JPH056285B2 - - Google Patents
Info
- Publication number
- JPH056285B2 JPH056285B2 JP58213204A JP21320483A JPH056285B2 JP H056285 B2 JPH056285 B2 JP H056285B2 JP 58213204 A JP58213204 A JP 58213204A JP 21320483 A JP21320483 A JP 21320483A JP H056285 B2 JPH056285 B2 JP H056285B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- substrate
- polymer film
- insulating polymer
- aromatic
- 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 - Lifetime
Links
- 239000000758 substrate Substances 0.000 claims description 54
- 229920006254 polymer film Polymers 0.000 claims description 52
- 125000003118 aryl group Chemical group 0.000 claims description 27
- 229920001940 conductive polymer Polymers 0.000 claims description 21
- 239000002861 polymer material Substances 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 31
- 238000006116 polymerization reaction Methods 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- 229920000128 polypyrrole Polymers 0.000 description 7
- 229920000915 polyvinyl chloride Polymers 0.000 description 7
- 239000004800 polyvinyl chloride Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- -1 polycyclic aromatic compounds Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- FEKWWZCCJDUWLY-UHFFFAOYSA-N 3-methyl-1h-pyrrole Chemical compound CC=1C=CNC=1 FEKWWZCCJDUWLY-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- QKFFSWPNFCXGIQ-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetraethylazanium Chemical compound CC[N+](CC)(CC)CC.CC1=CC=C(S([O-])(=O)=O)C=C1 QKFFSWPNFCXGIQ-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 1
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- MWBVUGIRAZQHGZ-UHFFFAOYSA-N acetonitrile;ethane-1,2-diol;hydrate Chemical compound O.CC#N.OCCO MWBVUGIRAZQHGZ-UHFFFAOYSA-N 0.000 description 1
- DSRXQXXHDIAVJT-UHFFFAOYSA-N acetonitrile;n,n-dimethylformamide Chemical compound CC#N.CN(C)C=O DSRXQXXHDIAVJT-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は改良された導電性高分子フイルムとそ
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an improved conductive polymer film and a method for producing the same.
ある種の芳香族化合物は電解質を添加した溶剤
中に溶解させ、電解酸化行うことにより、導電性
の高分子フイルムを電極基板上に形成させること
ができる。このような芳香族化合物としてはピロ
ール類、チオフエン類等の複素環式化合物、アズ
レン、ピレン、トリフエニレン等の多環芳香族化
合物が知られている〔例えばJ.バーゴン（J.
Bargon）、S.モーマンド（S.Mohmand）、R.J.ウ
オルトマン（R.J.Waltman）、IBMジヤーナル
オブ リサーチ エンド デベロツプメント
（IBM Journal of Reserch ＆ Development）
第27巻 第４号 第330頁（1983年）参照〕。
A conductive polymer film can be formed on an electrode substrate by dissolving certain aromatic compounds in a solvent containing an electrolyte and performing electrolytic oxidation. Known examples of such aromatic compounds include heterocyclic compounds such as pyrroles and thiophenes, and polycyclic aromatic compounds such as azulene, pyrene, and triphenylene [for example, J. Burgon (J.
Bargon), S. Mohmand, RJ Waltman, IBM Journal
IBM Journal of Research & Development
See Vol. 27, No. 4, p. 330 (1983)].
しかしながら、従来の電極基板上に直接電解酸
化して形成した導電性高分子フイルムは以下のよ
うな欠点があつた。 However, conventional conductive polymer films formed by direct electrolytic oxidation on electrode substrates have the following drawbacks.
(1) フイルムの機械的強度が弱いため、基板上で
もまたフイルムとして単離した状態でも破れや
すく取扱いが困難であつた。(1) Because the mechanical strength of the film is weak, it is easy to tear and difficult to handle both on a substrate and when isolated as a film.
(2) 電気伝導度を制御することが困難であつた。(2) It was difficult to control electrical conductivity.
(3) 基板との密着力が弱く、フイルム形成中ある
いは形成後の洗浄過程ではがれやすい。(3) It has weak adhesion to the substrate and is likely to peel off during film formation or during the cleaning process after formation.
(4) ネサガラスの様な、電解溶液や形成される芳
香族系高分子フイルムに比べて電気抵抗が同等
あるいはそれ以下の電極基板を用いると均一な
フイルムを形成できず、膜厚に大きなバラツキ
がみられた。(4) If an electrode substrate such as Nesa Glass, which has an electrical resistance equal to or lower than the electrolytic solution or the aromatic polymer film formed, is used, it will not be possible to form a uniform film, and there will be large variations in film thickness. It was seen.
(5) 空気中に放置すると電気伝導度が低下しやす
い。(5) Electrical conductivity tends to decrease when left in air.
本発明はこれらの欠点を除去するためになされ
たものであり、その目的は密着性、均一性、安定
性、基板表面性、電気伝導度制御性に優れた複合
導電性高分子フイルム及びその製造方法を提供す
ることにある。
The present invention was made to eliminate these drawbacks, and its purpose is to provide a composite conductive polymer film with excellent adhesion, uniformity, stability, substrate surface properties, and electrical conductivity controllability, and its production. The purpose is to provide a method.
本発明を概説すれば、本発明の第１の発明は複
合導電性高分子フイルムの発明であつて、電極基
板上に積層した２種以上の絶縁性高分子フイルム
と、該基板上に電解酸化により電気化学的に形成
した芳香族系高分子材料とから成ることを特徴と
する。
To summarize the present invention, the first invention of the present invention is an invention of a composite conductive polymer film, which comprises two or more types of insulating polymer films laminated on an electrode substrate, and electrolytic oxidation on the substrate. It is characterized by being made of an aromatic polymer material electrochemically formed by.
また、本発明の第２の発明は複合導電性高分子
フイルムの発明であつて、積層した２種以上の絶
縁性高分子フイルムと、電解酸化により電気化学
的に形成した芳香族系高分子材料とから成ること
を特徴とする。 Further, the second invention of the present invention is an invention of a composite conductive polymer film, which comprises two or more laminated insulating polymer films and an aromatic polymer material electrochemically formed by electrolytic oxidation. It is characterized by consisting of.
そして、本発明の第３の発明は複合導電性高分
子フイルムの製造方法の発明であつて、電極基板
上に絶縁性高分子フイルムを２種以上積層する工
程及びその上に電解酸化により芳香族系高分子材
料を電気化学的に形成する工程の各工程を包含す
ることを特徴とする。 The third invention of the present invention is an invention of a method for manufacturing a composite conductive polymer film, which includes a step of laminating two or more kinds of insulating polymer films on an electrode substrate, and an aromatic film is added thereon by electrolytic oxidation. The method is characterized in that it includes each step of electrochemically forming a polymeric material.
電解重合による導電性高分子フイルムは通常電
極基板を、アセトニトリル等の有機溶媒中に電解
重合用モノマーとなる芳香族系化合物と通電させ
るための電解質とを溶解させた溶液中に、対向電
極と共に入れ、両電極間に通電させることにより
形成される。この際、電極基板を絶縁性の高分子
フイルムでコーテイングすれば、当然通電できず
導電性フイルムは全く形成されない。しかしなが
ら本発明者等は電極基板上に各種の絶縁性高分子
フイルムを塗布し、これを溶解させることのない
適切な電解反応溶液を組合せることにより電解反
応が通常の電極上と同様に進むことを見出した。
このようにして得られたフイルムは第１図に示す
様に生成条件により絶縁性高分子フイルムの内部
に電解重合された芳香族系高分子材料の混入され
た導電性フイルムｂ、あるいは芳香族系高分子フ
イルムと絶縁性高分子フイルムの積層された２層
構造のフイルムｃを与える。更にｂとｃの中間の
一部分だけ芳香族系高分子材料が混入したフイル
ムも得られる。すなわち第１図は電極基板上に一
層の絶縁性高分子フイルムをコーテイングした場
合の電解重合の工程図であつて、ａは電解前、ｂ
は芳香族系高分子材料がフイルム中に混入した場
合、ｃは芳香族系絶縁性高分子材料が高分子フイ
ルムと共に電極表面に積層された場合を示す。第
１図中符号１は電極基板、２は絶縁性高分子フイ
ルム、３は芳香族系高分子材料が混入した導電性
フイルム、４は芳香族系高分子材料のみのフイル
ムを意味する。複合されたフイルムはいずれも導
電性の芳香族系高分子材料が含まれているため、
高い電気伝導度を示すと共に、電解重合時間によ
り、フイルムの電気伝導度を広い範囲で制御でき
る。また、絶縁性高分子フイルムを選択すること
によりフイルムの性質を変えることができる。 Conductive polymer films produced by electrolytic polymerization are usually produced by placing the electrode substrate together with a counter electrode in a solution containing an aromatic compound that will serve as a monomer for electrolytic polymerization and an electrolyte for conducting electricity in an organic solvent such as acetonitrile. , is formed by passing current between both electrodes. At this time, if the electrode substrate is coated with an insulating polymer film, it will naturally not be possible to conduct electricity and no conductive film will be formed. However, the present inventors have discovered that by coating various insulating polymer films on the electrode substrate and combining them with an appropriate electrolytic reaction solution that does not dissolve the film, the electrolytic reaction proceeds in the same way as on normal electrodes. I found out.
As shown in Figure 1, the film obtained in this way can be a conductive film b in which an electrolytically polymerized aromatic polymer material is mixed inside an insulating polymer film, or an aromatic polymer material mixed in the inside of an insulating polymer film, depending on the production conditions. A film c having a two-layer structure in which a polymer film and an insulating polymer film are laminated is provided. Furthermore, a film in which an aromatic polymer material is mixed only in a portion between b and c can also be obtained. That is, FIG. 1 is a process diagram of electrolytic polymerization when a single layer of insulating polymer film is coated on an electrode substrate, where a is before electrolysis, b is
c shows the case where the aromatic polymer material is mixed into the film, and c shows the case where the aromatic insulating polymer material is laminated on the electrode surface together with the polymer film. In FIG. 1, reference numeral 1 denotes an electrode substrate, 2 an insulating polymer film, 3 a conductive film mixed with an aromatic polymer material, and 4 a film made only of an aromatic polymer material. All composite films contain conductive aromatic polymer materials, so
In addition to exhibiting high electrical conductivity, the electrical conductivity of the film can be controlled over a wide range by changing the electrolytic polymerization time. Further, by selecting an insulating polymer film, the properties of the film can be changed.
本発明者等は更に本発明において、これらの各
種複合あるいは積層導電性フイルムを２種以上組
合せたフイルムの作製ができ、得られたフイルム
が単独の導電性フイルムに比べて著しく特性の良
い導電性高分子フイルムを与えることを見出し
た。 Furthermore, in the present invention, the present inventors have been able to produce a film that combines two or more of these various composite or laminated conductive films, and the resulting film has significantly better conductivity than a single conductive film. It was discovered that a polymer film can be obtained.
すなわち、第２図に示す様に電極基板上に第１
の絶縁性高分子フイルムをコーテイングし、更に
その上部に第２の絶縁性高分子フイルムを積層し
ｄ、この基板を芳香族系化合物を含む電解重合溶
液中で重合することにより２層構造の複合導電性
高分子フイルムが得られる。この場合、条件によ
りｅに示す様な２層共に芳香族系高分子材料が混
入した導電性フイルムを与える場合と、ｆのよう
に第１層のみ導電性フイルムを与える場合があ
る。第２図中符号５は１層目の絶縁性高分子フイ
ルム、６は２層目の絶縁性高分子フイルム、７は
芳香族系高分子材料が混入した１層目の導電性フ
イルムそして８は芳香族系高分子材料が混入した
２層目の導電性フイルムを意味する。 That is, as shown in FIG.
A second insulating polymer film is coated on top of the first insulating polymer film, and this substrate is polymerized in an electrolytic polymerization solution containing an aromatic compound to form a two-layer composite. A conductive polymer film is obtained. In this case, depending on the conditions, a conductive film mixed with an aromatic polymer material may be provided for both layers as shown in e, or a conductive film may be provided only in the first layer as shown in f. In FIG. 2, numeral 5 is the first layer of insulating polymer film, 6 is the second layer of insulating polymer film, 7 is the first layer of conductive film mixed with aromatic polymer material, and 8 is the first layer of conductive film. This refers to the second layer of conductive film mixed with an aromatic polymer material.
また、絶縁性高分子フイルムを３層以上に積層
しても膜厚と高分子フイルムの種類、溶剤を選択
することにより多層の複合導電性高分子フイルム
が得られる。 Furthermore, even if three or more layers of insulating polymer films are laminated, a multilayer composite conductive polymer film can be obtained by selecting the film thickness, type of polymer film, and solvent.
絶縁性高分子フイルムとしてポリグリシジルメ
タクリレート等のエポキシ基を含む高分子化合
物、あるいはノボラツク樹脂の様なOH基を含む
高分子化合物を用いる基板との密着性の良好な導
電性フイルムが形成される。 A conductive film with good adhesion to the substrate is formed using a polymer compound containing an epoxy group such as polyglycidyl methacrylate or a polymer compound containing an OH group such as novolak resin as the insulating polymer film.
他方、絶縁性高分子フイルムとしてポリステレ
ン、クロロメチル化ポリスチレン、ポリビニルナ
フタレン、ポリビニルカルバゾール等の芳香族高
分子化合物を用いると均一で電気伝導性の制御が
容易で電気伝導度の高い導電性フイルムができる
が基板との密着力は弱く、容易に基板からはがれ
る。 On the other hand, when an aromatic polymer compound such as polysterene, chloromethylated polystyrene, polyvinylnaphthalene, or polyvinylcarbazole is used as an insulating polymer film, a conductive film with uniform electrical conductivity and high electrical conductivity can be obtained with easy control of electrical conductivity. However, its adhesion to the substrate is weak and it easily peels off from the substrate.
したがつて、基板密着性の優れた高分子化合物
の上に芳香族高分子化合物を積層して電解重合を
行うことにより密着力、均一性、導電性いずれを
も良好な複合導電性フイルムが得られた。 Therefore, by laminating an aromatic polymer compound on a polymer compound with excellent substrate adhesion and performing electrolytic polymerization, a composite conductive film with good adhesion, uniformity, and conductivity can be obtained. It was done.
また、ポリ塩化ビニル、ポリフツ化ビニリデン
系の高分子化合物を絶縁性高分子フイルムとして
用いると電解重合芳香族系高分子材料と絶縁性高
分子フイルムの２層構造の積層フイルムが得られ
る。 Further, when a polyvinyl chloride or polyvinylidene fluoride-based polymer compound is used as the insulating polymer film, a laminated film having a two-layer structure of an electropolymerized aromatic polymer material and an insulating polymer film can be obtained.
したがつて、絶縁性高分子フイルムとしてまず
芳香族高分子化合物を用い、更にその上に積層フ
イルムが得られる高分子フイルムを形成して、電
解重合を行うことにより均一で導電性の制御され
た複合導電性高分子フイルムが絶縁性高分子フイ
ルムの表面コート付きで得られる。 Therefore, by first using an aromatic polymer compound as an insulating polymer film, and then forming a polymer film on top of which a laminated film can be obtained, and performing electrolytic polymerization, it is possible to obtain uniform and controlled conductivity. A composite conductive polymer film is obtained with a surface coating of an insulating polymer film.
更に３層に絶縁性高分子フイルムを積層すると
各層の組合せの複合導電性高分子フイルムを得る
ことができる。例えば第３図に示す様に、まず電
極基板１上に基板密着力のよい絶縁性高分子フイ
ルム（第１層）２をコーテイングし、次いで電気
伝導度制御用の芳香族高分子化合物（第２層）３
をコーテイングし、その上に積層構造を与える絶
縁性高分子フイルム（第３層）９をコーテイング
した基板ｇを用いて、電解重合することにより、
密着力、均一性、導電性のすべてについて良好な
複合導電性高分子フイルムを、表面に絶縁性高分
子フイルムがコートされた構造ｈで得られる。な
お第３図中で符号７及び８は第２図と同義であ
り、９は３層目の高分子フイルムを意味する。 Furthermore, by laminating three layers of insulating polymer films, a composite conductive polymer film with a combination of each layer can be obtained. For example, as shown in FIG. 3, an insulating polymer film (first layer) 2 with good adhesion to the substrate is first coated on the electrode substrate 1, and then an aromatic polymer compound (second layer) for controlling electrical conductivity is coated on the electrode substrate 1. layer) 3
By electrolytically polymerizing using a substrate g coated with an insulating polymer film (third layer) 9 that provides a laminated structure,
A composite conductive polymer film having good adhesion, uniformity, and conductivity can be obtained with structure h in which the surface is coated with an insulating polymer film. In FIG. 3, numerals 7 and 8 have the same meanings as in FIG. 2, and 9 means the third layer of polymer film.
したがつて、あらかじめ基板に設ける絶縁性高
分子フイルムは、いかなるものを用いてもよい。
そして電解液としては次の条件を満していればよ
い。 Therefore, any insulating polymer film may be used to provide the substrate in advance.
The electrolytic solution may satisfy the following conditions.
(1) 絶縁性高分子フイルムを溶かさないこと
(2) 電解塩と電解重合用モノマーを溶かすことが
できること
(3) あらかじめ基板上に形成した絶縁性高分子フ
イルム中に電解重合用モノマーを拡散させるこ
とができること
なお、本発明におけるフイルム用高分子材料中
には、可塑剤、顔料及び色素等の常用の添加剤を
添加してもよく、それらを添加した場合でも、そ
れら添加剤が電解液中に溶出することはなく、ま
た得られた導電性高分子フイルムの所望の特性は
変化しない。(1) Do not dissolve the insulating polymer film. (2) Be able to dissolve the electrolytic salt and monomer for electrolytic polymerization. (3) Diffuse the monomer for electrolytic polymerization into the insulating polymer film formed on the substrate in advance. Note that commonly used additives such as plasticizers, pigments, and dyes may be added to the polymeric material for films in the present invention, and even if these additives are added, they may not be present in the electrolyte. The conductive polymer film will not be eluted, and the desired properties of the obtained conductive polymer film will not change.
以下、本発明を実施例により更に具体的に説明
するが、本発明はこれらに限定されない。
EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
実施例 １
ネサガラス基板上にクロロメチル化ポリスチレ
ン（以下CMSと略記する）（分子量30万）を0.5μ
ｍの厚さに塗布した。このフイルムに500Wキセ
ノンランプを15分照射してCMSを三次元架橋さ
せた。このフイルムの上にポリ塩化ビニルを0.8μ
ｍの厚さに塗布した。この基板をピロール1M、
電解質としてテトラエチルアンモニウムテトラフ
ルオロボレート0.3Mを加えたアセトニトリル−
水−エチレングリコール（98：１：１）混合溶媒
に、対向電極としての白金メツシユと共に浸漬
し、1.3Vで20分間電解重合を行うと基板上に黒
色のポリピロールが析出した。このフイルムは膜
厚が1.7μｍでネサガラス基板より容易にひきはが
すことができ、膜の構造がCMSとポリピロール
の混合した黒色の導電性フイルムと透明な光沢を
もつポリ塩化ビニルのフイルムの２層膜になつて
いた。このポリ塩化ビニル膜は高い強度をもつて
いるため得られた２層膜は高い強度をもつてい
る。CMS−ポリピロール複合膜面の電気伝導度
は4.3／Ω・cmで、他方ポリ塩化ビニル面は
10-7／Ω・cm以上の絶縁性を示した。Example 1 Chloromethylated polystyrene (hereinafter abbreviated as CMS) (molecular weight 300,000) was deposited at 0.5μ on a Nesa glass substrate.
It was applied to a thickness of m. This film was irradiated with a 500W xenon lamp for 15 minutes to three-dimensionally crosslink CMS. PVC 0.8μ on top of this film
It was applied to a thickness of m. This substrate is pyrrole 1M,
Acetonitrile with 0.3M of tetraethylammonium tetrafluoroborate added as electrolyte.
The substrate was immersed in a water-ethylene glycol (98:1:1) mixed solvent together with a platinum mesh serving as a counter electrode, and electrolytically polymerized at 1.3 V for 20 minutes to deposit black polypyrrole on the substrate. This film has a thickness of 1.7 μm and can be easily peeled off from the Nesa glass substrate, and its structure is a two-layer film consisting of a black conductive film made of a mixture of CMS and polypyrrole, and a transparent glossy polyvinyl chloride film. I was getting used to it. Since this polyvinyl chloride film has high strength, the obtained two-layer film has high strength. The electrical conductivity of the CMS-polypyrrole composite film surface is 4.3/Ω・cm, while the polyvinyl chloride surface is
It showed insulation properties of 10 -7 /Ω・cm or more.
実施例 ２
実施例１と同様なCMS（0.5μｍ厚）とポリ塩化
ビニル（0.8μｍ厚）の２層フイルムを塗布したネ
サガラス基板を５枚作製した。この基板を実施例
１と同じ電解重合溶液に浸漬し、1.3Vの電圧で
10秒、30秒、２分、10分、60分でそれぞれ電解重
合した。重合時間が増加するに従つて膜厚が増加
した。いずれのフイルムも均一で滑らかなポリ塩
化ビニルのフイルムに覆われた。CMS−ポリピ
ロール複合フイルムになつており、基板からはく
離して測定したCMS−ポリピロール面の電気伝
導度はそれぞれ２×10-4、４×10-2、１×10-1、
3.2×10-1、9.2／Ω・cmであり、重合時間により
電気伝導度が制御できることが明らかになつた。Example 2 Five Nesa glass substrates coated with the same two-layer film of CMS (0.5 μm thick) and polyvinyl chloride (0.8 μm thick) as in Example 1 were prepared. This substrate was immersed in the same electrolytic polymerization solution as in Example 1, and a voltage of 1.3V was applied.
Electrolytic polymerization was performed for 10 seconds, 30 seconds, 2 minutes, 10 minutes, and 60 minutes, respectively. The film thickness increased as the polymerization time increased. Both films were covered with a uniform, smooth polyvinyl chloride film. It is a CMS-polypyrrole composite film, and the electrical conductivity of the CMS-polypyrrole surface measured after peeling it off from the substrate is 2×10 -4 , 4×10 -2 , 1×10 -1 , respectively.
3.2×10 −1 and 9.2/Ω·cm, and it became clear that the electrical conductivity could be controlled by the polymerization time.
実施例 ３
ｎ型シリコン基板上（抵抗5Ω・cm）にポリグ
リシジルメタクリレート（以下PGMAと略記す
る）（分子量８万５千）を0.2μｍ厚に塗布し、200
℃で30分ベーキングした。このフイルム上にポリ
ビニルカルバゾール（以下PVCzと略記する）
（分子量46万）を1.0μｍ厚に塗布した。この基板
を正極とし、チオフエンを1M、過塩素酸銀を
0.2M溶解させたアセトニトリル中に白金メツシ
ユの対向電極と共に入れ、窒素気流下1.4Vの電
圧で、20分間電解反応を行つたところ基板表面に
青黒色のポリチオフエンが析出した。このフイル
ムはほぼ均一で膜厚1.5μｍであり、基板との優れ
た密着性を示した。このフイルムを切出して、電
気伝導度を測定したところ0.75／Ω・cmで、
PGMA／PVCz両面にポリチオフエンが複合した
構造をもつていた。Example 3 Polyglycidyl methacrylate (hereinafter abbreviated as PGMA) (molecular weight 85,000) was coated to a thickness of 0.2 μm on an n-type silicon substrate (resistance 5 Ω cm), and
Bake for 30 minutes at ℃. On this film, polyvinylcarbazole (hereinafter abbreviated as PVCz)
(molecular weight 460,000) was applied to a thickness of 1.0 μm. Using this substrate as a positive electrode, 1M thiophene and silver perchlorate were added.
The substrate was placed in 0.2M acetonitrile with a platinum mesh counter electrode, and an electrolytic reaction was carried out for 20 minutes at a voltage of 1.4V under a nitrogen stream, resulting in the precipitation of blue-black polythiophene on the substrate surface. This film was almost uniform with a thickness of 1.5 μm, and showed excellent adhesion to the substrate. When this film was cut out and the electrical conductivity was measured, it was 0.75/Ω・cm.
It had a structure in which polythiophene was composited on both sides of PGMA/PVCz.
実施例 ４
実施例３と同様にｎ型シリコン基板上に
PGMAを0.2μｍ厚、その上にPVCz0.8μｍを塗布
し、更にポリフツ化ビニリデン（以下PVDFと略
記する）（分子量82万）を0.6μｍ厚にコーテイン
グした。この基板をピロール1M、テトラエチル
アンモニウムｐ−トルエンスルホン酸0.4Mを溶
解させたアセトニトリル−Ｎ，Ｎ−ジメチルホル
ムアミド（95：５）溶剤中に白金メツシユ対向電
極と共に入れ、1.2Vで35分間電解重合を行つた。
ポリピロールが析出し、膜厚は2.2μｍに増加し
た。このフイルムは基板と良好に密着しており、
また、フイルム表面は電解重合前とほぼ同様非常
に光沢があつた。フイルムを基板から切出して構
造及び電気伝導度を調べたところ、PGMA／
PVCz層にポリピロールが混合した複合フイルム
上にPVDFが積層された構造をとつており、
PGMA／PVCz面とPVDF面の電気伝導度は
6.5／Ω・cm及び２×10-4／Ω・cmであつた。こ
の基板に付着した積層フイルムと実施例３の
PVDFのないフイルムをそれぞれ空気中に１週間
放置したところ、実施例３のフイルムは電気伝導
度が1/4に低下したのに対し、実施例４のフイル
ムでは10％程度しか低下しなかつた。これらは明
らかに表面をコーテイングしているPVDFが保護
膜として働いていることを示しており、導電性高
分子フイルムの安定性を積層構造にすることによ
り向上させることができた。Example 4 Similar to Example 3, on an n-type silicon substrate
PGMA was applied to a thickness of 0.2 μm, PVCz was applied to a thickness of 0.8 μm, and polyvinylidene fluoride (hereinafter abbreviated as PVDF) (molecular weight: 820,000) was further coated to a thickness of 0.6 μm. This substrate was placed together with a platinum mesh counter electrode in acetonitrile-N,N-dimethylformamide (95:5) solvent in which 1M pyrrole and 0.4M tetraethylammonium p-toluenesulfonic acid were dissolved, and electrolytic polymerization was carried out at 1.2V for 35 minutes. I went.
Polypyrrole precipitated and the film thickness increased to 2.2 μm. This film adheres well to the substrate,
Furthermore, the surface of the film was very shiny, almost the same as before electropolymerization. When we cut out the film from the substrate and examined its structure and electrical conductivity, we found that it was PGMA/
It has a structure in which PVDF is laminated on a composite film that is a mixture of PVCz layer and polypyrrole.
The electrical conductivity of the PGMA/PVCz surface and the PVDF surface is
They were 6.5/Ω·cm and 2×10 -4 /Ω·cm. The laminated film attached to this substrate and Example 3
When each of the films without PVDF was left in the air for one week, the electrical conductivity of the film of Example 3 decreased to 1/4, while that of the film of Example 4 decreased by only about 10%. These clearly indicate that the PVDF coating the surface acts as a protective film, and the stability of the conductive polymer film could be improved by creating a layered structure.
実施例 ５
ネサガラス基板上にノボラツク樹脂（分子量
8000）を0.2μｍ厚にコーテイングし、200℃で30
分間加熱した。この上にポリ−２−ビニルナフタ
レン（分子量18000）を1.1μｍ厚にコーテイング
した。この基板を３−メチルピロール1M、テト
ラエチルアンモニウムｐ−トルエンスルホン酸
0.4Mを加えた、アセトニトリル−水−エチレン
グリコール（98：１：１）溶液に浸漬し、1.4V
で20分間電解重合すると青黒色のポリ−３−メチ
ルピロールが析出した。得られたフイルムは基板
との密着性に優れ、導電性のポリ−３−メチルピ
ロールがフイルム全体に混合されたものであつ
た。このフイルムを基板からはがして電気伝導度
を測定すると0.5／Ω・cmであつた。Example 5 Novolac resin (molecular weight
8000) to a thickness of 0.2μm and heated at 200℃ for 30 minutes.
Heated for minutes. This was coated with poly-2-vinylnaphthalene (molecular weight 18,000) to a thickness of 1.1 μm. This substrate was mixed with 1M 3-methylpyrrole and tetraethylammonium p-toluenesulfonic acid.
Immersed in acetonitrile-water-ethylene glycol (98:1:1) solution with 0.4M added, 1.4V
After electrolytic polymerization for 20 minutes, blue-black poly-3-methylpyrrole was precipitated. The obtained film had excellent adhesion to the substrate, and conductive poly-3-methylpyrrole was mixed throughout the film. When this film was peeled off from the substrate and the electrical conductivity was measured, it was 0.5/Ω·cm.
以上説明したように本発明は絶縁性高分子フイ
ルムを塗布した電極基板上で、芳香族系化合物の
電解重合を行うことにより導電性高分子を作製す
る際に、絶縁性高分子フイルムとして１種の高分
子フイルムだけでなく、２種以上の高分子フイル
ムを積層する方法で、２種類の高分子が絶縁性で
電極表面が覆われても重合溶媒がフイルムをわず
かに膨潤させる条件を設定することにより電解重
合高分子のモノマーが絶縁性高分子中を拡散して
電極に達し、重合を開始し、その後、積層された
絶縁性高分子中に成長することにより複合フイル
ムを得ることができる。
As explained above, the present invention is a type of insulating polymer film that can be used when producing a conductive polymer by electrolytically polymerizing an aromatic compound on an electrode substrate coated with an insulating polymer film. This method involves laminating not only a polymer film but also two or more types of polymer films to create conditions that allow the polymerization solvent to swell the film slightly even if the two types of polymers are insulating and cover the electrode surface. As a result, the monomer of the electrolytically polymerized polymer diffuses through the insulating polymer, reaches the electrode, starts polymerization, and then grows into the laminated insulating polymer, thereby making it possible to obtain a composite film.
本発明方法によれば、従来導電性の材料中又は
上にしか複合することができなかつた電解重合高
分子を絶縁性高分子中に複合化できる特徴を有す
るため、電気伝導度を絶縁性から高導電性まで幅
広く制御することができる。 According to the method of the present invention, the electropolymerized polymer, which could only be composited in or on conductive materials, can be composited into insulating polymers. It can be controlled over a wide range up to high conductivity.
更に、本発明方法によれば、絶縁性高分子を２
層以上にしているため、構造を膜の厚み方向に制
御でき、密着力、均一性、安定性に優れた複合導
電性フイルムも得られるという格別顕著な効果が
奏せられる。 Furthermore, according to the method of the present invention, the insulating polymer is
Since it is made up of more than one layer, the structure can be controlled in the thickness direction of the film, and a particularly remarkable effect can be achieved in that a composite conductive film with excellent adhesion, uniformity, and stability can be obtained.
この導電性高分子フイルムは、電磁干渉防止フ
イルム、静電気・帯防止フイルム、感光体イメー
ジセンサ、太陽電池フイルム等に適用することが
できる。 This conductive polymer film can be applied to electromagnetic interference prevention films, static electricity/band prevention films, photoreceptor image sensors, solar cell films, and the like.
第１図は電極基板上に一層の絶縁性高分子フイ
ルムをコーテイングした場合の電解重合の工程
図、第２図は本発明に従つて電極基板上に２層の
絶縁性高分子フイルムをコーテイングした場合の
電解重合の工程図そして第３図は同じく本発明に
従つて電極基板上に３層の絶縁性高分子フイルム
を積層した場合の電解重合の工程図である。
１：電極基板、２：絶縁性高分子フイルム、
３：芳香族系高分子材料が混入した導電性フイル
ム、４：芳香族系高分子材料のみのフイルム、
５：１層目の絶縁性高分子フイルム、６：２層目
の絶縁性高分子フイルム、７：芳香族系高分子材
料が混入した１層目の絶縁性高分子フイルム、
８：芳香族系高分子材料が混入した２層目の絶縁
性高分子フイルム、９：３層目の絶縁性高分子フ
イルム。
Figure 1 is a process diagram of electrolytic polymerization in which one layer of insulating polymer film is coated on an electrode substrate, and Figure 2 is a process diagram of electrolytic polymerization in which two layers of insulating polymer film are coated on an electrode substrate according to the present invention. FIG. 3 is a process diagram of electrolytic polymerization in the case where three layers of insulating polymer films are laminated on an electrode substrate according to the present invention. 1: Electrode substrate, 2: Insulating polymer film,
3: Conductive film mixed with aromatic polymer material, 4: Film containing only aromatic polymer material,
5: first layer insulating polymer film, 6: second layer insulating polymer film, 7: first layer insulating polymer film mixed with aromatic polymer material,
8: Second layer insulating polymer film mixed with aromatic polymer material, 9: Third layer insulating polymer film.
Claims (1)
子フイルムと、該基板上に電解酸化により電気化
学的に形成した芳香族系高分子材料とから成るこ
とを特徴とする複合導電性高分子フイルム。 ２ 積層した２種以上の絶縁性高分子フイルム
と、電解酸化により電気化学的に形成した芳香族
系高分子材料とから成ることを特徴とする複合導
電性高分子フイルム。 ３ 電極基板上に絶縁性高分子フイルムを２種以
上積層する工程、及びその上に電解酸化により芳
香族系高分子材料を電気化学的に形成する工程の
各工程を包含することを特徴とする複合導電性高
分子フイルムの製造方法。[Claims] 1. A method comprising two or more types of insulating polymer films laminated on an electrode substrate, and an aromatic polymer material electrochemically formed on the substrate by electrolytic oxidation. Composite conductive polymer film. 2. A composite conductive polymer film comprising two or more laminated insulating polymer films and an aromatic polymer material electrochemically formed by electrolytic oxidation. 3. It is characterized by including the steps of laminating two or more types of insulating polymer films on an electrode substrate, and electrochemically forming an aromatic polymer material thereon by electrolytic oxidation. A method for producing a composite conductive polymer film.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58213204A JPS60107214A (en) | 1983-11-15 | 1983-11-15 | Composite conductive polymer film and method of producing same |
| US06/657,314 US4559112A (en) | 1983-10-07 | 1984-10-02 | Electrically conducting polymer film and method of manufacturing the same |
| DE8787106076T DE3484598D1 (en) | 1983-10-07 | 1984-10-04 | ELECTRICALLY CONDUCTIVE POLYMER AND THEIR PRODUCTION. |
| CA000464743A CA1231670A (en) | 1983-10-07 | 1984-10-04 | Electrically conducting polymer film and method of manufacturing the same |
| EP19870106076 EP0247366B1 (en) | 1983-10-07 | 1984-10-04 | Electrically conducting polymer film and method of manufacturing the same |
| EP19840306764 EP0144127B1 (en) | 1983-10-07 | 1984-10-04 | Electrically conducting polymer film and method of manufacturing the same |
| DE8484306764T DE3481849D1 (en) | 1983-10-07 | 1984-10-04 | ELECTRICALLY CONDUCTIVE POLYMERS AND THEIR PRODUCTION. |
| KR1019840006200A KR890004938B1 (en) | 1983-10-07 | 1984-10-06 | Electrically conduction polymer film and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58213204A JPS60107214A (en) | 1983-11-15 | 1983-11-15 | Composite conductive polymer film and method of producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60107214A JPS60107214A (en) | 1985-06-12 |
| JPH056285B2 true JPH056285B2 (en) | 1993-01-26 |
Family
ID=16635256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58213204A Granted JPS60107214A (en) | 1983-10-07 | 1983-11-15 | Composite conductive polymer film and method of producing same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60107214A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01289013A (en) * | 1988-05-16 | 1989-11-21 | Nippon Telegr & Teleph Corp <Ntt> | Manufacture of organic functioning film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5889636A (en) * | 1981-11-24 | 1983-05-28 | Achilles Corp | Agricultural flexible vinyl chloride-based film |
-
1983
- 1983-11-15 JP JP58213204A patent/JPS60107214A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5889636A (en) * | 1981-11-24 | 1983-05-28 | Achilles Corp | Agricultural flexible vinyl chloride-based film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60107214A (en) | 1985-06-12 |
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