JPH04108825A - Production of dielectric composition and capacitor using the same - Google Patents
Production of dielectric composition and capacitor using the sameInfo
- Publication number
- JPH04108825A JPH04108825A JP2227019A JP22701990A JPH04108825A JP H04108825 A JPH04108825 A JP H04108825A JP 2227019 A JP2227019 A JP 2227019A JP 22701990 A JP22701990 A JP 22701990A JP H04108825 A JPH04108825 A JP H04108825A
- Authority
- JP
- Japan
- Prior art keywords
- lewis acid
- membered heterocyclic
- dielectric composition
- heterocyclic compound
- derivative
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 239000003990 capacitor Substances 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002841 Lewis acid Substances 0.000 claims abstract description 19
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 18
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 16
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 229930192474 thiophene Natural products 0.000 claims abstract description 6
- 229920000642 polymer Chemical class 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 abstract 1
- 239000013522 chelant Substances 0.000 abstract 1
- 239000012776 electronic material Substances 0.000 abstract 1
- -1 iron(III) metal complex Chemical class 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000002019 doping agent Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HPVXVIOTJPAXOH-UHFFFAOYSA-N 2-bromo-2H-pyran Chemical compound BrC1OC=CC=C1 HPVXVIOTJPAXOH-UHFFFAOYSA-N 0.000 description 1
- YCWPDFSNGOICAB-UHFFFAOYSA-N 2-bromo-3-decylthiophene Chemical compound CCCCCCCCCCC=1C=CSC=1Br YCWPDFSNGOICAB-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- ATWNFFKGYPYZPJ-UHFFFAOYSA-N 3-butyl-1h-pyrrole Chemical compound CCCCC=1C=CNC=1 ATWNFFKGYPYZPJ-UHFFFAOYSA-N 0.000 description 1
- 244000144725 Amygdalus communis Species 0.000 description 1
- FHDYSCSGDOLYJO-UHFFFAOYSA-N C(C=1C(N)=CC=CC1)(=O)O.C(C=1C(C(=O)O)=CC=CC1)(=O)O Chemical compound C(C=1C(N)=CC=CC1)(=O)O.C(C=1C(C(=O)O)=CC=CC1)(=O)O FHDYSCSGDOLYJO-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 1
- 239000008609 bushi Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- SGMHGVVTMOGJMX-UHFFFAOYSA-N n-naphthalen-2-yl-2-sulfanylacetamide Chemical compound C1=CC=CC2=CC(NC(=O)CS)=CC=C21 SGMHGVVTMOGJMX-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- WIDQNNDDTXUPAN-UHFFFAOYSA-I tungsten(v) chloride Chemical compound Cl[W](Cl)(Cl)(Cl)Cl WIDQNNDDTXUPAN-UHFFFAOYSA-I 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はエレクトロニクス用材料として応用が期待され
るπ電子共役系の高分子誘電体組成物の製造方法 及び
それを用いたコンデンサに関すも従来の技術
チオフェンあるいはピロールのような複素五員環化合物
を化学重合した後、触媒として用いたルイス酸（例えば
塩化鉄（ＩＩＩ）や塩化アルミニウム巻を溶出すること
によって、誘電体組成物が得られる （例えばポリマー
ブし７°リント シ９ヤバン第 ３７巻第 ３３５１
頁（Ｓ、ＨＯＴＴＡ 、Ｍ、５ＯＧＡ ＆ Ｎ、５ＯＮ
ＯＤＡ、 Ｐｏｌｙｍ、 Ｐｒｅｐ、 Ｊｐｎ、、３
７． ３３５１ （１９８８）） ）。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a π-electron conjugated polymer dielectric composition, which is expected to be applied as an electronics material, and a conventional technology related to a capacitor using the same. A dielectric composition can be obtained by chemically polymerizing a five-membered heterocyclic compound such as thiophene or pyrrole and then eluting a Lewis acid (e.g. iron(III) chloride or aluminum chloride) used as a catalyst (e.g. polymer Bushi 7° Lint Shi9 Yaban Volume 37 No. 3351
Page (S, HOTTA, M, 5OGA & N, 5ON
ODA, Polym, Prep, Jpn, 3
7. 3351 (1988))).
発明が解決しようとする課題
一般へ 例えばチオフェン誘導体やピロール誘導体のよ
うな複素五員環化合物誘導体又はその誘導体の重合体は
導電性高分子とよばれ アクセプター性のドーパントを
ドープすることによって高い導電性を発現するものであ
る。To the general problem to be solved by the invention For example, five-membered heterocyclic compound derivatives such as thiophene derivatives and pyrrole derivatives, or polymers of such derivatives are called conductive polymers, and they have high conductivity by doping them with acceptor dopants. It is something that expresses.
しかしながぺ 複素五員環化合物又はその誘導体ζ瓜
化学重合した後、大量の溶媒で洗浄したり、溶解・再沈
を繰り返して耘 触媒として用いた塩化鉄（ＩＩＩ）等
が重合物中に残留し 高抵抗の誘電体とはならないとい
う課題があっ九 すなゎ板 導電率が１Ｏ−９Ｓ／ｃｍ
程度を示し 高抵抗が要求されるコンデンサの誘電体と
しては使えないという欠点があった
しかしながら、 ドーパントが存在しない場合には本来
絶縁体であり、その誘電物性の応用も期待されてよい。However, Nagape Hetero5-membered ring compound or its derivative ζmelon
After chemical polymerization, the polymer must be washed with a large amount of solvent and repeatedly dissolved and reprecipitated.There is a problem in that iron chloride (III) used as a catalyst remains in the polymer, making it impossible to form a high-resistance dielectric. 9 Sunawa board Electrical conductivity is 1O-9S/cm
However, in the absence of a dopant, it is essentially an insulator, and its dielectric properties can be expected to be applied.
ところ力文 前述の化学重合において用いるルイス酸と
は すなわちアクセプターであり、ポリチオフェンやポ
リピロールに対しての有効なドーパントとなることから
、ポリマー七の強い相互作用のため重合反応終了後する
ことが困難なものと考えられる。Tokoro Rikibun: The Lewis acid used in the chemical polymerization mentioned above is an acceptor, and because it becomes an effective dopant for polythiophene and polypyrrole, it is difficult to remove it after the polymerization reaction is completed due to the strong interaction between the polymers. considered to be a thing.
本発明（よ 係る従来の課題に対してなされたもので、
化学重合した複素五員環化合物又はその誘導体の重合物
を高抵抗にすることを目的とする。The present invention (which has been made to solve such conventional problems,
The purpose is to make chemically polymerized five-membered heterocyclic compounds or polymers of derivatives thereof high in resistance.
課題を解決するための手段
本発明において（よ ルイス酸を用いての化学重合によ
って得られる複素五員環化合物又はその誘導体の重合物
く ルイス酸との錯形成剤を加えて誘電体組成物を製造
する。Means for Solving the Problems In the present invention, a dielectric composition is prepared by adding a complex-forming agent with a Lewis acid to a polymer of a five-membered heterocyclic compound or its derivative obtained by chemical polymerization using a Lewis acid. Manufacture.
作用
本発明者等ｉｔ 複素五員環化合物又はその誘導体の
重合物に残留するルイス酸すなわちドーパントと、非常
に強い相互作用を有する錯形成剤を添加することでミ
例え重合物中に残存してもドーパントとしての機能を失
った六 重合物は高抵抗を示す。Effect The present inventors have discovered that by adding a complex-forming agent that has a very strong interaction with the Lewis acid, that is, the dopant, remaining in the polymer of the five-membered heterocyclic compound or its derivative,
Even if it remains in the polymer, the hexapolymer that has lost its function as a dopant exhibits high resistance.
実施例
本発明は複素五員環化合物又はその誘導体を、ルイス酸
七ルイス酸の錯形成剤とを加えた化学重合法により重合
した誘電体組成物である。つまり本発明で反応触媒とし
て用いられるルイス酸との錯形成剤を加える必要性ζ友
例え（Ｌ 反応触媒として用いられ 重合反応終了後
も重合物中に残留している塩化鉄（ＩＩＩ）等が、例え
ばポリチオフェンに対するアクセプター（すなわちドー
パント）としても作用し ポリチオフェン主鎖と強い相
互作用しているものと考えられ 通常の手段では除去が
難しいた取 例えばキレート試薬としてのジアミン化合
物やジチオカルバミン酸を添加すると、非常に安定な鉄
（ＩＩＩ）の金属錯体を形成し 重合物中に残ったとし
てももはやドーパントとしては機能しなくなるものであ
る。その結果、重合物の誘電体としての応用が可能とな
るものである。Examples The present invention is a dielectric composition obtained by polymerizing a five-membered heterocyclic compound or a derivative thereof by a chemical polymerization method in which a complex forming agent of a Lewis acid and a hepta-Lewis acid is added. In other words, it is necessary to add a complex-forming agent with the Lewis acid used as a reaction catalyst in the present invention (L). For example, it acts as an acceptor (i.e., dopant) for polythiophene, and is thought to strongly interact with the polythiophene main chain, and is difficult to remove by normal means. It forms a very stable iron(III) metal complex, and even if it remains in the polymer, it no longer functions as a dopant.As a result, it can be used as a dielectric material for polymers. be.
本発明における複素五員環化合物及びその誘導体として
ζよ 有機溶媒への溶解性等の取扱易さの面から・炭素
数２以上のアルキル基 さらに好ましくは炭素数４以上
のアルキル基を有することが望ましｔ、Ｘｏ 炭素数
１のメチル誘導体またはアルキル基を持たない無置換の
もので（よ 高分子鎖間の分子間力が非常に強く、有機
溶媒に難溶て 取扱し難く、また化学重合時にドープさ
れたルイス酸と錯形成剤が反応することが困難である。In the present invention, the five-membered heterocyclic compound and its derivatives preferably have an alkyl group having 2 or more carbon atoms, and more preferably an alkyl group having 4 or more carbon atoms, from the viewpoint of ease of handling such as solubility in organic solvents. Desirably, t, Sometimes it is difficult for doped Lewis acids and complexing agents to react.
複素五員環化合物の例としてζよ チオフェン、ピロー
／ｌｚ、 フラン、セレノフェン、テルノフェン、ベ
ンゾフラン、チェノフラン、インドールなどがあげられ
る。この中でもチオフェン、ピロールもしくはフランｃ
ヨ 原料が入手し易く又安価であるため好ましｕ％
本発明におけるルイス酸として（友 通常のフリーデル
クラフト反応に用いられる金属ハロゲン化物が一射的テ
アリ、ＡｌＣｌ３、ＡｌＢｒ３．５ｂＣ１ｓ、ＦｅＣ１
５、ＦｅＢｒ５．５ｎＣ１４、ＴｉＣ１ｚ、ＷＣｌ５、
Ｍｏ１ｌｓ等が挙げられる。Examples of five-membered heterocyclic compounds include ζ, thiophene, pyro/lz, furan, selenophene, telnophene, benzofuran, chenofuran, and indole. Among these, thiophene, pyrrole or furan c
Preferable u% Because the raw materials are easily available and inexpensive, the Lewis acids used in the present invention include metal halides used in ordinary Friedel-Crafts reactions, such as flash tearly, AlCl3, AlBr3.5bC1s, FeC1
5, FeBr5.5nC14, TiC1z, WCl5,
Examples include Mo1ls and the like.
ルイス酸と錯体を形成する錯形成剤としては分析用の滴
定試薬のように非常に強固な錯体を形成するものであれ
ば何でもよいが、 例えばオキシン、ブロムオキシン、
クペロン、チオナリド、α−ペンゾインオキシベ α−
ニトロソ−β−ナフ） −）ｋ リン醜 シュウ醒
マンデル観 ピクロロン醜 ジメチルグリオキシベ α
−ベンジルジオキシ八へサリチルアルドキシベ ジベン
ゾイルメタン、チオフェノ−／ｌｚ、 チオ原点 ジ
チオカルバミン醜 アントラニル酸 フタル酸、エチレ
ンジアミンテトラ酢酸（ＥＤＴＡ）、ニトリロトリ酢酸
（ＮＴＡ）、 シクロヘキサジアミンテトラ酢酸（Ｃ
ｙＤＴＡ）、０−フェナントロリン、α、α′−ビピリ
ジＡｖ。Any complex forming agent that forms a complex with a Lewis acid may be used as long as it forms a very strong complex such as an analytical titration reagent, such as oxine, bromooxine,
Cuperone, thionalide, α-penzoinoxybe α-
nitroso-β-naph) -)k
Mandel's view Picloron ugly Dimethylglyoxybe α
-benzyldioxyoctahesalicylardoxybe dibenzoylmethane, thiopheno-/lz, thio origin dithiocarbamine anthranilic acid phthalic acid, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), cyclohexadiaminetetraacetic acid (C
yDTA), 0-phenanthroline, α, α'-bipyridiAv.
α、α″ α −ターピリジ／ｌｚ、 エチレンジア
ミン、シクロヘキサンジアミン等が挙げられ なかで耘
単座の配位子よりＬ 錯体の安定性や錯体形成能力の点
で２座以上のキレート配位子が望ましｔ、％加える錯形
成剤の量ｃｔ 残存するルイス酸の当量程度が望まし
いが、反応の促進のために本発明の効果を阻害しない範
囲で適宜増量することも可能である。Examples include α, α″ α-terpyridine/lz, ethylenediamine, cyclohexanediamine, etc. Among them, chelating ligands with two or more dentate positions are preferable to monodentate ligands in terms of stability of the L complex and ability to form a complex. t, % Amount of complex forming agent added ct The amount ct is preferably about the equivalent of the remaining Lewis acid, but the amount can be increased as appropriate to promote the reaction within a range that does not impede the effects of the present invention.
また 錯体形成反応によってζ戴 酸や塩を副生ずる場
合があり、溶媒抽出等の適当な手段によって除去するこ
とが望ましｔ、％
次に具体的な実施例を用いて本発明を説明する。In addition, the complex formation reaction may produce ζ-acid or salt as a by-product, and it is desirable to remove it by appropriate means such as solvent extraction.Next, the present invention will be explained using specific examples.
実施例１
シゝヤーナル オフゝ アメリカン ケミカル ソサエ
ティ第９４巻ｍ４ ３ ７４頁（Ｋ、Ｔａｍａｏ ｅｔ
ａＬ Ｊ、Ａｍ、Ｃｈｅｍ、Ｓｏｃ、、９４．４３７
４（１９７２））に記載されている方法によって、 ３
−ヘキシルチオフェンを合成し 乾燥後、真空蒸留した
滴下ロートを取り付けた２日フラスコ４Ｑ 塩化鉄（
ＩＩＩ） （Ｆ ｅ Ｃｌ ａ） ０．０４モル（６，
５ｇ）を乾燥窒素中で投入し 加熱しながら真空乾燥し
九
ここに １００ｍ１の乾燥したクロロホルムを注入し撹
拌しながら、得られた懸濁液に前記の３−へキシルチオ
フェンを滴下ロートにより加えた これを室温下、約４
時間撹拌を続けて脱水素縮合反応反応を終了し 濃青色
に変化した懸濁液を、 １リツトルのメタノール中に投
入して、暗青色の粉末を焦 さらに１昼夜メタノールで
ソックスレー抽出器を用いて繰り返し洗浄しな
得られた暗褐色の粉末０．５ｇを、約１００ｍ１の２−
メチルテトラヒドロフランに加熱溶解させ、残渣を濾過
で除去した後、大量のメタノール中に投入し再沈させる
ことによって、精製したポリ （３−へキシルチオフェ
ン）を得た
このポリ（３−へキシルチオフェン）をクロロホルムに
５０ ｍｇ／ｍｌの割合で溶解り、 Ｉ Ｔ Ｏ（Ｉ
ｎｄｉｕｍ−ｔｉｎ−ｏｘｉｄｅ）ガラス上にキャスト
し 約１０μ厚のフィルムを得ム
さら？Ｑ このフィルム上に金蒸着電極を形成しＩＴ
Ｏ電極との間で導電率を測定したところ約１０−”８７
ｃｍであり、誘電体としては絶縁性が不足してい九
このキャストフィルムを発光分光法により分析したとこ
へ 数百ｐｐｍのオーダーで鉄（Ｆｅ）が検出された
従って、この鉄がポリ（３−へキシルチオフェン）のド
ーパントとして作用した結果絶縁性を下げた（すなわ板
導電性を上げた）ものと考えられる。Example 1 Annual Offshore American Chemical Society Vol. 94 m4 3 p. 74 (K, Tamao et al.
aL J, Am, Chem, Soc,,94.437
4 (1972)) by the method described in 3
- Hexylthiophene was synthesized, dried, and vacuum distilled into a 2-day flask 4Q equipped with a dropping funnel. Iron chloride (
III) (FeCl a) 0.04 mol (6,
5 g) was put in dry nitrogen and dried under vacuum while heating. 100 ml of dry chloroform was poured into the suspension, and while stirring, the above-mentioned 3-hexylthiophene was added to the resulting suspension using a dropping funnel. At room temperature, about 4
After the dehydrogenation condensation reaction was completed by continuous stirring for an hour, the suspension, which turned dark blue, was poured into 1 liter of methanol, the dark blue powder was scorched, and then the mixture was soaked in methanol for a day and a night using a Soxhlet extractor. After repeated washing, 0.5 g of the obtained dark brown powder was added to about 100 ml of 2-
Purified poly(3-hexylthiophene) was obtained by heating and dissolving it in methyltetrahydrofuran, removing the residue by filtration, and pouring it into a large amount of methanol for reprecipitation. was dissolved in chloroform at a ratio of 50 mg/ml, and I TO (I
ndium-tin-oxide) on glass to obtain a film approximately 10μ thick. Q Form a gold vapor-deposited electrode on this film and perform IT
When the conductivity was measured between the O electrode and the conductivity, it was approximately 10-”87
cm, and as a dielectric, it lacks insulating properties.When this cast film was analyzed by emission spectroscopy, iron (Fe) was detected on the order of several hundred ppm.
Therefore, it is considered that this iron acted as a dopant for poly(3-hexylthiophene), thereby lowering the insulation properties (in other words, increasing the conductivity of the plate).
そこで、本実施例で（よ この鉄に対する錯形成剤とし
て、 ０−フェナントロリンを用℃＼ ポリ （３−へ
キシルチオフェン）の溶液に 検出された鉄と当量を添
加し よく撹拌した後、この溶液を用いてキャストフィ
ルムを作製し 導電率を測定したところ１０−”８７ｃ
ｍであり、誘電体として十分高抵抗であることがわかっ
た
実施例２
出発物質に２−ブロモ−３−デシルチオフェンを用いて
実施例１と殆ど同様に反応（ここでＵ脱ハロゲン化水素
反応）を進取 得られた重合物溶液に同様にα、 α゛
−ビピリジルを添加することに寄って１０−、”Ｓ／
Ｃｍの誘電体を得た実施例３
実施例１の３−へキシルチオフェンを、３−ブチルピロ
ールに代えて同様の実験をした触媒としてはＡｌＣｌ３
を、錯形成剤としてオキシンを用いて導電率が１０−１
２Ｓ／ｃｍの誘電体組成物を得た
この場合に（よ クロロホルム溶液に希薄なアルカリ水
溶液を加え 振盪することにより副生じた塩酸を取り除
くことがより有効であっな実施例４
実施例２の２−ブロモ−３−デシルチオフェンを、 ２
−ブロモ−３−オクチルピロールに代えて同様の実験を
し八
触媒としては５ｎＣ１ｚ、錯形成剤としてはクペロンを
用いて導電率が１０−１２Ｓ／ｃｍの誘電体組成物を得
実施例５
実施例１の３−へキシルチオフェンを、チオフェンもし
くは３−メチルチオフェンに代えて同様の実験を行い重
合物を得九
この重合物は溶媒に不溶であり、粉末をペレット状にし
て見かけの導電率を測定したとこ７）、１Ｏ−６Ｓ／ｃ
ｍであっ九
一方この粉末を錯形成剤のクロロホルム溶液で繰り返し
洗浄して、導電率が１０−”Ｓ／ｃｍ程度の誘電体組成
物を得九
実施例６
実施例１〜４で得られた誘電体組成物を用いて、厚さ１
００μｍのアルミ箔上にキャストフィルムを作成し九
アルミ箔と反対面にアルミニウムを蒸着し電極とした
この試料を５ｍｍｘ１５ｍｍに切取り、折り重ね画電極
にリード線を取り付はフィルムコンデンサ素子を試作し
な
得られたコンデンサの絶縁破壊強度を測定したとこへ
４５〜８０ｋＶ／ｍｍを示し 優れた絶縁特性を示しな
発明の効果
本発明（よ 複素五員環化合物又はその誘導体を化学重
合法を用いる重合方法であって、ルイス酸との錯形成剤
を加える誘電体組成物の製造方法であるたへ 複素五員
環化合物又はその誘導体の重合物（π電子共役系高分子
）からなる誘電体組成物が容易に得られる。Therefore, in this example, 0-phenanthroline was used as a complexing agent for iron. An amount equivalent to the detected iron was added to a solution of poly(3-hexylthiophene), stirred well, and then the solution was added. A cast film was made using
Example 2: 2-bromo-3-decylthiophene was used as the starting material and the reaction was carried out in the same manner as in Example 1 (here, the U dehydrohalogenation reaction ) by similarly adding α,α゛-bipyridyl to the obtained polymer solution, 10-,”S/
Example 3 in which a Cm dielectric was obtained A similar experiment was carried out in Example 1 by replacing 3-hexylthiophene with 3-butylpyrrole.As a catalyst, AlCl3 was used.
using oxine as a complexing agent, the conductivity is 10-1.
In this case, where a dielectric composition of 2S/cm was obtained, it was more effective to add a dilute aqueous alkaline solution to the chloroform solution and shake it to remove the by-product hydrochloric acid.Example 4 Example 2-2 -bromo-3-decylthiophene, 2
Example 5 A similar experiment was carried out in place of -bromo-3-octylpyrrole, and a dielectric composition with a conductivity of 10-12 S/cm was obtained using 5nC1z as the catalyst and cuperone as the complex forming agent. A similar experiment was carried out by replacing 3-hexylthiophene in 1 with thiophene or 3-methylthiophene, and a polymer was obtained.9 This polymer was insoluble in the solvent, and the powder was made into pellets and the apparent conductivity was measured. Shitoko 7), 1O-6S/c
Meanwhile, this powder was washed repeatedly with a chloroform solution of a complexing agent to obtain a dielectric composition having a conductivity of about 10-''S/cm. using a dielectric composition with a thickness of 1
A cast film was made on 00 μm aluminum foil, aluminum was vapor-deposited on the opposite side of the aluminum foil, and this sample was cut into 5 mm x 15 mm, and a lead wire was attached to the folded image electrode to make a prototype film capacitor element. The dielectric breakdown strength of the obtained capacitor was measured.
45 to 80 kV/mm and exhibits excellent insulating properties Effects of the Invention The present invention provides a method for polymerizing a five-membered heterocyclic compound or a derivative thereof using a chemical polymerization method, in which a complex forming agent with a Lewis acid is added. A dielectric composition comprising a polymer of a five-membered heterocyclic compound or a derivative thereof (π-electron conjugated polymer) can be easily obtained.
また 本発明で得られた誘電体組成物は高抵抗であるた
敢 フィルムコンデンサとして用いた場合、絶縁破壊強
度の優れたものが得られる。Furthermore, the dielectric composition obtained in the present invention has a high resistance, and when used as a film capacitor, one with excellent dielectric breakdown strength can be obtained.
Claims (5)
用いる重合方法であって、ルイス酸との錯形成剤を加え
ることに特徴を有する誘電体組成物の製造方法。(1) A method for producing a dielectric composition, which is a method for polymerizing a five-membered heterocyclic compound or a derivative thereof using a chemical polymerization method, and is characterized in that a complex forming agent with a Lewis acid is added.
、ピロールもしくはフランの少なくとも１つを含むこと
を特徴とする、請求項１記載の誘電体組成物の製造方法
。(2) The method for producing a dielectric composition according to claim 1, wherein the five-membered heterocyclic compound or its derivative contains at least one of thiophene, pyrrole, or furan.
上のアルキル基を有することを特徴とする、請求項１も
しくは２いずれかに記載の誘電体組成物の製造方法。(3) The method for producing a dielectric composition according to claim 1 or 2, wherein the five-membered heterocyclic compound or its derivative has an alkyl group having two or more carbon atoms.
る、請求項１記載の誘電体組成物の製造方法。(4) The method for producing a dielectric composition according to claim 1, wherein the complex forming agent is a chelating reagent.
ス酸との錯形成剤とを含む誘電体組成物を誘電層に用い
たことを特徴とするコンデンサ。(5) A capacitor characterized in that a dielectric composition containing a five-membered heterocyclic compound or a polymer derivative thereof and a complex forming agent with a Lewis acid is used in the dielectric layer.
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|---|---|---|---|
| JP02227019A JP3094432B2 (en) | 1990-08-28 | 1990-08-28 | Capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02227019A JP3094432B2 (en) | 1990-08-28 | 1990-08-28 | Capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04108825A true JPH04108825A (en) | 1992-04-09 |
| JP3094432B2 JP3094432B2 (en) | 2000-10-03 |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011208016A (en) * | 2009-03-31 | 2011-10-20 | Arakawa Chem Ind Co Ltd | Electroconductive polymer/dopant dispersion, electroconductive composition and electroconductive film |
| JP2013139543A (en) * | 2011-12-30 | 2013-07-18 | Eternal Chemical Co Ltd | Electrolytic material formulation, electrolytic material polymer formed therefrom and use thereof |
-
1990
- 1990-08-28 JP JP02227019A patent/JP3094432B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011208016A (en) * | 2009-03-31 | 2011-10-20 | Arakawa Chem Ind Co Ltd | Electroconductive polymer/dopant dispersion, electroconductive composition and electroconductive film |
| JP2013139543A (en) * | 2011-12-30 | 2013-07-18 | Eternal Chemical Co Ltd | Electrolytic material formulation, electrolytic material polymer formed therefrom and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3094432B2 (en) | 2000-10-03 |
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