JPH0356567A - Electrically conductive high polymer and electrolytic condenser using same high polymer - Google Patents
Electrically conductive high polymer and electrolytic condenser using same high polymerInfo
- Publication number
- JPH0356567A JPH0356567A JP19296289A JP19296289A JPH0356567A JP H0356567 A JPH0356567 A JP H0356567A JP 19296289 A JP19296289 A JP 19296289A JP 19296289 A JP19296289 A JP 19296289A JP H0356567 A JPH0356567 A JP H0356567A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- oligomer
- polymerization
- high polymer
- sulfonic acid
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 50
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 239000002019 doping agent Substances 0.000 claims abstract description 18
- 238000009833 condensation Methods 0.000 claims abstract description 11
- 230000005494 condensation Effects 0.000 claims abstract description 11
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 10
- 125000003010 ionic group Chemical group 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 5
- 239000006252 electrolytic conductor Substances 0.000 claims abstract description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 5
- 229920001940 conductive polymer Polymers 0.000 claims description 24
- 229920000547 conjugated polymer Polymers 0.000 claims description 11
- 239000003990 capacitor Substances 0.000 claims description 9
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 4
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 230000005684 electric field Effects 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- -1 Polyphenylene sulfite Polymers 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000208140 Acer Species 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 241000270708 Testudinidae Species 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- XPKFJIVNCKUXOI-UHFFFAOYSA-N formaldehyde;2-hydroxybenzoic acid Chemical compound O=C.OC(=O)C1=CC=CC=C1O XPKFJIVNCKUXOI-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- NUSQOFAKCBLANB-UHFFFAOYSA-N phthalocyanine tetrasulfonic acid Chemical compound C12=CC(S(=O)(=O)O)=CC=C2C(N=C2NC(C3=CC=C(C=C32)S(O)(=O)=O)=N2)=NC1=NC([C]1C=CC(=CC1=1)S(O)(=O)=O)=NC=1N=C1[C]3C=CC(S(O)(=O)=O)=CC3=C2N1 NUSQOFAKCBLANB-UHFFFAOYSA-N 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明ζよ 経時安定性に優れる導電性高分子およびそ
れを用いた電解コンデンサに関すん従来の技術
導電性高分子はポリアセチレン、ポリビローノｋボリチ
オフェン、ポリアニリン、ボリアセンなどの大きく広が
った共役π電子系をもつ高分子よりなり、電子供与体ま
たは電子受容体（ルイス亀プロトン酸などのア二オン）
をドーパントとして含有して高導電性を示すことが広く
知られていも発明が解決しようとする課題
しかし これらのドーパントは高分子マトリクス中を電
界により拡散し導電率を低下させてしまうという大きな
欠点を有していた
この欠点に鑑ヘ フタロシアニンテトラスルフォン醜
ボリスチレンスルフォン酸などの高分子量ドーパントが
ジャーナル オプ ケミカル ソサエティ第６８４頁１
９８３年版（ Ｋ．Ｏｋａｂａｙａｓｈｉ、Ｊ．Ｃｈｅ
ｍ．Ｓｃｉ．，Ｃｈｅｆｆｉ．Ｃｏｍｍｕｎ．． ｐ６
ｇ４（１９８３））およびイビド第８７１頁１９８５年
版（Ｎ． Ｂａｔｅｓ ｅｔａｌ，ｉｂｉｄ．． ｐ８
７１（１９８５））にすでに開示されていもしかしなが
転 これらのドーパントを鋭意検討した結凰 フタロシ
アニンテトラスルフォン酸はバルキーなフタロシアニン
核のためボリマー生戒時に導電性高分子鎖の結晶配列を
乱す上 電界による移動も比較的太きかつｔも
また 一方ポリスチレンスルフォン酸は重合度が大きす
ぎるせい力＼ 導電性高分子マトリクスと相溶性が悪く
均一な分子分散体が得られなかっ九本発明はこれらの現
象に鑑へ 鋭意検討の結果得られたちの玄 耐熱怯 電
界による経時安定性に優れる導電性高分子を与えると共
に これを用いた電解コンデンサを提供することを目的
とすも課題を解決するための手段
本発明（よ イオン性基を有する平均重合度３から１２
の重合体オリゴマーをドーバントとして電子共役性高分
子中に分子分散することによって耐熱怯 電界による経
時安定性に優れる導電性高分子を構威するものであも
作用
イオン性基を有する平均重合度３から１２の重合体オリ
ゴマーがドーパントとして電子共役性高分子中に分子分
散された昧 そのイオン性基含有重合体オリゴマーはパ
ルキーな分子であるため電子共役性高分子中で容易に移
動できな賎 それ肱直流電界下でも経時的に安定した導
電率を示も実施例
本発明に用いるイオン性基を有する重合体オリゴマーと
してＣ友 スルフオン酸基 オキシ安息香酸基のいず
れかを有する重合体が好ましＬ１スルフォン酸基を有す
る重合体オリゴマーとして《ヨトルエンスルフォン酸−
アルデヒド縮重合像 ベンゼンスルフォン酸−アルデヒ
ド縮重合体ポリスチレンスルフォン酸等を用いも
また スルフォン酸基を有する重合体オリゴマーとして
、両端にスルフォン酸基の結合した平均重合度３から１
２α ボリフェニレンサルファイド、ポリスルフォン、
ボリフェニレンオキサイドである場合もあも
オキシ安息香酸基を有する重合体オリゴマーとしてＣＬ
ｐ−オキシ安息香酸−アルデヒド縮重合体 サリチ
ル酸−アルデヒド縮重合体などを用い本発明に用いる重
合体オリゴマーの平均重合度は３〜１２の範囲であも
平均重合度が３以下ではモノマーと挙動があまり違わず
１２以上では高分子的になり電子共役性高分子の相溶怯
凝集性等に悪い影響を与えもまた このイオン性基含
有重合体オリゴマーはスルフォン酸基やオキシ安息番酸
基を有しており、電子共役性高分子のドーパントとして
働き、導電率の向上（キャリャ数の増加）に大きく寄与
すも本発明のイオン性基含有重合体オリゴマーは重合度
が３〜１２と小さいたべ 重合の際低粘度のモノマー溶
液中では低分子にように挙動μ 生戒した導電性高分子
中ではそれほどバルキーな分子ではないた取 結晶性や
凝集構造には高重合体ほど影響を与えず電子共役性高分
子中に比較的均一に分子分散されるという大きな特徴を
有していも中で転 両端にスルフォン酸基の結合した平
均重合度３から１２α ボリフエニレンサルファイＫ
ポリスルフオン、ポリフエニレンオキサイドなどは芳香
族分子で電子共役性高分子中と相溶性を有するドーパン
トとなり、良質のフィルムを形成すも
電子共役性高分子として（よ ボリビロ−７１４ ポ
リフェニレンサルファイド、ポリチオフエン、ポリアニ
リン、及びその誘導体などがあり、これらは化学重合ま
たは電解重合（陽極酸化重合、陰極還元重合）などによ
って得られ為
陽極酸化重合は 電子共役性モノマーの溶液中にア二オ
ン性基を有する重合体オリゴマーを溶解させ、少なくと
も一対の電極による電場により、前記電子共役性モノマ
ーを陽極上に電解重合するもの弘 前記アニオン性基を
有する重合体オリゴマーがドーパントとして分子分散さ
れて或る導電性高分子が得られも
このようにして得られたアニオン性基を有する重合体オ
リゴマーを含有する導電性高分子（よ アニオンが親水
性であるため導．電性が湿度依存性を受ける場合があん
この場合には例えば不溶性塩を生じる金属イオン（例
えばＢａ”° Ｐｂ”・など）によって処理することに
よって耐水化することが出来も
本発明における導電性高分子？ｉ 金属陽徴 酸化物
誘電凰 電解性導電依 陰極よりなる電解コンデンサの
電解性導電体として、応用することができも この場合
には本発明の導電性高分子の特徴である耐熱怯 電界に
よる経時安定性によって、優れた特性のコンデンサーを
得ることができもまｆ：＝ｐ−ｎ接合素子とする場合に
も安定した接合特性が得られも
次に実施例を用いて本発明を説明する。[Detailed Description of the Invention] Industrial Field of Application The present invention relates to conductive polymers with excellent stability over time and electrolytic capacitors using the same.Conventional techniques of conductive polymers include polyacetylene, polyvirono-k polythiophene, Consists of polymers with widely spread conjugated π-electron systems such as polyaniline and boriacene, which act as electron donors or electron acceptors (anions such as Lewis tortoise protonic acid)
However, these dopants have a major drawback in that they diffuse through the polymer matrix due to an electric field and reduce the conductivity. In light of this drawback, phthalocyanine tetrasulfone is ugly.
High molecular weight dopants such as polystyrene sulfonic acid have been reported in the Journal Op Chemical Society, p. 684, 1.
983 edition (K. Okabayashi, J. Che
m. Sci. , Cheffi. Commun. ．． p6
g4 (1983)) and Ibid p. 871, 1985 edition (N. Bates et al, ibid. p8
71 (1985)), however, the result of intensive study of these dopants is that phthalocyanine tetrasulfonic acid has a bulky phthalocyanine nucleus, which may disturb the crystalline arrangement of conductive polymer chains when used as a polymer. On the other hand, polystyrene sulfonic acid has a relatively large degree of polymerization and is not compatible with the conductive polymer matrix, making it difficult to obtain a uniform molecular dispersion. In light of the phenomenon, we have developed a new technology that we have developed through intensive research to provide a conductive polymer that is highly stable over time due to electric fields, as well as to provide an electrolytic capacitor using the same. Means of the present invention (average degree of polymerization with ionic groups from 3 to 12)
By molecularly dispersing a polymer oligomer as a dopant into an electronically conjugated polymer, a conductive polymer with excellent resistance to heat shrinkage and stability over time due to electric fields is constructed. 12 polymer oligomers were molecularly dispersed in the electron-conjugated polymer as a dopant.Since the ionic group-containing polymer oligomer is a bulky molecule, it cannot easily move in the electron-conjugated polymer. Examples of polymer oligomers having ionic groups used in the present invention include polymers having any of C, sulfonic acid groups, and oxybenzoic acid groups, which exhibit stable electrical conductivity over time even under a direct current electric field.L1 As a polymer oligomer having a sulfonic acid group, 《Yotoluenesulfonic acid-
Image of aldehyde condensation polymerization Benzene sulfonic acid-aldehyde condensation polymer polystyrene sulfonic acid, etc. can also be used as a polymer oligomer having sulfonic acid groups, with an average degree of polymerization of 3 to 1, with sulfonic acid groups bonded to both ends.
2α polyphenylene sulfide, polysulfone,
In the case of polyphenylene oxide, CL as a polymer oligomer having an oxybenzoic acid group
Although the average degree of polymerization of the polymer oligomer used in the present invention using p-oxybenzoic acid-aldehyde condensation polymer, salicylic acid-aldehyde condensation polymer, etc. is in the range of 3 to 12, if the average degree of polymerization is 3 or less, it will behave poorly with the monomer. There is not much difference, and if it is more than 12, it becomes polymeric and has a negative effect on the compatibility, flocculation, etc. of the electron-conjugated polymer. The ionic group-containing polymer oligomer of the present invention has a small degree of polymerization of 3 to 12. In a low-viscosity monomer solution, it behaves like a small molecule.In a controlled conductive polymer, it is not a very bulky molecule.It has no effect on crystallinity or agglomerated structure as much as a high polymer, and conjugation Polyphenylene sulfite K has a major feature of being relatively uniformly dispersed in the polymer, with an average degree of polymerization of 3 to 12α, with sulfonic acid groups bonded to both ends.
Polysulfone, polyphenylene oxide, etc. are aromatic molecules that act as dopants that are compatible with electron-conjugated polymers, forming high-quality films. , and its derivatives, etc., and these are obtained by chemical polymerization or electrolytic polymerization (anodic oxidation polymerization, cathodic reduction polymerization), etc. Anodic oxidation polymerization is a polymer that has an anionic group in a solution of an electron-conjugated monomer. The oligomer is dissolved and the electronically conjugated monomer is electrolytically polymerized on the anode using an electric field from at least one pair of electrodes.The polymer oligomer having an anionic group is molecularly dispersed as a dopant to form a conductive polymer. The conductive polymer containing the polymer oligomer having an anionic group obtained in this way (because the anion is hydrophilic, the conductivity may be humidity dependent). The conductive polymer of the present invention can be made water resistant by treatment with metal ions (e.g. Ba"° Pb") that produce insoluble salts. It can be applied as an electrolytic conductor in an electrolytic capacitor consisting of a cathode. Even if f:=pn junction element is used, stable junction characteristics can be obtained.Next, the present invention will be explained using Examples.
実施例ｌ
２００ｍｌのセパラプルフラスコ中に ４ｇのピロール
と２ｇのトルエンスルフォン酸一ホルムアルデヒド縮重
合体（平均重合度４）および１００ｍｌのアセトニトリ
ルを入れて、反応溶液を得ｔも
この溶液にインジウムースズ酸化物（ＩＴ○）を陽極と
ｔ，，Ｐｔ板を陰極として窒素気流中で通電し 陽極上
に約２５μｍのボリピロール膜を得ｔ４ この膜を電
極よりはがし 銀ペイントを塗布し 導電率を測定した
とこ＆ １８Ｓ／Ｃｍ（２５℃）であっｔも
さらに この膜８０℃炉中にセットし直流電場を印加し
電流の経時変化を測定したとこ水 ３００時間後の変
化は１０％であっｔ４ この安定性は従来の低分子ド
ーパントの場合の特性に比べ著しく安定した特性であっ
１，
実施例２
２ ０ ０ｍｌのセパラプルフラスコ中ＧＱ５ｇの３−
メチルチオフェンと３ｇのサリチル酸一ホルムアルデヒ
ド縮重合体（平均重合度３）および１５ ０ｍｌのニト
ロベンゼンを入れて、重合溶液を得ｔも
この溶液にインジウムースズ酸化物（ＩＴＯ）を陽極と
Ｌ Ｐｔ板を陰極として窒素気流中で通電Ｌ，ｌｌｉ
極上に約２０μｍのポリ （３−メチルチオフェン）膜
を得丸 この膜を電極よりはがし銀ペイントを塗布レ
導電率を測定したとこム７Ｓ／ａｍ（２５℃）であッタ
さらに この膜を８０℃炉中にセットし直流電場を印加
し 電流の経時変化を測定したとこム３００時間後の変
化は１６％であつ九 この安定性は従来の低分子ドーバ
ントの場合の特性に比べ著しく安定した特性であつ九
実施例３
２ ０ ０ｍｌのセパラプルフラスコ中４，Ｑ５ｇの３
−メチルチオフェンと３ｇの両端にスルフオン基を付け
たポリフエニレンサルファイド（平均重合度６）および
１５０ｍｌのニトロベンゼンを入れて、重合溶液を得ｔ
４
この溶液にインジウムースズ酸化物（ＩＴＯ）を陽極と
Ｌ Ｐｔ板を陰極として窒素気流中で通電し 陽極上
に約２３μｍのポリ（３−メチルチオフェン）膜を得九
この膜を電極よりはがし銀ペイントを塗布し 導電率
を測定したとこム９ ０ Ｓ／ｃｍ （２ ５℃）であ
ツ氾さらに この膜８０℃炉中にセットし直流電場を印
加し 電流の経時変化を測定したとこム ３００時間後
の変化は１１％であつｔラ この安定性は従来の低分
子ドーパントの場合の特性に比べ著しく安定した特性で
ありｔラ
実施例４
０．０３ｍｍ厚の粗面化処理したアルミニウムフィルム
にまず酸化物誘電層を形或したのべ 導電核を形或ａ
ついで導電性高分子形戒糟を通して実施例ｌと同じ反応
溶液組或にて導電性高分子膜を形或した
ついでそれを折り畳んだ後銀ペイントで陰極を形或して
、リード線を取出しそれに外装樹脂を被覆しｔも
こうして得た固体電解コンデンサーは低分子ドーパント
を用いた同じ型の積層形コンデンサーとほぼ同じ靜電容
量を示し九
これの周波数特性並びに経時安定性を測定したとこ＆
周波数特性は低分子ドーバントのものとほぼ同一であっ
た力交 経時安定性は大きく改善さ；ｉｔ． １２５
℃ ２０００時間以上の寿命を示しｔラ発明の効果
このように本発明（よ イオン性基を有する平均重合度
３から１２の重合体オリゴマーをドーパントとして電子
共役性高分子中に分子分散することによって、耐熱怯
電界による経時安定性に優れる導電性高分子を得るもの
であも
上記重合体オリゴマーはドーパントとして電子共役性高
分子中に分散された昧 低分子に比較してバルキーな分
子であるため電子共役性高分子中で容易に移動でき衣
直流電界下でも経時的に安定した導電率を示す効果があ
も
また 本発明のイオン性基含有重合体オリゴマーは重合
度が小さいたべ 重合の際低粘度のモノマー溶液中では
低分子にように挙動レ 生或した導電性高分子中ではそ
れほどバルキーな分子ではないたへ 結晶性や凝集構造
には高重合体ほど影響を与え哄 電子共役性高分子中に
比較的均一に分子分散され 良質の導電性高分子フィル
ムを与えるという特徴があも
本発明における導電性高分子ζ上 金属陽楓 酸化物誘
電凰 電解性導電恢 陰極よりなる電解コンデンサの電
解性導電体として、応用することができも この場合に
は本発明の導電性高分子の特徴である耐熱怯 電界によ
る経時安定性によって、優れた特性のコンデンサーを得
ることができもまｆ；ｐ−ｎ接合素子とする場合にも安
定した接合特性が得られも
このように本発明は工業的価値の大なるものであもExample 1 4 g of pyrrole, 2 g of toluenesulfonic acid-monoformaldehyde condensation polymer (average degree of polymerization 4) and 100 ml of acetonitrile were placed in a 200 ml separate flask to obtain a reaction solution. (IT○) was used as an anode and a Pt plate was used as a cathode, and electricity was applied in a nitrogen stream to obtain a polypyrrole film of about 25 μm on the anode. This film was peeled off from the electrode, silver paint was applied, and the conductivity was measured. This film was placed in a furnace at 80°C, a DC electric field was applied, and the change in current over time was measured, and the change after 300 hours was 10%. The characteristics were significantly more stable than those of conventional low-molecular-weight dopants.
Add methylthiophene, 3 g of salicylic acid-formaldehyde condensation polymer (average degree of polymerization 3), and 150 ml of nitrobenzene to obtain a polymerization solution.To this solution, indium-tin oxide (ITO) was added as an anode and L Pt plate was used as a cathode. Electrification L,lli in nitrogen stream
A poly(3-methylthiophene) film of approximately 20 μm is obtained on top of the circle. Peel off this film from the electrode and apply silver paint.
The conductivity was measured at 7 S/am (25°C).Furthermore, this film was placed in an 80°C furnace, a DC electric field was applied, and the change in current over time was measured.The change after 300 hours was 16%. This stability is significantly more stable than that of conventional low-molecular-weight dopant.
- Add methylthiophene, 3 g of polyphenylene sulfide with sulfon groups attached to both ends (average degree of polymerization 6), and 150 ml of nitrobenzene to obtain a polymerization solution.
4 Apply current to this solution in a nitrogen stream using indium-tin oxide (ITO) as an anode and L Pt plate as a cathode to obtain a poly(3-methylthiophene) film of approximately 23 μm on the anode. 9 Peel off this film from the electrode and paint with silver. The conductivity was measured after coating the film, which was then flooded with 90 S/cm (25°C).The film was then placed in an 80°C furnace, a DC electric field was applied, and the change in current over time was measured for 300 hours. The subsequent change was 11%, and this stability was significantly more stable than that of conventional low-molecular-weight dopants. After forming the oxide dielectric layer, the conductive core is formed.
Next, a conductive polymer film was formed using the same reaction solution as in Example 1 through a conductive polymer film, and after folding it, a cathode was formed with silver paint, and a lead wire was taken out and attached to it. The solid electrolytic capacitor coated with an exterior resin and thus obtained exhibited almost the same static capacitance as the same type of multilayer capacitor using a low-molecular dopant.The frequency characteristics and stability over time were measured.
The frequency characteristics were almost the same as those of the low-molecular-weight dopant.The stability over time was greatly improved; it. 125
℃ exhibiting a lifetime of 2,000 hours or more.The effects of the present invention (by molecularly dispersing a polymer oligomer having an ionic group and an average degree of polymerization of 3 to 12 as a dopant into an electronically conjugated polymer) , heat resistance
Although the purpose is to obtain conductive polymers with excellent stability over time under electric fields, the above polymer oligomers are dispersed as dopants in electron-conjugated polymers. Easily moveable in polymers
The ionic group-containing polymer oligomer of the present invention has a low degree of polymerization and behaves like a low molecule in a low-viscosity monomer solution during polymerization. However, since they are not very bulky molecules in some conductive polymers, higher polymers have more influence on crystallinity and agglomerated structure, and molecules are dispersed relatively uniformly in electron-conjugated polymers, resulting in good conductivity. In addition to the characteristic of providing a conductive polymer film in the present invention, it can also be applied as an electrolytic conductor of an electrolytic capacitor consisting of a conductive polymer ζ, a metal positive maple, an oxide dielectric film, an electrolytic conductive film, and a cathode. In some cases, it is possible to obtain capacitors with excellent characteristics due to the characteristics of the conductive polymer of the present invention, such as heat resistance and stability over time due to electric fields. Even if these characteristics are obtained, the present invention has great industrial value.
Claims (7)
体オリゴマーがドーパントとして電子共役性高分子中に
分子分散されてなる導電性高分子。(1) A conductive polymer obtained by molecularly dispersing a polymer oligomer having an ionic group and an average degree of polymerization of 3 to 12 as a dopant in an electronically conjugated polymer.
息香酸基のいずれかを有する重合体である請求項１に記
載の導電性高分子。(2) The conductive polymer according to claim 1, wherein the polymer oligomer is a polymer having either a sulfonic acid group or an oxybenzoic acid group.
ルエンスルフォン酸−アルデヒド縮重合体、ベンゼンス
ルフォン酸−アルデヒド縮重合体、ポリスチレンスルフ
ォン酸より選ばれた少なくとも１種の重合体である請求
項２に記載の導電性高分子。(3) The polymer oligomer having a sulfonic acid group is at least one kind of polymer selected from toluenesulfonic acid-aldehyde condensation polymer, benzenesulfonic acid-aldehyde condensation polymer, and polystyrene sulfonic acid. The conductive polymer described.
端にスルフォン酸基の結合した平均重合度３から１２の
、ポリフェニレンサルファイド、ポリスルフオン、ポリ
フェニレンオキサイドより選ばれた少なくとも１種の重
合体である請求項２に記載の導電性高分子。(4) A claim in which the polymer oligomer having sulfonic acid groups is at least one kind of polymer selected from polyphenylene sulfide, polysulfone, and polyphenylene oxide, which has sulfonic acid groups bonded to both ends and has an average degree of polymerization of 3 to 12. 2. The conductive polymer according to 2.
ｐ−オキシ安息香酸−アルデヒド縮重合体、サリチル酸
−アルデヒド縮重合体より選ばれた少なくとも１種であ
る請求項２に記載の導電性高分子。(5) A polymer oligomer having an oxybenzoic acid group,
The conductive polymer according to claim 2, which is at least one selected from p-oxybenzoic acid-aldehyde condensation polymer and salicylic acid-aldehyde condensation polymer.
レンサルファイド、ポリチオフェン、ポリアニリン、及
びその誘導体より選ばれた少なくとも１種である請求項
１に記載の導電性高分子。(6) The conductive polymer according to claim 1, wherein the electronically conjugated polymer is at least one selected from polypyrrole, polyphenylene sulfide, polythiophene, polyaniline, and derivatives thereof.
りなる電解コンデンサにおいて、前記電解性導電体が、
平均重合度３から１２の重合体オリゴマーをドーパント
として電子共役性高分子中に分散してなる導電性高分子
よりなる電解コンデンサ。(7) In an electrolytic capacitor consisting of a metal anode, an oxide dielectric layer, an electrolytic conductor, and a cathode, the electrolytic conductor is
An electrolytic capacitor made of a conductive polymer in which a polymer oligomer having an average degree of polymerization of 3 to 12 is dispersed as a dopant in an electronically conjugated polymer.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19296289A JPH0674382B2 (en) | 1989-07-25 | 1989-07-25 | Conductive polymer and electrolytic capacitor using the same |
| EP19900113540 EP0409124A3 (en) | 1989-07-19 | 1990-07-14 | Electrically conducting polymer, method for preparing the same and electrolytic capacitor comprising the same |
| US07/758,196 US5130886A (en) | 1989-07-19 | 1991-09-11 | Electrically conducting polymer, method for preparing the same and electrolytic capacitor comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19296289A JPH0674382B2 (en) | 1989-07-25 | 1989-07-25 | Conductive polymer and electrolytic capacitor using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0356567A true JPH0356567A (en) | 1991-03-12 |
| JPH0674382B2 JPH0674382B2 (en) | 1994-09-21 |
Family
ID=16299937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19296289A Expired - Fee Related JPH0674382B2 (en) | 1989-07-19 | 1989-07-25 | Conductive polymer and electrolytic capacitor using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0674382B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3034680U (en) * | 1996-08-12 | 1997-02-25 | 麻沼総業株式会社 | Pencil-shaped makeup tools |
-
1989
- 1989-07-25 JP JP19296289A patent/JPH0674382B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0674382B2 (en) | 1994-09-21 |
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