JPS62214199A - Production of composite body having surface electric conductivity - Google Patents
Production of composite body having surface electric conductivityInfo
- Publication number
- JPS62214199A JPS62214199A JP61055111A JP5511186A JPS62214199A JP S62214199 A JPS62214199 A JP S62214199A JP 61055111 A JP61055111 A JP 61055111A JP 5511186 A JP5511186 A JP 5511186A JP S62214199 A JPS62214199 A JP S62214199A
- Authority
- JP
- Japan
- Prior art keywords
- base material
- conductive
- film
- electrical conductivity
- polymerization
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000463 material Substances 0.000 claims abstract description 63
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 33
- 229920001940 conductive polymer Polymers 0.000 claims description 28
- 239000004020 conductor Substances 0.000 claims description 12
- 239000002585 base Substances 0.000 description 44
- 238000000034 method Methods 0.000 description 28
- -1 quality Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920000128 polypyrrole Polymers 0.000 description 5
- 229920000123 polythiophene Polymers 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 2
- 229920006332 epoxy adhesive Polymers 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000005289 physical deposition Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000175448 Citrus madurensis Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000017317 Fortunella Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- ZRZKFGDGIPLXIB-UHFFFAOYSA-N fluoroform;sulfuric acid Chemical compound FC(F)F.OS(O)(=O)=O ZRZKFGDGIPLXIB-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 125000005059 halophenyl group Chemical group 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000015 polydiacetylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical class CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、基材の表面に、該基材よシ高い電気伝導度を
有する電導性高分子化合物の被膜を電解重合により形成
させた、表面導電性を有する複合体の製造方法に関する
ものである。[Detailed Description of the Invention] [Industrial Field of Application] The present invention provides a method of forming a coating of a conductive polymer compound having higher electrical conductivity than the base material on the surface of the base material by electrolytic polymerization. The present invention relates to a method for producing a composite having surface conductivity.
従来、電気伝導度の低い基材に導電性を付与する方法と
しては、導電性を付与したい基材の中に該基材より電気
伝導度の高い導電物質を分散させる体積的な方法と、基
材の表面に該基材より電気伝導度の高い導電層を積層す
る表面的な方法とが知られている。Conventionally, methods for imparting conductivity to a base material with low electrical conductivity include a volumetric method in which a conductive substance having a higher electrical conductivity than that of the base material is dispersed into the base material to be imparted with conductivity; A superficial method is known in which a conductive layer having higher electrical conductivity than the base material is laminated on the surface of the material.
しかし、前者の方法では成形後の基材を導電化する場合
には、ｍｉｇｒａｔｉｏｎ等により基材中に導電物質が
入り込んで行かねばならず、従って導電物、質も導電性
を付与したい基材も特定の組合せに制限されるばかりで
はなく、導電化後の電気伝導度をあまり高くできないと
いう欠点があった。However, in the former method, when making the base material conductive after molding, the conductive substance must enter the base material by migration etc. Therefore, the conductive substance, quality, and base material to which conductivity is to be imparted must be mixed. There is a drawback that not only is the combination limited to a specific one, but also that the electrical conductivity after conductivity cannot be made very high.
一方、後者の方法の中には、気相中で導電層を析出させ
る物理的な堆積法として、真空蒸着法、スノｆツタリン
グ法、イオンシレーティング法などがあり、化学的な堆
積法としては化学反応法と熱分解法があり、その他にス
プレー法、メッキ法、コーティング法、ラミネート法な
どが知られている。しかしながら、これらの方法は、基
材の種類、特性、形状、或いは導電物質の種類などによ
る制限があり、各々欠点があった。On the other hand, among the latter methods, there are physical deposition methods for depositing a conductive layer in a gas phase, such as vacuum evaporation, snowfalling, and ion silating, while chemical deposition methods include There are chemical reaction methods and thermal decomposition methods, and other well-known methods include spray methods, plating methods, coating methods, and laminating methods. However, these methods have limitations due to the type, characteristics, shape of the base material, type of conductive material, etc., and each has drawbacks.
例えば真空蒸着法、スパッタリング法では、多くの場合
、基材との付着性が悪い。イオンブレーティング法では
基材の温度が上がりゃすぐ、基材として使えるものに制
限がある。また、これらの物理的な堆積法は、これらを
行うための設備投資が大きい・さらに、一般に導電物質
として金属やその他の無機物質を用いているため、導電
層の可撓性が少なく、しなやかさに欠けていて、基材上
に積層した後で基材を変形する場合などの時に導電層が
剥離することが多かった。For example, in vacuum evaporation methods and sputtering methods, adhesion to the substrate is often poor. In the ion blating method, once the temperature of the substrate rises, there are limits to what can be used as the substrate. In addition, these physical deposition methods require a large investment in equipment.Furthermore, since metals or other inorganic materials are generally used as conductive materials, the conductive layer has less flexibility and is less flexible. The conductive layer often peeled off when the base material was deformed after being laminated on the base material.
化学的な堆積法を用いた場合は、導電層が不均一になシ
表面の電気伝導度も不均一になることが多く、また電気
伝導度自身あまり高くできないという欠点があった。When a chemical deposition method is used, the conductive layer is often non-uniform and the electrical conductivity of the surface is also non-uniform, and the electrical conductivity itself cannot be very high.
スプレー法では基材表面に導電物質を直接吹きつけるの
で付着性が悪い。また基材の形状によっては導電化でき
ない部分がでてくる。メッキ法は、基材の電気伝導度が
低い場合は無電解メッキを用いなければならないのでラ
ンニングコストカ高い。In the spray method, the conductive material is directly sprayed onto the surface of the base material, resulting in poor adhesion. Furthermore, depending on the shape of the base material, there may be some parts that cannot be made conductive. In the plating method, running costs are high because electroless plating must be used if the electrical conductivity of the base material is low.
コーティング法では導電層を形成する液を基材表面に塗
工するため、導電層の粘度、基材の形状などによる制限
があり、付着性も劣る。ラミネート法は単に導電シート
を基材に貼り合わせるだけのものなので、付着性が悪く
、また基材の形状が複雑な場合などは表面の導電化はで
きなくなる。これらもまた導電層の可撓性が少なく、し
なやかさに欠けている場合が多く、基材上に積層した後
で基材を変形する場合などの時に導電層が剥離すること
が多かった。In the coating method, the liquid forming the conductive layer is applied to the surface of the base material, so there are limitations due to the viscosity of the conductive layer, the shape of the base material, etc., and the adhesion is also poor. Since the lamination method simply attaches a conductive sheet to a base material, the adhesion is poor, and if the shape of the base material is complex, it may not be possible to make the surface conductive. These conductive layers also often have low flexibility and lack pliability, and the conductive layer often peels off when the base material is deformed after being laminated on the base material.
本発明の目的は、上述した従来技術の問題点を解決し、
基材の種類、特性、形状にかかわらず、基材上に該基材
よシミ気侭導度が高く、均一でしかも可撓性の良いしな
やかな電導性高分子化合物の被膜を付着性よく形成し、
基材の導電化を可能とし、さらに製造コストの低い、表
面導電性を有する複合体の製造方法を提供することにあ
る。The purpose of the present invention is to solve the above-mentioned problems of the prior art,
Regardless of the type, characteristics, or shape of the substrate, it is possible to form a uniform, flexible, and pliable film of a conductive polymer compound on the substrate with high stain resistance and good adhesion. ,
It is an object of the present invention to provide a method for producing a composite having surface conductivity, which enables a base material to be electrically conductive and which is inexpensive to produce.
本発明に従えば、基材表面上に、該基材より高い電気伝
導度を有する電導性高分子化合物の被膜を形成させる表
面導電性を有する複合体の製造方法において、電導性高
分子化合物の被膜を上記基材表面上の一部に設けた、基
材よ□り高い電気伝導度を有する導電材料を重合の開始
点として電解重合を実施することにより、上記基材表面
に析出・成長させることを特徴とする表面導電性を有す
る複合体の製造方法が提供される。According to the present invention, in the method for producing a composite having surface conductivity, in which a film of a conductive polymer compound having higher electrical conductivity than the base material is formed on the surface of the base material, A coating is provided on a part of the surface of the base material, and electrolytic polymerization is performed using a conductive material having higher electrical conductivity than the base material as a starting point for polymerization, so that it is deposited and grown on the surface of the base material. A method for producing a composite having surface conductivity is provided.
本発明方法において、基材表面に電解重合法によって析
出・成長させて導電性被膜とするために用いられる電導
性高分子化合物とは、π電子共役系を有する高分子化合
物のことであり、基材よす電気伝導度が高く、電気伝導
度が１０−８８／Ｉｎ以上の値を有するもの、さらに好
ましくは電気伝導度が１０ Ｓ／ｃＩｎ以上の値を有
するものが望ましい。このような電導性高分子層金物の
代表例としては、ポリアセチレン、ポリパラフェニレン
、ポリピロール、ポリチオフェン、ポリシアノアセチレ
ン、′ポリイソチアナフテン、ポリジアセチレン、ポリ
アニリン、ポリフタロシアニン及びこれらのポリマーを
構成するモノマーの誘導体の重合体等をあげることかで
きる。これらの電導性高分子化合物のうち、好ましい電
導性高分子化合物としては、ポリチオフェン、ポリイン
チアナフテン、ポリピロールをあげることができ、さら
に好ましくはポリチオフェンをあげることができる。In the method of the present invention, the conductive polymer compound used to form a conductive film by depositing and growing on the surface of a substrate by electrolytic polymerization is a polymer compound having a π-electron conjugated system, and is a base material. It is desirable that the material has a high electrical conductivity of 10-88/In or more, more preferably 10 S/cIn or more. Typical examples of such conductive polymer layer metals include polyacetylene, polyparaphenylene, polypyrrole, polythiophene, polycyanoacetylene, polyisothianaphthene, polydiacetylene, polyaniline, polyphthalocyanine, and monomers constituting these polymers. Examples include polymers of derivatives of Among these conductive polymer compounds, preferred conductive polymer compounds include polythiophene, polyinthianaphthene, and polypyrrole, and more preferably polythiophene.
上記の電導性高分子化合物の中には、中性の状態で１０
Ｓ／ｃＩｎ以上の電気伝導度を有するものもあれば、電
子供与性あるいは電子吸引性のドーパントをド−グする
ことによって１Ｏ−８ｓ／ｃｆｎ以上の電気伝導度を有
するものもあり、いずれも導電性被膜を与える電導性高
分子化合物として用いることができる。また、ドーピン
グによって、或いは中性の状態でも１０−’Ｓ／ｃ１ｎ
以上の電気伝導度を発現するものはさらに好ましい導電
性被膜を与える電導性高分子化合物として用いることが
できる。Some of the above conductive polymer compounds contain 10
Some have electrical conductivity of S/cIn or higher, while others have electrical conductivity of 1O-8s/cfn or higher by doping with electron-donating or electron-withdrawing dopants. It can be used as a conductive polymer compound that provides a conductive film. In addition, by doping or even in a neutral state, 10-'S/c1n
Those exhibiting the above electrical conductivity can be used as conductive polymer compounds that provide more preferable conductive coatings.
電解重合法では、該電導性高分子化合物の析出と同時に
、使用した電解電位に対応したドーピングが生じるのが
普通であり、このような場合には製膜と同時に電気化学
的なドーーングが行われることになる。この電導性高分
子化合物から、電解重合時にドーピングされたドーパン
トを脱ドープして中性にすることも可能である。また、
脱ドープして中性化した電導性高分子化合物、あるいは
電解重合時にドーピングされない中性の電導性高分子化
合物を、さらに適当なドーパントでドーピングすること
も可能である。この場合、ドーピングは化学的ドーピン
グ、電気化学的ドーピングのいずれの方法を採用しても
よい。以上のように電解重合法で得られる電導性高分子
化合物は種々なドーピング状態を取りうるが、いずれの
場合にも導電性被膜として用いることができる。またこ
れら種々外ドーピング状態を取りうろことによって、導
電性被膜作製後も例えば化学的ドーピングによる後ドー
ピングなどを用いて、導電性被膜の電気伝導度を変化さ
せることも可能である。In the electrolytic polymerization method, doping corresponding to the electrolytic potential used usually occurs at the same time as the deposition of the conductive polymer compound, and in such cases, electrochemical doping is performed at the same time as film formation. It turns out. It is also possible to make the conductive polymer compound neutral by dedoping the dopant doped during electrolytic polymerization. Also,
It is also possible to further dope a conductive polymer compound that has been neutralized by dedoping or a neutral conductive polymer compound that is not doped during electrolytic polymerization with a suitable dopant. In this case, doping may be done by either chemical doping or electrochemical doping. As described above, the conductive polymer compound obtained by the electrolytic polymerization method can have various doping states, and in any case, it can be used as a conductive film. Further, by changing these various external doping states, it is also possible to change the electrical conductivity of the conductive film even after the conductive film has been formed by using, for example, post-doping using chemical doping.
電気化学的にドーピングするドー・ぐントとしては、（
Ｉ） ＰＦ６−１ＳｂＦ６−１Ａ ｓ Ｆ 、ｓ、５ｂ
Ｃ１６−””きＶａ族の元素のハロゲン化物アニオン、
ＢＦ４−の如き１ｌｌａ族の元素のノ・ロケ゛ン化物ア
ニオｙ、 Ｔ−（Ｉ３−）、Ｂｒ−１ｃｔ、−の如きハ
ロダンアニオン、Ｃ４０４−の如き過塩素酸アニオン等
の陰イオン・ドーパント及び（１）Ｌｉ＋、Ｎａ＋、Ｋ
＋、Ｒｂ＋、Ｃｓ’−の如きアルカリ金属イオン、一般
式Ｒ，ｘＭＨ！またはＲ３Ｍ１（式中、ＲハＣ１カラＣ
１ｏのアルキル基、フェニル、ハロフェニル、アルキル
フェニル等のアリール基、ＭはＮ 、 Ｐ 、 Ａｓ
、 Ｍｌは０又はＳ、ｘはＯ又は１を表す。）で示され
るテトラアルキルアンモニウムイオン、テトラアルキル
ホスホニウムイオン、テトラアルキルアルソニウムイオ
ン、トリアルキルオキソニウム、トリアルキルスルホニ
ウムイオン等の陽イオン・ドーパント等をあげることが
できる。一方、化学的にドーピングするドーＡ？ントと
しては、従来から知られている種々の電子受容性化合物
及び電子供与性化合物、例えば、（１）沃素、臭素及び
沃化臭素の如きハロダン、（ＩＩ）丘部化砒素、丘部化
アンチモン、四弗化珪素、五塩化燐、丘部比隣、塩化ア
ルミニウム、臭化アルミニウム及び弗化アルミニウムの
如き金属ハロゲン化物、（２）硫酸、硝酸、フルオロ硫
酸、トリフルオロメタン硫酸及びクロロ硫酸の如きプロ
トン酸、■三酸化硫黄、二酸化窒素、ジフルオロスルホ
ニルパーオキシドの如き酸化剤、（Ｖ） Ａｇｃｚｏ４
． （Ｖｆｌテトラシアノエチレン、テトラシアノキノ
ジメタン、クロラニール、２．３−ジクロル−５，６−
ジシアツバラペンソキノン、２．３−ジブロム−５，６
−ジシアツパラペンゾキノン、（ロ）Ｌｔ 、Ｎａ 、
にの如きアリカリ金属等を用いることができるが、必ず
しもこれらに限定されるものではない。For electrochemical doping, do-gundt (
I) PF6-1SbF6-1A s F , s, 5b
C16-halide anion of a group Va element,
Anionic dopants such as chloride anions of elements of the 1lla group such as BF4-, halodane anions such as T-(I3-), Br-1ct, -, perchlorate anions such as C404-, and ( 1) Li+, Na+, K
+, Rb+, Cs'- alkali metal ions, general formula R, xMH! or R3M1 (in the formula, R H C1 Kara C
1o alkyl group, aryl group such as phenyl, halophenyl, alkylphenyl, M is N, P, As
, Ml represents 0 or S, x represents O or 1. ), cations and dopants such as tetraalkylammonium ion, tetraalkylphosphonium ion, tetraalkylarsonium ion, trialkyloxonium, and trialkylsulfonium ion can be mentioned. On the other hand, chemical doping DoA? Examples of the compounds include various conventionally known electron-accepting compounds and electron-donating compounds, such as (1) halodane such as iodine, bromine, and bromine iodide; (II) arsenic oxides and antimony oxides; (2) protons such as sulfuric acid, nitric acid, fluorosulfuric acid, trifluoromethanesulfuric acid and chlorosulfuric acid; acid, ■ oxidizing agent such as sulfur trioxide, nitrogen dioxide, difluorosulfonyl peroxide, (V) Agczo4
．． (Vfl tetracyanoethylene, tetracyanoquinodimethane, chloranil, 2,3-dichloro-5,6-
Dicyatsubara pensoquinone, 2,3-dibrome-5,6
- dithiazparabenzoquinone, (b) Lt, Na,
Alkali metals such as silver can be used, but are not necessarily limited to these.
本発明において用いられる基材は、電導性高分子化合物
の被膜の電気伝導度より低い電気伝導度を有し、かつ重
合に用いる電解液に安定であれば、その種類、特性、形
状には特に制限はなく、例えばガラス板、シリコンウェ
ハー、ポリフッ化ビニリデン、ポリ、テトラフルオロ、
エチレン、ポリクロロトリフルオロエ≠レン、ポリ塩化
ビニル、ポリエチレンテレフタレート等の熱可塑性樹脂
が好適に使用することができる。The base material used in the present invention has an electrical conductivity lower than that of the conductive polymer film, and is stable in the electrolyte used for polymerization. There are no limitations, such as glass plates, silicon wafers, polyvinylidene fluoride, poly, tetrafluoro,
Thermoplastic resins such as ethylene, polychlorotrifluoroethylene, polyvinyl chloride, and polyethylene terephthalate can be suitably used.
基材表面上の一部に重合の開始点として設ける導電材料
は、基材よシ高い電気伝導度を有するものであればいず
れでもよく、例えば１Ｏ−３Ｓ／ｚ以上の電気伝導度を
有するものが好１しく、代表的にはポリエステルフィル
ムの上に金属を蒸着した導電フィルムを好適に使用する
ことができる。重合の開始点として基材表面上に導電材
料を設ける位置には特に制限はなく、任意の場所でよい
が、特に好ましくは基材の外周部に設けることができる
。また必要とされる導電材料の面積は、電導性高分子化
合物の被膜を与える重合用モノマーの種類によって異な
るので一部には決められないが、一般には基材の全表面
積に対して０．００１ ％〜５０チ、好ましくは１チ〜
２０チの範囲である。The conductive material provided as a polymerization initiation point on a part of the surface of the base material may be any material as long as it has a higher electrical conductivity than the base material, for example, one having an electrical conductivity of 1O-3S/z or higher. is preferable, and typically a conductive film in which metal is vapor-deposited on a polyester film can be suitably used. There is no particular restriction on the position where the conductive material is provided on the surface of the base material as a starting point for polymerization, and it may be provided at any location, but it is particularly preferably provided on the outer periphery of the base material. The area of the conductive material required cannot be determined in part because it varies depending on the type of polymerization monomer that provides the coating of the conductive polymer, but it is generally 0.001% of the total surface area of the base material. %~50 inches, preferably 1 inch~
It is in the range of 20 inches.
基材表面上の一部に導電材料を設ける方法には特に制限
はなく、例えば導電フィルムを適当な形状や面積に切断
し、基材表面上に接着剤例えばエポキシ系接着剤等を用
いて張り合わせ接着することによって設けることができ
る。基材表面に重合の開始点が存在しない場合は、重合
反応が全く進行しないか（基材が絶縁体の場合）、また
は重合反応が行表われても反応が円滑に進行せず、性能
の良好な複合体が得られない。There are no particular restrictions on the method of providing a conductive material on a part of the surface of the base material; for example, a conductive film may be cut into an appropriate shape or area, and then laminated onto the surface of the base material using an adhesive such as an epoxy adhesive. It can be provided by gluing. If there is no starting point for polymerization on the surface of the substrate, the polymerization reaction will not proceed at all (if the substrate is an insulator), or even if the polymerization reaction does occur, it will not proceed smoothly and performance may deteriorate. A good composite cannot be obtained.
本発明における電解重合とは、例えば前記電導性高分子
化合物の被膜を与える重合用モノマーを含む電解液を電
解して、モノマーの酸化重合を行う方法のことであり、
各種重合用モノマーに対し、公知の適切な重合条件を選
ぶことによって行うことができる。これまでに知られて
いる電解重合法では、陽極として、例えば金、白金など
の金属材料が使用されているが、本発明においては、電
解液に対して安定な物質ならば、その種類、特性、形状
にかかわらず、電導性高分子化合物の被膜より電気伝導
度の低い基材を用いることができ、その表面上の一部に
導電材料を重合の開始点として設けて陽極として使用す
る。この導電材料を重合の開始点として、重合反応は円
滑に副反応もなく速やかに進行し、電導性高分子化合物
の被膜が基材表面を覆うように、しかも均一な厚みで基
材との付着性良く成長して行き、これが導電性被膜とし
て基板上に積層される。Electrolytic polymerization in the present invention refers to a method of performing oxidative polymerization of monomers by electrolyzing an electrolytic solution containing a polymerization monomer that provides a film of the conductive polymer compound, for example,
This can be carried out by selecting appropriate known polymerization conditions for various polymerization monomers. In the electrolytic polymerization methods known so far, metal materials such as gold and platinum are used as the anode, but in the present invention, as long as the material is stable against the electrolyte, its type and characteristics can be used. Regardless of the shape, a base material having lower electrical conductivity than the film of the conductive polymer compound can be used, and a conductive material is provided on a portion of the surface thereof as a polymerization initiation point to be used as an anode. With this conductive material as the starting point for polymerization, the polymerization reaction proceeds smoothly and quickly without any side reactions, and the film of the conductive polymer compound adheres to the base material with a uniform thickness and covers the surface of the base material. It grows smoothly and is laminated on the substrate as a conductive film.
電解重合の重合温度には特に限定はないが、一般には一
６０℃から８０℃、好ましくは一２０℃から３０℃の間
の温度で実施する。重合時間は、導電性被膜の析出・成
長程度を観察判断することにより適宜選定されるが、一
般には数分〜数時間程度である。重合圧力には特に限定
はないが、一般には常圧で重合操作を実施する。The polymerization temperature for electrolytic polymerization is not particularly limited, but it is generally carried out at a temperature between -60°C and 80°C, preferably between -20°C and 30°C. The polymerization time is appropriately selected by observing and judging the degree of precipitation and growth of the conductive film, but is generally about several minutes to several hours. Although there is no particular limitation on the polymerization pressure, the polymerization operation is generally carried out at normal pressure.
本発明の方法によって製造される表面導電性を有する複
合体は、従来の金属材料や無機化合物を表面導電材料と
して用いた製品に比較して、以下のような利点を有して
いる・
■ 有機物である電導性高分子化合物を導電性被膜とし
て用いており、その電導性高分子化合物は互いに絡みあ
った３次元構造をしているので、可撓性がよくしなやか
である。従って、導電性被膜を積層した後でもこの材料
の加工性が良く、また加工操作によって基材から導電性
被膜が剥離することがない。Composites with surface conductivity produced by the method of the present invention have the following advantages compared to products using conventional metal materials or inorganic compounds as surface conductive materials. A conductive polymer compound is used as the conductive coating, and since the conductive polymer compound has a three-dimensional structure in which the conductive polymer compounds are intertwined with each other, it is highly flexible and pliable. Therefore, even after laminating the conductive film, the material has good workability, and the conductive film does not peel off from the base material during processing operations.
■ 電解重合時に、基材ヘアンカーを打ち込む様に重合
するので、導電性被膜と基材との付着性が良い。■During electrolytic polymerization, polymerization occurs as if a hair anchor is driven into the base material, resulting in good adhesion between the conductive coating and the base material.
■ 電導性高分子化合物はドーピング、脱ドーピング操
作によって電気伝導度を変更することができる。従って
、導電性被膜を積層した後でも、複合体の表面の電気伝
導度を自由に変えることができる。■ The electrical conductivity of conductive polymer compounds can be changed by doping and dedoping operations. Therefore, even after laminating the conductive film, the electrical conductivity of the surface of the composite can be freely changed.
■ 電導性高分子化合物は、多くの場合高温まで安定で
あるので、耐熱性がよい。■ Conductive polymer compounds are stable up to high temperatures in most cases, so they have good heat resistance.
また、本発明による導電化方法は、従来公知の導電化方
法に比較して、以下のような利点を有している。Furthermore, the conductivity method according to the present invention has the following advantages over conventionally known conductivity methods.
■ 電解液に対して安定である限り、基材となる物質の
種類、特性、形状にかかわらず、同様の方法で導電化で
きる。■ As long as it is stable to the electrolyte, it can be made conductive using the same method regardless of the type, characteristics, or shape of the base material.
■ 電導性高分子化合物は分子デザインやモロフォロジ
ーの変更が可能であるので、導電化の目的に応じて最適
のものを選び、容易に同様の設備、方法で導電化するこ
とができる。■ Since the molecular design and morphology of conductive polymer compounds can be changed, it is possible to select the most suitable one depending on the purpose of conductivity, and easily make it conductive using similar equipment and methods.
■ 基材の表面全体を同時に導電化することができる。■ The entire surface of the base material can be made conductive at the same time.
■ 導電化するための設備コスト、ランニング・コスト
が低い。■ Equipment costs and running costs for making it conductive are low.
以下、実施例をあげて本発明を更に詳細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例に
軸延伸ポリエステルフィルム上に金を蒸着して作製した
電気伝導度が約１０Ｓ／ｃｒｎの導電フィルムを幅１岨
程度に切断し、４０Ｉ＋＋＋＋＋×４５１１ＩＩ＋ｌＸ
１ｆＷｎのサイズで電気伝導度が１０ Ｓ／１Ｍ以下
のガラス板の外周部にエポキシ系接着剤を用いて張シ合
わせた。In the example, a conductive film with an electrical conductivity of about 10 S/crn, which was prepared by vapor-depositing gold on an axially stretched polyester film, was cut into a width of about 1 m, and the film was 40I + + + + + × 4511 II + lX.
The outer periphery of a glass plate having a size of 1 fWn and an electrical conductivity of 10 S/1 M or less was bonded using an epoxy adhesive.
この時ガラス板の面積は６ｃｍ 、導電フィルムの面積
は全体に対して１７チであった。このガラス板と導電フ
ィルムとを陽極として使用し、白金板を陰極として使用
して、０．１モル／ｌのチオフェンと０．０５モル／ｌ
のＬ ＊ ＢＦ ４とを含むベンゾニトリル溶液にアル
ゴンガス雰囲気中、常準常圧で４〜５ Ｖ 、 ２ ｍ
Ａ／／ｃＩｎの電流を２時間流し、チオフェンを電気化
学的に重合して前記陽極板上に均一なプリチオフェンフ
ィルムを析出させた。このポリチオフェンフィルムの電
気伝導度は２０Ｓ／ｃｒｎであった。得られた複合体は
、ガラス板とポリチオフェンフィルムとの付着性にすぐ
れていた。At this time, the area of the glass plate was 6 cm, and the area of the conductive film was 17 cm. Using this glass plate and the conductive film as an anode and the platinum plate as a cathode, 0.1 mol/l of thiophene and 0.05 mol/l
A benzonitrile solution containing L*BF4 was heated at 4 to 5 V and 2 m at normal atmospheric pressure in an argon gas atmosphere.
A current of A//cIn was applied for 2 hours to electrochemically polymerize thiophene and deposit a uniform prethiophene film on the anode plate. The electrical conductivity of this polythiophene film was 20 S/crn. The obtained composite had excellent adhesion between the glass plate and the polythiophene film.
実施例２
基材として、表面を凹凸に加工した電気伝導度が１０Ｓ
／ｃｒｎのポリエチレンテレフタレート板を用いた他は
実施例１と同様にして陽極を作製し、炭素板を陰極とし
て使用して、０．１５モル／ｌの１．３−イソチアナフ
テンと０．１モル／ｌのテトラフェニルフォスフオニウ
ムクロライド（！： ”ｆ 含ｔｒアセトニトリル溶液
にアルゴンガス雰囲気中、常温常圧で２ｖ、０．５〜１
ｍＡ／ ｃｍ の電流を２時間流し、１，３−イソ
チアナフテンを電気化学的に重合して陽極板上に、凹凸
表面にそって均一なポリ（１，３−インチアナフテン）
フィルムを析出させた。このポリ（１，３−イソチアナ
フテン）フィルムの電気伝導度は１０Ｓ／ｃＩｎであっ
た。得られた複合体は、ポリエチレンテレフタレート板
とポリ（１，３−イソチアナフテン）フィルムとの付着
性が良好であった。Example 2 A base material with an electrical conductivity of 10S with an uneven surface
An anode was prepared in the same manner as in Example 1, except that a polyethylene terephthalate plate of /crn was used, and a carbon plate was used as a cathode, and 0.15 mol/l of 1.3-isothianaphthene and 0.1 mol/l of tetraphenylphosphonium chloride (!: "f) in a tr-containing acetonitrile solution in an argon gas atmosphere at room temperature and normal pressure at 2v, 0.5-1
A current of mA/cm was applied for 2 hours to electrochemically polymerize 1,3-isothianaphthene to form a uniform poly(1,3-inch-anaphthene) on the anode plate along the uneven surface.
A film was deposited. The electrical conductivity of this poly(1,3-isothianaphthene) film was 10 S/cIn. The obtained composite had good adhesion between the polyethylene terephthalate plate and the poly(1,3-isothianaphthene) film.
実施例３
基材として、表面に微細加工をほとこした電気伝導度が
１ＯＳ／２＋＋＋のシリコンウェハー金柑いた他は実施
例１と同様にして陽極を作製し、白金板を陰極として使
用して、０．１モル／ｌのピロールと０．０５モル／ｌ
のｐ−）ルエンスルホン酸のトリーｎ−ブチルアンモニ
ウム塩とを含むアセトニトリル溶液にアルゴンガス雰囲
気中、常温常圧で３〜４ Ｖ 、 １ ｍＡ／ｚの電流
を２時間流し、ピロールを電気化学的に重合して陽極板
上にポリピロールフィルムを析出させた。このポリピロ
ールフィルムの電気伝導度は５０Ｓ／ｃｔｎであった。Example 3 An anode was prepared in the same manner as in Example 1, except that a silicon wafer kumquat with a finely processed surface and an electrical conductivity of 1OS/2+++ was used as a base material, and a platinum plate was used as a cathode. 0.1 mol/l pyrrole and 0.05 mol/l
A current of 3 to 4 V and 1 mA/z was applied for 2 hours at room temperature and pressure in an argon gas atmosphere to an acetonitrile solution containing tri-n-butylammonium salt of p-)luenesulfonic acid to electrochemically remove pyrrole. Polypyrrole film was deposited on the anode plate. The electrical conductivity of this polypyrrole film was 50 S/ctn.
得られた複合体ハ、シリコンウェハーとポリピロールフ
ィルムとの付着性が良好であった。The resulting composite exhibited good adhesion between the silicon wafer and the polypyrrole film.
Claims (1)
性高分子化合物の被膜を形成させる表面導電性を有する
複合体の製造方法において、電導性高分子化合物の被膜
を上記基材表面上の一部に設けた、基材より高い電気伝
導度を有する導電材料を重合の開始点として電解重合を
実施することにより、上記基材表面に析出・成長させる
ことを特徴とする表面導電性を有する複合体の製造方法
。In a method for producing a composite having surface conductivity, in which a film of a conductive polymer compound having a higher electrical conductivity than the base material is formed on the surface of the base material, a film of the conductive polymer compound is formed on the surface of the base material. Surface conductivity characterized by depositing and growing on the surface of the base material by performing electrolytic polymerization using a conductive material provided on a part of the top and having a higher electrical conductivity than the base material as a starting point for polymerization. A method for producing a composite having the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61055111A JPH0660438B2 (en) | 1986-03-14 | 1986-03-14 | Method for producing composite having surface conductivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61055111A JPH0660438B2 (en) | 1986-03-14 | 1986-03-14 | Method for producing composite having surface conductivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62214199A true JPS62214199A (en) | 1987-09-19 |
| JPH0660438B2 JPH0660438B2 (en) | 1994-08-10 |
Family
ID=12989639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61055111A Expired - Lifetime JPH0660438B2 (en) | 1986-03-14 | 1986-03-14 | Method for producing composite having surface conductivity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0660438B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS624898A (en) * | 1985-07-01 | 1987-01-10 | Agency Of Ind Science & Technol | Production of electrically conductive polymer film containing particle |
-
1986
- 1986-03-14 JP JP61055111A patent/JPH0660438B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS624898A (en) * | 1985-07-01 | 1987-01-10 | Agency Of Ind Science & Technol | Production of electrically conductive polymer film containing particle |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0660438B2 (en) | 1994-08-10 |
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