JPH0727732B2 - Method for making surface of resin molded body conductive - Google Patents
Method for making surface of resin molded body conductiveInfo
- Publication number
- JPH0727732B2 JPH0727732B2 JP60275053A JP27505385A JPH0727732B2 JP H0727732 B2 JPH0727732 B2 JP H0727732B2 JP 60275053 A JP60275053 A JP 60275053A JP 27505385 A JP27505385 A JP 27505385A JP H0727732 B2 JPH0727732 B2 JP H0727732B2
- Authority
- JP
- Japan
- Prior art keywords
- resin molded
- molded body
- hetero
- cyclic compound
- membered cyclic
- 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
- 238000000034 method Methods 0.000 title claims description 20
- 239000011347 resin Substances 0.000 title claims description 19
- 229920005989 resin Polymers 0.000 title claims description 19
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 150000001923 cyclic compounds Chemical class 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 2
- -1 electronic devices Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 9
- 239000004926 polymethyl methacrylate Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000128 polypyrrole Polymers 0.000 description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000000565 5-membered heterocyclic compounds Chemical class 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- TULWUZJYDBGXMY-UHFFFAOYSA-N tellurophene Chemical compound [Te]1C=CC=C1 TULWUZJYDBGXMY-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (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〕 本発明は樹脂成形体表面を導電化する方法に関する。さ
らに詳しくは、樹脂成形体表面に複素５員環式化合物重
合体との複合体を形成して樹脂成形体表面を導電化する
方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a method for making a surface of a resin molded body conductive. More specifically, it relates to a method of forming a complex with a 5-membered heterocyclic compound polymer on the surface of a resin molded body to make the surface of the resin molded body conductive.
複素５員環式化合物の重合体は比較的安定な導電性高分
子であって、電池材料、センサー材料、オプトエレクト
ロニクス材料、エレクトロニクスデバイスあるいは触媒
などに利用できる有機導電性材料として最近注目されて
いる。これらの複素５員環式化合物重合体を基材上に生
成させる方法として、電気化学的重合法がたとえばNiwa
ら（J.Chem.Soc.,Chem.Communication（1984）817;J.Ch
em.Soc.Chem.Communication（1984）1015）により提示
されている。しかしこの方法は高価な電解質や特別の電
解装置を必要とし、しかも重合体膜の大きさは電極の大
きさに支配される。一方本発明者らは化学酸化反応法を
利用した重合方法で種々の基材上に複素５員環式化合物
重合体膜を製造する方法を提案した（特願昭59−171430
号）。この方法によれば製造コストが低く、大面積化が
可能で、種々の材料の表面に、しかも任意の形状に表面
に複素５員環式化合物重合体膜を形成することができ
る。Polymers of 5-membered heterocyclic compounds are relatively stable conductive polymers, and have recently attracted attention as organic conductive materials that can be used in battery materials, sensor materials, optoelectronic materials, electronic devices, catalysts and the like. . As a method for producing these hetero 5-membered cyclic compound polymers on a substrate, an electrochemical polymerization method is used, for example, Niwa
(J.Chem.Soc., Chem.Communication (1984) 817; J.Ch.
em.Soc.Chem.Communication (1984) 1015). However, this method requires an expensive electrolyte and a special electrolytic device, and the size of the polymer film is governed by the size of the electrode. On the other hand, the present inventors have proposed a method for producing a hetero 5-membered cyclic compound polymer film on various substrates by a polymerization method utilizing a chemical oxidation reaction method (Japanese Patent Application No. 59-171430).
issue). According to this method, the production cost is low, the area can be increased, and the hetero 5-membered cyclic compound polymer film can be formed on the surface of various materials and in any shape.
しかしながらこれらの電解重合法においても、また化学
的酸化反応法においても生成した複素５員環式化合物重
合体膜と基材との結合があまり強固でなく、実用上問題
となっていた。However, the bond between the hetero five-membered cyclic compound polymer film produced in these electrolytic polymerization methods and in the chemical oxidation reaction method and the substrate is not so strong, which has been a practical problem.
本発明の目的は、叙上の観点にたって、樹脂基材に強固
に結合した複素５員環式化合物重合体を形成させ、ひい
ては樹脂成形体表面を良好に導電化する方法を提供する
ことにある。It is an object of the present invention to provide a method for forming a hetero five-membered cyclic compound polymer firmly bonded to a resin base material, and thus making the surface of the resin molded body good conductive, from the above viewpoint. is there.
本発明者らは上記問題点を解決するために鋭意検討し、
本発明を完成させた。The inventors diligently studied to solve the above problems,
The present invention has been completed.
即ち本発明は 樹脂成形体表面に、酸化剤を溶存する樹脂可溶性溶剤を
塗布あるいは流延して、樹脂成形体表面に酸化剤を含む
複合層を形成せしめた後、複素５員環式化合物と接触さ
せることを特徴とする樹脂成形体表面の導電化方法であ
る。That is, in the present invention, a resin-soluble solvent in which an oxidant is dissolved is applied or cast onto the surface of a resin molded product to form a composite layer containing the oxidant on the surface of the resin molded product, and then a hetero 5-membered cyclic compound It is a method for making a surface of a resin molded body electrically conductive, which is characterized by contacting it.
本発明の方法において使用される樹脂成形体を形成する
ポリマーとしては、それらを溶解する溶媒が存在するも
のであれば良く、公知のものが使用できる。これらのポ
リマーとしては、ポリエチレン、ポリプロピレン、ポリ
ブタジエン、ポリイソプレン、ポリ塩化ビニル、ポリビ
ニルアルコール、ポリ酢酸ビニル、ポリメチルメタクリ
レート、ポリアクリルアミド、ポリスチレンなどの付加
重合体、エチレン−プロピレン共重合物、スチレン−ア
クリロニトリル共重合物などのような共重合体、あるい
はエチルセルロースなどの天然高分子誘導体などが使用
される。The polymer forming the resin molded body used in the method of the present invention may be any polymer in which a solvent capable of dissolving them is present, and known polymers can be used. Examples of these polymers include polyethylene, polypropylene, polybutadiene, polyisoprene, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polymethyl methacrylate, polyacrylamide, addition polymers such as polystyrene, ethylene-propylene copolymers, styrene-acrylonitrile. A copolymer such as a copolymer or a natural polymer derivative such as ethyl cellulose is used.
本発明の方法で使用される複素５員環式化合物とは４個
の炭素原子と１個のヘテロ原子を有する不飽和５員環を
基本骨格とする化合物であって、たとえばピロール、チ
オフェン、フラン、セレノフェン、テルロフェンおよび
それらの誘導体である。これらの化合物は単独でも、ま
た２種以上を用いることもできる。The hetero 5-membered cyclic compound used in the method of the present invention is a compound having an unsaturated 5-membered ring having 4 carbon atoms and 1 hetero atom as a basic skeleton, and examples thereof include pyrrole, thiophene and furan. , Selenophene, tellurophene and their derivatives. These compounds may be used alone or in combination of two or more.
本発明の方法において酸化剤としては無機酸、金属の化
合物、あるいは無機や有機の酸化物、過酸化物などが用
いられる。具体的には例えば塩酸、硫酸、硝酸、クロル
スルホン酸などの無機酸類、チタン、ジルコニウム、ク
ロム、モリブデン、タングステン、マンガン、鉄、ルテ
ニウム、パラジウム、白金、銅、アルミニウム、スズな
どの金属のハロゲン化物、あるいはそれらの金属の無機
酸塩類が挙げられ、殊にこれらの金属の化合物でもルイ
ス酸として知られている化合物が好適な酸化剤として挙
げられ、さらにはそれらの金属のアセチルアセトナート
などの配位化合物も挙げられる。さらにはまたペルオキ
ソ二硫酸や過炭酸などの過酸の塩類や、ベンゾキノンや
有機過酸化物も挙げられる。これらの酸化剤は単独で
も、また２種以上の混合としても用いることができる。In the method of the present invention, an inorganic acid, a metal compound, or an inorganic or organic oxide or peroxide is used as the oxidizing agent. Specifically, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and chlorosulfonic acid, and metal halides such as titanium, zirconium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, palladium, platinum, copper, aluminum and tin. , Or inorganic acid salts of these metals, particularly compounds of these metals, also known as Lewis acids, are mentioned as suitable oxidizing agents, and further compounds such as acetylacetonate of these metals are mentioned. Position compounds are also included. Furthermore, salts of peracids such as peroxodisulfuric acid and percarbonate, benzoquinone and organic peroxides can also be mentioned. These oxidizing agents can be used alone or as a mixture of two or more kinds.
本発明において使用する溶剤としては、樹脂成形体を形
成するポリマーと酸化剤を共に溶解するものが使用さ
れ、例えばアルコール類、ハロゲン化炭化水素類、芳香
族炭化水素類、ニトロ化炭化水素類、エーテル類、ニト
リル類、水などが挙げられる。As the solvent used in the present invention, those that dissolve both the polymer forming the resin molded body and the oxidizing agent are used, and examples thereof include alcohols, halogenated hydrocarbons, aromatic hydrocarbons, nitrated hydrocarbons, Examples thereof include ethers, nitriles and water.
溶剤に対する酸化剤の量は特に制限はないが、一般的に
0.01〜１重量％比使用する。The amount of the oxidizing agent with respect to the solvent is not particularly limited, but generally
Use 0.01 to 1 wt% ratio.
これらの酸化剤を含む溶剤を樹脂成形体表面に塗布した
り、樹脂成形体表面にこれらの溶剤を流延したりするこ
とにより成形体表面に酸化剤を含んだ複合層が形成され
る。A composite layer containing an oxidizing agent is formed on the surface of the molded body by applying a solvent containing the oxidizing agent onto the surface of the resin molded body or casting the solvent on the surface of the resin molded body.
複素５員環式化合物と接触させる方法は特に限定はな
く、複素５員環式化合物を含む溶液中に上記成形体を含
浸する方法や、不活性ガス中あるいは空気中あるいは水
蒸気中などで複素５員環式化合物の蒸気と接触させるこ
とにより、表面に複素５員環式化合物重合体を含む複合
層が形成され、必要に応じてドーピングすることにより
表面が導電化された樹脂成形体が得られる。The method of contacting with the hetero 5-membered cyclic compound is not particularly limited, and the method of impregnating the above-mentioned molded product in a solution containing the hetero 5-membered cyclic compound, or the method of contacting the hetero 5 By contacting with the vapor of the membered cyclic compound, a composite layer containing the polymer of the heterocyclic 5-membered cyclic compound is formed on the surface, and if necessary, doping is carried out to obtain a resin molded product whose surface is made conductive. .
以下実施例により本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例−１ ポリメチルメタクリレートの成形板（大きさ5cm×5cm、
厚さ3mm）の上に塩化鉄（III）・６水塩0.6gを酢酸エチ
ル20mlに溶解した溶液を1ml流延した。Example-1 Polymethylmethacrylate molded plate (size 5 cm × 5 cm,
1 ml of a solution prepared by dissolving 0.6 g of iron (III) chloride hexahydrate in 20 ml of ethyl acetate was cast on a thickness of 3 mm.
指にべとつかない程度まで乾燥したのちピロール水溶液
（ピロール／水 1ml/1ml）を底に入れたデシケータ中
に入れ、10時間重合した。After drying to the extent that it was not sticky to the fingers, an aqueous pyrrole solution (pyrrole / water 1 ml / 1 ml) was placed in a desiccator at the bottom, and polymerization was performed for 10 hours.
デシケータから取り出してメタノールで充分洗浄したの
ち乾燥させたところポリメチルメタクリレート成形板の
表面には灰褐色のポリピロール複合層が均一に生成して
おり、表面抵抗を測定したところ2KΩであった。またこ
の表面をプラスチック消しゴムで強くこすっても表面導
電率に変化がなかった。When taken out from the desiccator, thoroughly washed with methanol and dried, a gray-brown polypyrrole composite layer was uniformly formed on the surface of the polymethylmethacrylate molded plate, and the surface resistance was measured to be 2 KΩ. Even if the surface was strongly rubbed with a plastic eraser, the surface conductivity did not change.
比較例 実施例−１において溶剤としてポリメチルメタクリレー
トを全く溶かさない水を用いて実施例−１と同様にして
ポリピロールを表面に形成させた。ポリメチルメタクリ
レート成形板表面にはポリピロールの薄膜が生成してお
り、表面導電率は600Ωであった。この表面をプラスチ
ック消しゴムで強くこすったところポリピロールの薄膜
がポリメチルメタクリレート成形板表面から完全にはが
れてしまった。Comparative Example Polypyrrole was formed on the surface in the same manner as in Example 1 by using water that did not dissolve polymethylmethacrylate as a solvent in Example-1. A thin film of polypyrrole was formed on the surface of the polymethylmethacrylate molded plate, and the surface conductivity was 600Ω. When this surface was strongly rubbed with a plastic eraser, a thin film of polypyrrole was completely peeled off from the surface of the polymethylmethacrylate molded plate.
実施例−２ 実施例−１においてポリメチルメタクリレートの代わり
にポリ塩化ビニルフィルム（5cm×5cm、厚さ0.5mm）を
用いて、溶剤としてテトラヒドロフランを用いた以外は
実施例−１と同様にして行なったところ、ポリ塩化ビニ
ルフィルム上にポリピロール複合層が均一に生成してお
り、その表面抵抗は15KΩであった。表面の強度は実施
例−１の結果と同様であった。Example-2 In the same manner as in Example-1, except that a polyvinyl chloride film (5 cm × 5 cm, thickness 0.5 mm) was used instead of polymethylmethacrylate in Example-1, and tetrahydrofuran was used as the solvent. As a result, a polypyrrole composite layer was uniformly formed on the polyvinyl chloride film, and its surface resistance was 15 KΩ. The surface strength was similar to the result of Example-1.
実施例−３ ポリメチルメタクリレート板上に無水塩化鉄（III）0.5
gを塩化メチレン20mlに溶解した溶液を1ml流延し、指に
べとつかない程度に乾燥したのちデシケータ中に入れ、
チオフェンで飽和した窒素ガスを流通させた。１時間重
合したのちデシケータから取り出してメタノールで余分
の酸化剤を除いた。ポリメチルメタクリレート板の上に
は赤色のポリチオフェン複合層が均一に形成されてお
り、表面をヨウ素の蒸気にさらしてヨウ素ドープを行な
った後、表面抵抗を測定したところ、250Ωであった。
電導層の強度は実施例−１の結果と同様であった。Example 3 Anhydrous iron (III) chloride 0.5 on a polymethylmethacrylate plate
Cast 1 ml of a solution of g dissolved in 20 ml of methylene chloride, dry it so that it does not stick to the fingers, and put it in a desiccator.
Nitrogen gas saturated with thiophene was passed. After polymerizing for 1 hour, it was taken out from the desiccator and the excess oxidizing agent was removed with methanol. A red polythiophene composite layer was uniformly formed on the polymethylmethacrylate plate, and the surface resistance was measured to be 250Ω after the surface was exposed to vapor of iodine for iodine doping.
The strength of the conductive layer was similar to the result of Example-1.
本発明の方法によれば、樹脂成形体表面に強固に結合さ
れた導電層を、簡便かつ工業的に有利に形成することが
できる。According to the method of the present invention, the conductive layer firmly bonded to the surface of the resin molded body can be formed easily and industrially advantageously.
Claims (1)
可溶性溶剤を塗布あるいは流延して、樹脂成形体表面に
酸化剤を含む複合層を形成せしめた後、複素５員環式化
合物と接触させることを特徴とする樹脂成形体表面の導
電化方法。1. A hetero five-membered cyclic compound is obtained by applying or casting a resin-soluble solvent in which an oxidizing agent is dissolved on the surface of a resin molded body to form a composite layer containing the oxidizing agent on the surface of the resin molded body. A method for making a surface of a resin molded body electrically conductive, which comprises contacting the surface with a resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60275053A JPH0727732B2 (en) | 1985-12-09 | 1985-12-09 | Method for making surface of resin molded body conductive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60275053A JPH0727732B2 (en) | 1985-12-09 | 1985-12-09 | Method for making surface of resin molded body conductive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62136712A JPS62136712A (en) | 1987-06-19 |
| JPH0727732B2 true JPH0727732B2 (en) | 1995-03-29 |
Family
ID=17550187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60275053A Expired - Lifetime JPH0727732B2 (en) | 1985-12-09 | 1985-12-09 | Method for making surface of resin molded body conductive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0727732B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326936C (en) * | 2005-06-16 | 2007-07-18 | 同济大学 | Transparent polymer non-aqueous proton conducting material and its preparing method |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0743968B2 (en) * | 1987-01-26 | 1995-05-15 | 凸版印刷株式会社 | Method for manufacturing conductive film |
| DE3729875A1 (en) * | 1987-09-05 | 1989-03-23 | Bayer Ag | METHOD FOR THE ANTISTATIC FINISHING OF MELT GLUE LAYERS |
| JPS6476613A (en) * | 1987-09-18 | 1989-03-22 | Japan Carlit Co Ltd | Making base material with electric insulation conductive continuously |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3001904B2 (en) * | 1989-08-10 | 2000-01-24 | キヤノン株式会社 | Image recording device |
-
1985
- 1985-12-09 JP JP60275053A patent/JPH0727732B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326936C (en) * | 2005-06-16 | 2007-07-18 | 同济大学 | Transparent polymer non-aqueous proton conducting material and its preparing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62136712A (en) | 1987-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3544957C3 (en) | Process for the production of an electrically conductive composite polymer molded body, Schottky junction or semiconductor diodes and patterned electrodes | |
| Waltman et al. | Electrochemical studies of some conducting polythiophene films | |
| Daoust et al. | Structure-property relationships in alkoxy-substituted polythiophenes | |
| JP2721700B2 (en) | Production method of polythiophene | |
| JP3040113B2 (en) | Solid electrolyte and electrolytic capacitor containing the same | |
| JPH04491B2 (en) | ||
| JPH0727732B2 (en) | Method for making surface of resin molded body conductive | |
| JPH0349287B2 (en) | ||
| JPH0363971B2 (en) | ||
| GB2181367A (en) | A method of manufacturing an electrically conductive layer | |
| JPH0618909B2 (en) | Manufacturing method of composite materials | |
| JPH0348933B2 (en) | ||
| JPH0727731B2 (en) | Method for manufacturing conductive composite film | |
| JPH0369369B2 (en) | ||
| JPS62267321A (en) | Electrically conductive polymer solution | |
| JPS62136709A (en) | Manufacture of conductive pattern | |
| JPH0274019A (en) | Manufacture of solid electrolytic condenser | |
| JPH0535843B2 (en) | ||
| JPH0419253B2 (en) | ||
| JPH0684440B2 (en) | Method for manufacturing conductive film | |
| JPH0664928B2 (en) | Conductive material | |
| JPH0351246B2 (en) | ||
| KR920003106B1 (en) | Process for the preparation of electric conductive composition | |
| JP2525488B2 (en) | Highly conductive polypyrrole molding | |
| Zhao et al. | Studies of electropolymerisation of sodium 2-(3-thienyl) ethyl sulfonate |