JPH0674382B2 - Conductive polymer and electrolytic capacitor using the same - Google Patents
Conductive polymer and electrolytic capacitor using the sameInfo
- Publication number
- JPH0674382B2 JPH0674382B2 JP19296289A JP19296289A JPH0674382B2 JP H0674382 B2 JPH0674382 B2 JP H0674382B2 JP 19296289 A JP19296289 A JP 19296289A JP 19296289 A JP19296289 A JP 19296289A JP H0674382 B2 JPH0674382 B2 JP H0674382B2
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- polymer
- sulfonic acid
- conductive polymer
- oligomer
- polymerization
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Description
【発明の詳細な説明】 産業上の利用分野 本発明は、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る。TECHNICAL FIELD The present invention relates to a conductive polymer excellent in stability over time and an electrolytic capacitor using the same.
従来の技術 導電性高分子はポリアセチレン、ポリピロール、ポリチ
オフェン、ポリアニリン、ポ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（ルイス酸、プロトン酸などのアニオ
ン）をドーパントとして含有して高導電性を示すことが
広く知られている。2. Description of the Related Art A conductive polymer is a polymer having a greatly expanded conjugated π-electron system, such as polyacetylene, polypyrrole, polythiophene, polyaniline, and polyacene, and is an electron donor or electron acceptor (anion such as Lewis acid or protonic acid). It is widely known to contain as a dopant to exhibit high conductivity.
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。However, these dopants have a major drawback that they diffuse in the polymer matrix due to an electric field and reduce the conductivity.
この欠点に鑑み、フタロシアニンテトラスルフォン酸、
ポ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 オブ ケミカル ソサエティ第684頁1983
年版（K.Okabayashi、J.Chem.Sci.,Chem.Commun.,p684
（1983））およびイビド第871頁1985年版（N.Bates eta
l,ibib.,p871（1985））にすでに開示されている。In view of this drawback, phthalocyanine tetrasulfonic acid,
High molecular weight dopants such as polystyrene sulphonic acid are published in Journal of Chemical Society, page 684, 1983.
Annual edition (K.Okabayashi, J.Chem.Sci., Chem.Commun., P684
(1983)) and Ibid, pp. 871, 1985 edition (N. Bates eta.
l, ibib., p871 (1985)).
しかしながら、これらのドーパントを鋭意検討した結
果、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ポリマー生成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大きかっ
た。However, as a result of diligent examination of these dopants, phthalocyanine tetrasulfonic acid was a bulky phthalocyanine nucleus, which disturbed the crystalline alignment of the conductive polymer chains during polymer formation, and the movement by the electric field was relatively large.
また、一方ポリスチレンスルフォン酸は重合度が大きす
ぎるせいか、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た。On the other hand, because polystyrene sulfonic acid has a too high degree of polymerization, it has poor compatibility with the conductive polymer matrix and a uniform molecular dispersion cannot be obtained.
本発明はこれらの現象に鑑み、鋭意検討の結果得られた
もので、耐熱性、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る。In view of these phenomena, the present invention has been obtained as a result of earnest studies, and an object thereof is to provide a conductive polymer excellent in heat resistance and stability over time by an electric field, and to provide an electrolytic capacitor using the same. To do.
課題を解決するための手段 本発明は、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性、電界による経時安
定性に優れる導電性高分子を構成するものである。Means for Solving the Problems The present invention provides a polymer oligomer having an ionic group and an average degree of polymerization of 3 to 12 as a dopant, which is molecularly dispersed in an electron-conjugated polymer to improve heat resistance and stability over time due to an electric field. It constitutes an excellent conductive polymer.
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
マーがドーパントして電子共役性高分子中に分子分散さ
れた時、そのイオン性基含有重合体オリゴマーはバルキ
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
きない。それ故、直流電界下でも経時的に安定した導電
率を示す。When a polymer oligomer having an average degree of polymerization of 3 to 12 having an ionic group is used as a dopant and is molecularly dispersed in an electron-conjugated polymer, the polymer oligomer containing an ionic group is a bulky molecule, and thus is an electron. It cannot move easily in conjugated polymers. Therefore, it exhibits stable electrical conductivity over time even under a DC electric field.
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
しては、スルフォン酸基、オキシ安息香酸基のいずれか
を有する重合体が好ましい。Examples As the polymer oligomer having an ionic group used in the present invention, a polymer having either a sulfonic acid group or an oxybenzoic acid group is preferable.
スルフォン酸基を有する重合体オリゴマーとしては、ト
ルエンスルフォン酸−アルデヒド縮重合体、ペンゼンス
ルフォン酸−アルデヒド縮重合体、ポリスチレンスルフ
ォン酸等を用いる。As the polymer oligomer having a sulfonic acid group, toluene sulfonic acid-aldehyde polycondensate, penzen sulfonic acid-aldehyde polycondensate, polystyrene sulfonic acid, and the like are used.
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
12の、ポリフェニレンサルファイド、ポリスルフォン、
ポリフェニレンオキサイドである場合もある。In addition, as a polymer oligomer having a sulfonic acid group, from the average degree of polymerization 3 in which sulfonic acid groups are bonded at both ends,
12, polyphenylene sulfide, polysulfone,
It may be polyphenylene oxide.
オキシ安息香酸基を有する重合体オリゴマーとしては、
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る。As the polymer oligomer having an oxybenzoic acid group,
A p-oxybenzoic acid-aldehyde condensation polymer, salicylic acid-aldehyde condensation polymer, or the like is used.
本発明に用いる重合体オリゴマーの平均重合度は３〜12
の範囲である。The average degree of polymerization of the polymer oligomer used in the present invention is 3-12.
Is the range.
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かなり電子共役性高分子の相溶
性、凝集性等に悪い影響を与える。If the average degree of polymerization is 3 or less, the behavior is not much different from that of the monomer.
When it is 12 or more, it has a bad influence on the compatibility and cohesiveness of the electron-conjugated polymer.
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香酸を有しており、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（キャリヤ数
の増加）に大きく寄与する。Further, this ionic group-containing polymer oligomer has a sulfonic acid group and oxybenzoic acid, and acts as a dopant of the electron-conjugated polymer and greatly contributes to the improvement of conductivity (increase in the number of carriers).
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と小さいため、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し、生成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め、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
いる。The ionic group-containing polymer oligomer of the present invention has a degree of polymerization of 3
Since it is as small as ~ 12, it behaves like a low molecule in a low viscosity monomer solution during polymerization, and is not so bulky in the resulting conductive polymer. It has a great feature that it is relatively uniformly dispersed in the electron-conjugated polymer without much influence.
中でも、両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、ポリスルフォ
ン、ポリフェ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る。Above all, the average degree of polymerization in which sulfonic acid groups are bonded to both ends is 3
The polyphenylene sulfide, polysulfone, polyphenylene oxide, etc. of No. 1 to No. 12 are aromatic molecules which are dopants having compatibility with the electron-conjugated polymer and form high quality films.
電子共役性高分子としては、ポリピロール、ポリフェニ
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
れる。Examples of the electron-conjugated polymer include polypyrrole, polyphenylene sulfide, polythiophene, polyaniline, and derivatives thereof, which are obtained by chemical polymerization or electrolytic polymerization (anodic oxidation polymerization, cathodic reduction polymerization) and the like.
陽極酸化重合は、電子共役性モノマーの溶液中にアニオ
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で、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
れて成る導電性高分子が得られる。Anodizing polymerization is a method in which a polymer oligomer having an anionic group is dissolved in a solution of an electron-conjugated monomer, and the electron-conjugated monomer is electrolytically polymerized on an anode by an electric field generated by at least a pair of electrodes. A conductive polymer is obtained in which a polymer oligomer having a functional group is molecularly dispersed as a dopant.
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は、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る。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
Ba２＋、Pb２＋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る。The conductive polymer containing the polymer oligomer having an anionic group thus obtained may have humidity-dependent conductivity because the anion is hydrophilic. In this case, for example, metal ions that produce insoluble salts (for example,
Water resistance can be achieved by treating with Ba 2+ , Pb 2+, etc.).
本発明における導電性高分子は、金属陽極、酸化物誘電
層、電解性導電体、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る。この場合に本
発明の導電性高分子の特徴である耐熱性、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
とができる。The conductive polymer in the present invention can be applied as an electrolytic conductor of an electrolytic capacitor including a metal anode, an oxide dielectric layer, an electrolytic conductor, and a cathode. In this case, it is possible to obtain a capacitor having excellent characteristics due to the heat resistance and the stability over time due to an electric field, which are the characteristics of the conductive polymer of the present invention.
また、ｐ−ｎ接合素子とする場合にも安定した接合特性
が得られる。In addition, stable junction characteristics can be obtained even when using a pn junction element.
次に実施例を用いて本発明を説明する。Next, the present invention will be described using examples.
実施例１ 200mlのセパラブルフラスコ中に、4gのピロールと2gの
トルエンスルフォン酸−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、
反応溶液を得た。Example 1 In a 200 ml separable flask, 4 g of pyrrole, 2 g of toluenesulfonic acid-formaldehyde condensation polymer (average degree of polymerization 4) and 100 ml of acetonitrile were placed.
A reaction solution was obtained.
この溶液にインジウム−スズ酸化物（ITO）を陽極と
し、Pt板を陰極として窒素気流中で通電し、陽極上に約
25μｍのポリピロール膜を得た。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ろ、18
S/cm（25℃）であった。Indium-tin oxide (ITO) was used as an anode in this solution, and a Pt plate was used as a cathode to conduct electricity in a nitrogen stream, and the solution was applied on the anode.
A 25 μm polypyrrole film was obtained. This film was peeled off from the electrode, silver paint was applied, and the conductivity was measured.
It was S / cm (25 ° C).
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ろ、300時間後の変化は1
0％であった。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た。Furthermore, this film was set in an 80 ° C furnace and a DC electric field was applied,
The change over time of the current was measured, and after 300 hours, the change was 1
It was 0%. This stability was remarkably more stable than the conventional low molecular weight dopant.
実施例２ 200mlのセパラブルフラスコ中に、5gの３−メチルチオ
フェンと3gのサリチル酸−ホルムアルデヒド縮重合体
（平均重合度３）および150mlのニトロベンゼンを入れ
て、重合溶液を得た。Example 2 A 200 ml separable flask was charged with 5 g of 3-methylthiophene, 3 g of a salicylic acid-formaldehyde condensation polymer (average degree of polymerization 3) and 150 ml of nitrobenzene to obtain a polymerization solution.
この溶液にインジウム−スズ酸化物（ITO）を陽極と
し、Pt板を陰極として窒素気流中で通電し、陽極上に約
20μｍのポリ（３−メチルチオフェン）膜を得た。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
定したところ、7S/cm（25℃）であった。Indium-tin oxide (ITO) was used as an anode in this solution, and a Pt plate was used as a cathode to conduct electricity in a nitrogen stream, and the solution was applied on the anode.
A 20 μm poly (3-methylthiophene) film was obtained. This film was peeled from the electrode, silver paint was applied, and the conductivity was measured and found to be 7 S / cm (25 ° C.).
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ろ、300時間後の変化は1
6％であった。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た。Furthermore, this film was set in an 80 ° C furnace and a DC electric field was applied,
The change over time of the current was measured, and after 300 hours, the change was 1
It was 6%. This stability was remarkably more stable than the conventional low molecular weight dopant.
実施例３ 200mlのセパラブルフラスコ中に、5gの３−メチルチオ
フェンと3gの両端にスルフォン基を付けたポリフェニレ
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、重合溶液を得た。Example 3 In a 200 ml separable flask, 5 g of 3-methylthiophene, 3 g of polyphenylene sulfide having an sulfo group at both ends (average degree of polymerization 6), and 150 ml of nitrobenzene were placed to obtain a polymerization solution.
この溶液にインジウム−スズ酸化物（ITO）を陽極と
し、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）膜を得た。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
定したところ、90S/cm（25℃）であった。Indium-tin oxide (ITO) was used as an anode in this solution, and a Pt plate was used as a cathode to conduct electricity in a nitrogen stream, and the solution was applied on the anode.
A 23 μm poly (3-methylthiophene) film was obtained. The film was peeled off from the electrode, silver paint was applied, and the conductivity was measured and found to be 90 S / cm (25 ° C.).
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ろ、300時間後の変化は1
1％であった。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た。Furthermore, this film was set in an 80 ° C furnace and a DC electric field was applied,
The change over time of the current was measured, and after 300 hours, the change was 1
It was 1%. This stability was remarkably more stable than the conventional low molecular weight dopant.
実施例４ 0.03mmの粗面化処理したアルミニウムフィルムにまず酸
化物誘電層を形成したのち、導電核を形成し、ついで導
電性高分子形成糟を通して実施例１と同じ反応溶液組成
にて導電性高分子膜を形成した。Example 4 A 0.03 mm surface-roughened aluminum film was first formed with an oxide dielectric layer, then conductive nuclei were formed, and then the conductive polymer was used to form a conductive solution with the same reaction solution composition as in Example 1. A polymer film was formed.
ついでそれを折り畳んだ後銀ペイントで陰極を形成し
て、リード線を取出しそれに外装樹脂を被覆した。Then, after folding it, the cathode was formed with silver paint, the lead wire was taken out, and the exterior resin was coated on it.
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静電容
量を示した。The thus obtained solid electrolytic capacitor showed almost the same capacitance as the same type of multilayer capacitor using a low molecular weight dopant.
これの周波数特性並びに経時安定性を測定したところ、
周波数特性は低分子ドーパントのものとほぼ同一であっ
たが、経時安定性は大きく改善され、125℃ 2000時間
以上の寿命を示した。When the frequency characteristics and stability over time of this were measured,
The frequency characteristics were almost the same as those of the low molecular weight dopant, but the stability with time was greatly improved, and the lifetime was over 125 hours at 125 ° C.
発明の効果 このように本発明は、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、耐熱性、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
る。EFFECTS OF THE INVENTION As described above, the present invention has an average degree of polymerization of 3 having an ionic group.
Nos. 12 to 12 are molecularly dispersed in the electron-conjugated polymer by using the polymer oligomer as a dopant to obtain a conductive polymer having excellent heat resistance and stability over time under an electric field.
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時、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ず、
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
る。When the polymer oligomer is dispersed in the electron-conjugated polymer as a dopant, it cannot move easily in the electron-conjugated polymer because it is a bulky molecule compared to a low molecule.
It has the effect of exhibiting stable conductivity over time even under a DC electric field.
また、本発明のイオン性基含有重合体オリゴマーは重合
度が小さいため、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し、生成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め、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、良質の導電性高分子フィル
ムを与えるという特徴がある。In addition, since the ionic group-containing polymer oligomer of the present invention has a small degree of polymerization, it behaves like a low molecule in a low viscosity monomer solution during polymerization, and is not so bulky in a generated conductive polymer. Since it does not exist, the crystallinity and the agglomeration structure are not affected as much as a high polymer, and are characterized in that they are relatively uniformly molecularly dispersed in the electron-conjugated polymer to give a good quality conductive polymer film.
本発明における導電性高分子は、金属陽極、酸化物誘電
層、電解性導電体、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る。この場合には
本発明の導電性高分子の特徴である耐熱性、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
ことができる。The conductive polymer in the present invention can be applied as an electrolytic conductor of an electrolytic capacitor including a metal anode, an oxide dielectric layer, an electrolytic conductor, and a cathode. In this case, a capacitor having excellent characteristics can be obtained due to the heat resistance and the stability with time due to an electric field, which are the characteristics of the conductive polymer of the present invention.
また、ｐ−ｎ接合素子とする場合にも安定した接合特性
が得られる。In addition, stable junction characteristics can be obtained even when using a pn junction element.
このように本発明は工業的価値の大なるものである。As described above, the present invention has great industrial value.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 81/06 ＬＲＦ 7308−4Ｊ Ｈ０１Ｂ 1/12 Ｚ 7244−5Ｇ Ｈ０１Ｇ 9/02 ３３１ 9375−5Ｅ Continuation of front page (51) Int.Cl. 5 Identification number Office reference number FI Technical display location C08L 81/06 LRF 7308-4J H01B 1/12 Z 7244-5G H01G 9/02 331 9375-5E
Claims (7)
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
中に分子分散されてなる導電性高分子。1. A conductive polymer in which a polymer oligomer having an ionic group and an average degree of polymerization of 3 to 12 is molecularly dispersed in an electron-conjugated polymer as a dopant.
キシ安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.
が、ト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. A polymer oligomer having a sulfonic acid group is at least one polymer selected from a toluene sulfonic acid-aldehyde condensed polymer, a benzene sulfonic acid-aldehyde condensed polymer, and a polystyrene sulfonic acid. 2. The conductive polymer described in 2.
が、両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、ポリスルフォン、
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 polymer oligomer having a sulfonic acid group has an average degree of polymerization of 3 having sulfonic acid groups bonded at both ends.
12, polyphenylene sulfide, polysulfone,
The conductive polymer according to claim 2, which is at least one polymer selected from polyphenylene oxide.
ーが、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. The polymer oligomer having an oxybenzoic acid group is at least one selected from p-oxybenzoic acid-aldehyde condensation polymers and salicylic acid-aldehyde condensation polymers.
The conductive polymer according to claim 2, which is a seed.
フェニレンサルファイド、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 electron-conjugated polymer is at least one selected from polypyrrole, polyphenylene sulfide, polythiophene, polyaniline, and derivatives thereof.
陰極よ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−をド−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. A metal anode, an oxide dielectric layer, an electrolytic conductor,
An electrolytic capacitor comprising a cathode, wherein the electrolytic conductor comprises 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 electron-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 JPH0356567A (en) | 1991-03-12 |
| JPH0674382B2 true 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) |
Cited By (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
Cited By (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0356567A (en) | 1991-03-12 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |