またテトラシアノキノジメタン塩（TCNQ
塩）、あるいはポリ（ビニルピリジニウム）−（TCNQ）
−やポリ（１−メチル−２−ビニルピリジニウム）−
（TCNQ）2 -のような高分子−TCNQ塩なども使用できる。
さらに、ポリフッ化ビニリデンや液晶ポリエステルなど
の強い配向性を持つ高分子も用いられる。Next, the organic compound dielectric used in the present invention is in the form of particles. The size depends on the application, but it is preferable that the size is not too large because it will eventually form a composite with the polymer.
It is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. A specific example is a dielectric organic pigment. This includes cyan pigments such as metal phthalocyanines such as copper phthalocyanine and metal-free phthalocyanines; azo pigments such as chlorodian blue;
Alternatively, there are cyanine pigments such as cryptocyanine and cyanine. A phthalocyanine pigment is particularly preferable from the viewpoint of stability. Also, tetracyanoquinodimethane salt (TCNQ
Salt) or poly (vinylpyridinium)-(TCNQ)
- and poly (1-methyl-2-vinyl pyridinium) -
(TCNQ) 2 - such as a polymer -TCNQ salts such as can be used.
Further, polymers having strong orientation such as polyvinylidene fluoride and liquid crystal polyester are also used.
特に強い配向を持ち、安定な結晶微粒子となるものが好
ましい。そのような物は、例えば、 のような通常用いられる芳香族ポリエステルまたはコポ
リエステルの微粒子化物（m,nは２以上の整数）があ
る。It is particularly preferable that the crystalline fine particles have a strong orientation and are stable. Such things are, for example, There is a fine particle product (m, n is an integer of 2 or more) of aromatic polyester or copolyester which is usually used.
また、本発明で使用する有機共役系高分子としては、ポ
リピロール、ポリチオフェン、ポリフラン、ポリアニリ
ン、ポリアセチレン、ポリフェニレンスルフィド、ポリ
ジアセチレン等がある。これら有機共役系高分子の電気
伝導率を調整するために、通常、FeCl3,AsF5,BF4,I3等
のドーパントを添加するが、これを用いなくてもよい。Examples of the organic conjugated polymer used in the present invention include polypyrrole, polythiophene, polyfuran, polyaniline, polyacetylene, polyphenylene sulfide, and polydiacetylene. In order to adjust the electric conductivity of these organic conjugated polymers, a dopant such as FeCl 3 , AsF 5 , BF 4 , I 3 or the like is usually added, but this may not be used.
有機共役系高分子を非共役系有機高分子と有機化合物誘
電体粒子との間に存在させる方法は種々あるが、例え
ば、有機化合物誘電体粒子の表面に有機共役系高分子を
付着させてから、これを非共役系有機高分子と複合体す
る方法、または、三者を一緒に配合して複合化し、結果
として有機共役系高分子が有機化合物誘電体粒子の表面
に集まるように、有機共役系高分子の非共役系有機高分
子に対する親和性よりも有機化合物誘電体粒子に対する
親和性の方が大きくなるように選択する方法を採用する
ことができる。There are various methods of allowing the organic conjugated polymer to exist between the non-conjugated organic polymer and the organic compound dielectric particles. For example, after the organic conjugated polymer is attached to the surface of the organic compound dielectric particles, , A method in which this is combined with a non-conjugated organic polymer, or a method in which the three are compounded together to form a composite, and as a result, the organic conjugated polymer is collected on the surface of the organic compound dielectric particles, the organic conjugated It is possible to adopt a method of selecting such that the affinity of the organic polymer for the organic compound dielectric particles is higher than the affinity of the non-conjugated organic polymer for the organic polymer.
ここで、有機共役系高分子を有機化合物誘電体粒子の表
面に付着させる方法としては、有機化合物誘電体粒子
を懸濁させた溶媒中に有機共役系高分子を溶かし、その
後溶剤を除去する方法、有機共役系高分子を蒸着して
該誘電体粒子表面に付着させる方法、有機化合物誘電
体粒子の表面に重合開始剤を付着させ、その有機共役系
単量体を接触、重合させる方法などである。これらの方
法で最も好ましいのはの方法である。Here, as a method of attaching the organic conjugated polymer to the surface of the organic compound dielectric particles, a method of dissolving the organic conjugated polymer in a solvent in which the organic compound dielectric particles are suspended, and then removing the solvent , A method of depositing an organic conjugated polymer on the surface of the dielectric particle, a method of attaching a polymerization initiator to the surface of the organic compound dielectric particle, and contacting and polymerizing the organic conjugated monomer. is there. The most preferred of these methods is.
複合体は、非共役有機高分子がマトリクス相となる程の
多量でも構わず、また、有機化合物誘電体粒子が大部分
を構成し、それら粒子間を保持できる接着機能を有する
程度の量の非共役有機高分子がバインダーとして存在す
るものであってもよい。The composite may have a large amount such that the non-conjugated organic polymer becomes a matrix phase, and the organic compound dielectric particles make up a large part of the composite, and an amount of non-conjugated organic polymer having an adhesive function capable of holding the particles is sufficient. The conjugated organic polymer may be present as a binder.
有機化合物誘電体粒子の量は、希望の誘電特性により選
択し得るが、0.1重量％以上、特に１重量％以上が好ま
しい。The amount of organic compound dielectric particles can be selected according to the desired dielectric properties, but is preferably 0.1% by weight or more, and particularly preferably 1% by weight or more.
また、有機共役系高分子の量は、該誘電体粒子に対して
0.1〜90重量％、特に0.2〜50重量％が好ましい。Further, the amount of the organic conjugated polymer is based on the dielectric particles.
0.1 to 90% by weight, particularly 0.2 to 50% by weight are preferred.
複合化は、非共役有機高分子が熱可塑性の場合は通常の
混練法または溶液混合後に乾燥する方法により、また、
熱硬化性の場合は混合後に硬化させる方法により行なう
ことができる。When the non-conjugated organic polymer is thermoplastic, the compounding is carried out by a usual kneading method or a method of drying after solution mixing,
In the case of thermosetting, it can be performed by a method of curing after mixing.
実施例１ 平均粒径約12μの銅フタロシアニンをジェット粉砕機で
平均粒径約１μに粉砕した後、真空乾燥器にて50℃で８
時間乾燥した。この銅フタロシアニン60gを500cc三つ口
フラスコに投入し、さらにFeCl33gを溶解したメタノー
ル200ccを投入して窒素雰囲気下、室温で２時間十分に
撹拌混合した。次に、これからメタノールを除去し、さ
らに真空乾燥器にて50℃で12時間乾燥した。これにｎ−
ヘプタン250ccを投入して懸濁させ、窒素雰囲気下でピ
ロール25gを滴下しつつ80℃で３時間反応させた。反応
終了後冷却してメタノールを加えた。沈澱物を過し、
さらにメタノールで洗浄した。過物を乾燥して生成物
63gを得た。このものを30重量部とポリメチルメタクリ
レート70重量部をブラベンダープラストミルにて200℃
で５分間混練して複合誘電体を得た。このものの誘電率
を測定したところ、100Hzで4.7、1kHzで4.3、10kHzで4.
0であった。Example 1 Copper phthalocyanine having an average particle size of about 12μ was crushed to an average particle size of about 1μ by a jet crusher and then dried at 50 ° C. in a vacuum dryer for 8 hours.
Dried for hours. 60 g of this copper phthalocyanine was charged into a 500 cc three-necked flask, and 200 cc of methanol in which 3 g of FeCl 3 was dissolved was added thereto and sufficiently stirred and mixed at room temperature for 2 hours under a nitrogen atmosphere. Next, methanol was removed from this and further dried in a vacuum dryer at 50 ° C. for 12 hours. N-
250 cc of heptane was added and suspended, and 25 g of pyrrole was added dropwise under a nitrogen atmosphere and the reaction was carried out at 80 ° C. for 3 hours. After completion of the reaction, the mixture was cooled and methanol was added. Have a precipitate,
Further, it was washed with methanol. Dry the excess product
63 g are obtained. 30 parts by weight of this product and 70 parts by weight of polymethylmethacrylate at 200 ° C. in a Brabender Plastomill.
The mixture was kneaded for 5 minutes to obtain a composite dielectric. When the dielectric constant of this product was measured, it was 4.7 at 100 Hz, 4.3 at 1 kHz, and 4.
It was 0.
なお、上記反応生成物の誘電率は100Hzで3.6、1kHzで3.
0、10kHzで2.8であった。The dielectric constant of the above reaction product is 3.6 at 100 Hz and 3 at 1 kHz.
It was 2.8 at 0 and 10 kHz.
比較例１ 実施例１において、銅フタロシアニン粒子をピロール重
合することなく、同様にして複合誘電体を得た。このも
のの誘電率は100Hzで3.5、1kHzで3.2、10kHzで3.1であ
った。Comparative Example 1 A composite dielectric was obtained in the same manner as in Example 1, except that the copper phthalocyanine particles were not subjected to pyrrole polymerization. The dielectric constant of this product was 3.5 at 100 Hz, 3.2 at 1 kHz, and 3.1 at 10 kHz.
Claims (1)
子との間に有機共役系高分子が少なくとも部分的に存在
している構成からなることを特徴とする複合有機誘電
体。1. A composite organic dielectric having a structure in which an organic conjugated polymer is at least partially present between a non-conjugated organic polymer and organic compound dielectric particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12929686A JPH0717838B2 (en) | 1986-06-05 | 1986-06-05 | Composite organic dielectric |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12929686A JPH0717838B2 (en) | 1986-06-05 | 1986-06-05 | Composite organic dielectric |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62285953A JPS62285953A (en) | 1987-12-11 |
| JPH0717838B2 true JPH0717838B2 (en) | 1995-03-01 |
Family
ID=15006061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12929686A Expired - Fee Related JPH0717838B2 (en) | 1986-06-05 | 1986-06-05 | Composite organic dielectric |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0717838B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL9101750A (en) * | 1991-10-21 | 1993-05-17 | Dsm Nv | POLYMER COMPOSITION. |
-
1986
- 1986-06-05 JP JP12929686A patent/JPH0717838B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62285953A (en) | 1987-12-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |