JPS61197636A - Production of electrically conductive composite material - Google Patents
Production of electrically conductive composite materialInfo
- Publication number
- JPS61197636A JPS61197636A JP3952085A JP3952085A JPS61197636A JP S61197636 A JPS61197636 A JP S61197636A JP 3952085 A JP3952085 A JP 3952085A JP 3952085 A JP3952085 A JP 3952085A JP S61197636 A JPS61197636 A JP S61197636A
- Authority
- JP
- Japan
- Prior art keywords
- composite material
- electrically conductive
- conductive composite
- support
- film
- 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.)
- Pending
Links
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規な導電性複合材料の製造方法に関し、詳し
くは、用いる支持体の種々の物理的及び／又は化学的特
性を保有する新規な導電性複合材料の製造方法に関する
。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for manufacturing a novel conductive composite material, and more particularly, to a method for manufacturing a novel conductive composite material, which has various physical and/or chemical properties of the support used. The present invention relates to a method for manufacturing a conductive composite material.
（従来の技術）
従来、ピロール、チオフェン、フランやこれらの誘導体
等の複素環式化合物が電解酸化重合又は化学酸化重合に
よって容易に導電性重合体を与えることは知られており
、このような導電性重合体は、ポリアセチレンと異なり
、熱的及び化学的に比較的安定な導電性重合体として、
種々の実用的な展開が進められている。しかし、従来の
このような方法によれば、多くの場合、導電性重合体は
粉末として得られ、また、フィルムとして得られる場合
も、大きい面積を有し、且つ、均質である重合体を得る
ことが困難である。更に、得られる重合体が殆どの有機
溶剤に対して不溶性であるので成形性に劣り、更に、機
械的強度に劣るために実用化が妨げられている。(Prior Art) It has been known that heterocyclic compounds such as pyrrole, thiophene, furan, and their derivatives can be easily formed into conductive polymers by electrolytic oxidative polymerization or chemical oxidative polymerization. Unlike polyacetylene, the conductive polymer is a relatively thermally and chemically stable conductive polymer.
Various practical developments are underway. However, according to such conventional methods, conductive polymers are often obtained as a powder, and even when obtained as a film, it is difficult to obtain a homogeneous polymer with a large area. It is difficult to do so. Furthermore, the resulting polymer is insoluble in most organic solvents, resulting in poor moldability, and furthermore, poor mechanical strength, which hinders its practical use.
例えば、ピロールを電解酸化重合することによって、電
極上にポリピロールからなる導電性フィルムを得ること
ができることが知られているが、このフィルムは脆く、
機械的強度に劣り、また、二次加工が困難である。For example, it is known that a conductive film made of polypyrrole can be obtained on an electrode by electrolytic oxidative polymerization of pyrrole, but this film is brittle and
It has poor mechanical strength and is difficult to perform secondary processing.
（発明の目的）
本発明は、導電性材料における上記した問題を解決する
ためになされたものであって、熱的、化学的特性のみな
らず、成形性、機械的強度等の物理的特性にもすぐれ、
更に、大きい面積を有する導電性複合材料をも容易に製
造し得る方法を提供することを目的とする。(Objective of the Invention) The present invention was made to solve the above-mentioned problems in conductive materials, and is aimed at improving not only thermal and chemical properties but also physical properties such as formability and mechanical strength. Good morning,
Furthermore, it is an object of the present invention to provide a method that can easily produce a conductive composite material having a large area.
（発明の構成）
本発明による導電性複合材料の製造方法は、重合性を有
する複素環式化合物単量体を支持体の内部及び／又は表
面で化学的に酸化重合させて導電性重合体を形成させる
ことを特徴とする。(Structure of the Invention) The method for producing a conductive composite material according to the present invention involves chemically oxidatively polymerizing a polymerizable heterocyclic compound monomer inside and/or on the surface of a support to form a conductive polymer. It is characterized by forming.
本発明において用いる単量体は、酸化剤による酸化重合
によって導電性重合体を生成する複素環式化合物であっ
て、その具体例として、ピロール、その窒素、３位及び
／又は４位に置換基を有する誘導体、チオフェン、その
３位及び／又は４位に置換基を有する誘導体、フラン、
その３位及び／又は４位に置換基を有する誘導体を挙げ
ることができる。これらの重合性単量体は、酸化剤によ
って重合して導電性重合体を与え得るように、その酸化
電位が用いる化学酸化剤の酸化電位よりも低いことが必
要であり、且つ、上記導電性重合体は、化学的に重合体
主鎖に部分酸化、即ち、ドーピングが生じて、高い導電
性を有するように、その酸化電位が上記重合性単量体の
酸化電位よりも低いことが必要である。The monomer used in the present invention is a heterocyclic compound that produces a conductive polymer by oxidative polymerization using an oxidizing agent, and specific examples thereof include pyrrole, a substituent at the nitrogen, 3-position, and/or 4-position. derivatives having substituents at the 3- and/or 4-positions, thiophene, furan,
Derivatives having a substituent at the 3rd and/or 4th position can be mentioned. These polymerizable monomers must have an oxidation potential lower than the oxidation potential of the chemical oxidizing agent used so that they can be polymerized by the oxidizing agent to give a conductive polymer; The oxidation potential of the polymer must be lower than that of the polymerizable monomer so that partial oxidation, that is, doping, occurs chemically in the polymer main chain and the polymer has high conductivity. be.
本発明において用いる支持体は、上記したような重合性
単量体及び／又は酸化剤がその内部に拡散し、浸透し、
或いは透過し、又はその表面に吸着される性質を有する
と共に、本発明において用いる後述する酸化剤によって
その支持体自体の化学的及び物理的特性が損なわれない
程度に、熱的、化学的及び物理的に安定であればよく、
特に、限定されない。従って、かかる支持体は、用いる
酸化剤や、得られる導電性複合材料の用途等に応じて、
適宜に選ぶことができる。The support used in the present invention is such that the polymerizable monomer and/or oxidizing agent as described above diffuses and permeates into the support.
Alternatively, it has the property of being able to permeate or be adsorbed on its surface, and is thermally, chemically and physically resistant to the extent that the chemical and physical properties of the support itself are not impaired by the oxidizing agent used in the present invention, which will be described later. As long as it is stable,
In particular, it is not limited. Therefore, such supports can be used depending on the oxidizing agent used and the use of the resulting conductive composite material.
You can choose as appropriate.
このような支持体の代表的な例として、例えば、フッ素
系樹脂やポリアクリロニトリルからなる多孔性フィルム
又は膜を挙げることができる。また、ポリエチレン、ポ
リプロピレン、ポリスチレン等の合成樹脂からなる緻密
な均質フィルムも重合性単量体に対して上記条件を満足
する限りは、支持体として用いることができる。必要に
応じて、天然樹脂からなる緻密な均質フィルムも用いる
ことができる。これらの均質フィルムは、重合性単量体
の酸化重合を行なう反応系の溶剤を選択して、フィルム
を膨潤させれば、重合性単量体及び／又は酸化剤の拡散
性や浸透性を高めることができる。Typical examples of such supports include, for example, porous films or membranes made of fluororesin or polyacrylonitrile. Further, a dense homogeneous film made of synthetic resin such as polyethylene, polypropylene, polystyrene, etc. can also be used as the support as long as the above conditions are satisfied for the polymerizable monomer. If necessary, a dense homogeneous film made of natural resin can also be used. These homogeneous films can be created by selecting a reaction solvent for oxidative polymerization of the polymerizable monomer and swelling the film to increase the diffusivity and permeability of the polymerizable monomer and/or oxidizing agent. be able to.
上記のような多孔性膜や樹脂フィルムを支持体として用
いるとき、柔軟で且つ強靭であり、更に、二次加工性に
すぐれる導電性複合材料を得ることができる。When a porous membrane or resin film as described above is used as a support, it is possible to obtain a conductive composite material that is flexible and strong and has excellent secondary processability.
また、多孔質のガラスやセラミックスも支持体として用
いることができる。これら支持体を用いるときは、剛性
のある導電性複合材料を得ることができる。Further, porous glass or ceramics can also be used as the support. When using these supports, rigid conductive composite materials can be obtained.
本発明において用いる酸化剤は、前記した重合性単量体
を酸化重合させて導電性重合体を生成させる酸化剤であ
り、重合性単量体の酸化電位よりも高い酸化電位を有す
るものであれば、特に制限されない。かかる酸化剤の具
体例として、Ｆｅ”、ＨｚＯｚ、ｓ２ｏ、”−１Ｃ１ｚ
、Ｂｒｚのほか、ＲｕＯ，−５Ｏｓ０４．−１Ｍｎ０４
−のような高酸化オキシ酸イオン、ＩｒＣｌ６”−１Ｐ
ｔＣ１＆”−１ＰｄＣ１４”−１ＡｕＣ１ａ−のような
貴金属酸イオンを挙げることができる。この際の重合性
単量体及び酸化剤の濃度は、特に限定されないが、０．
００１モル／１乃至飽和溶液が好ましい。The oxidizing agent used in the present invention is an oxidizing agent that causes oxidative polymerization of the above-mentioned polymerizable monomer to produce a conductive polymer, and may have an oxidation potential higher than that of the polymerizable monomer. However, there are no particular restrictions. Specific examples of such oxidizing agents include Fe", HzOz, s2o, "-1C1z
, Brz, as well as RuO,-5Os04. -1Mn04
- highly oxidized oxyacid ions such as IrCl6”-1P
Mention may be made of noble metal acid ions such as tC1&"-1PdC14"-1AuC1a-. The concentrations of the polymerizable monomer and oxidizing agent at this time are not particularly limited, but are 0.
001 mol/1 to a saturated solution is preferred.
尚、これらの酸化剤のうち、例えば、Ｃ１□、Ｂｒ２、
ｓ、ｏ＊”−等は、重合性単量体を酸化すると共に、自
体は負電荷を有する還元体に還元され、これが導電性重
合体主鎖における正電荷によって捕捉されて、導電性重
合体にドープさる。従って、本発明の方法においては、
酸化剤として機能性分子を利用すれば、得られる導電性
複合材料にエレクトロクロミズムや光電変換等の機能性
を付与す・ることができる。このような機能性分子の例
として、ルテニウム（■）トリス（バソフエナンスロリ
ンスルホン酸）やルテニウム（■）トリス（ビピリジン
ジスルホン酸）等を挙げることができる。Incidentally, among these oxidizing agents, for example, C1□, Br2,
s, o*''-, etc. oxidize the polymerizable monomer and are themselves reduced to a reductant having a negative charge, which is captured by the positive charge in the main chain of the conductive polymer and becomes a conductive polymer. Therefore, in the method of the present invention,
By using a functional molecule as an oxidizing agent, it is possible to impart functionality such as electrochromism and photoelectric conversion to the resulting conductive composite material. Examples of such functional molecules include ruthenium (■) tris (basophenanthrolinesulfonic acid) and ruthenium (■) tris (bipyridine disulfonic acid).
本発明においては、前記した複素環式化合物単量体を支
持体の内部及び／又は表面で化学的に酸化重合させて導
電性重合体を形成させるが、その主要な態様として、支
持体に重合性単量体溶液を塗布又は含浸した後、これを
酸化剤溶液中に浸漬する方法や、支持体に酸化剤溶液を
塗布又は含浸した後、これを重合性単量体溶液中に浸漬
する方法を挙げることができる。更に、支持体を形成し
得゛る樹脂の高濃度溶液に重合性単量体を混合し、所要
形状の支持体、例えば、シートに成形した後これを酸化
剤溶液に浸漬する方法や、支持体を形成し得る樹脂の高
濃度溶液に酸化剤を混合し、所要形状の支持体、例えば
、シートに成形した後、これを重合性単量体溶液に浸漬
する方法を挙げることができる。In the present invention, the above-described heterocyclic compound monomer is chemically oxidatively polymerized inside and/or on the surface of the support to form a conductive polymer. A method in which a support is coated or impregnated with a polymerizable monomer solution and then immersed in an oxidizing agent solution, or a method in which a support is coated or impregnated with an oxidizing agent solution and then immersed in a polymerizable monomer solution. can be mentioned. Furthermore, there is a method in which a polymerizable monomer is mixed with a highly concentrated solution of a resin that can form a support, formed into a support of a desired shape, for example, a sheet, and then immersed in an oxidizing agent solution. For example, a method can be mentioned in which an oxidizing agent is mixed with a highly concentrated solution of a resin capable of forming a polymer, formed into a support of a desired shape, for example, a sheet, and then immersed in a polymerizable monomer solution.
従って、本発明の方法によれば、例えば、シート状支持
体に導電性重合体を複合化してなる導電性複合材料にお
いて、シート状支持体の表面近傍のみに導電性重合体を
形成させれば、異方性の導電性複合材料を得ることがで
き、また、シート状支持体の厚み方向に実質的に均一に
導電性重合体を形成させて、等方性の導電性複合材料を
得ることもできる。このようにして、得られる導電性複
合材料の導電性を重合条件によって制御することも可能
である。Therefore, according to the method of the present invention, for example, in a conductive composite material made of a sheet-like support and a conductive polymer, if the conductive polymer is formed only near the surface of the sheet-like support, , an anisotropic conductive composite material can be obtained, and a conductive polymer can be formed substantially uniformly in the thickness direction of a sheet-like support to obtain an isotropic conductive composite material. You can also do it. In this way, it is also possible to control the conductivity of the resulting conductive composite material by controlling the polymerization conditions.
（発明の効果）
゛ 本発明の方法によれば、以上のように、複素環式
化合物単量体を支持体の内部及び／又は表面で化学的に
酸化重合させて導電性重合体を形成させるので、大きい
面積を有する導電性複合材料を容易に得ることができる
のみならず、得られる複合材料は支持体によって補強さ
れているために機械的強度にすぐれ、更に、支持体が熱
可塑性樹脂からなる場合は、導電性複合材料を得た後、
これを加熱して、二次加工することも容易である。(Effects of the Invention) According to the method of the present invention, as described above, the heterocyclic compound monomer is chemically oxidatively polymerized inside and/or on the surface of the support to form a conductive polymer. Therefore, not only can a conductive composite material with a large area be easily obtained, but also the resulting composite material has excellent mechanical strength because it is reinforced by the support, and furthermore, the support is made of thermoplastic resin. If the conductive composite material is obtained,
It is also easy to heat this and perform secondary processing.
また、本発明の方法によれば、導電性複合材料の製造に
際して、ホトクロミック材料、光電変換材料等の各種の
機能分子を共存させることによって、機能性を拡大する
ことができる。Furthermore, according to the method of the present invention, functionality can be expanded by allowing various functional molecules such as photochromic materials and photoelectric conversion materials to coexist when producing a conductive composite material.
（実施例）
以下に実施例を挙げて本発明の方法を具体的に説明する
。(Example) The method of the present invention will be specifically explained with reference to Examples below.
実施例１
厚さ０．１２５１ｍのフッ素系樹脂膜（デュポン社製ナ
フィオン（Ｎａｆｆｏｎ）膜）をピロールの飽和水溶液
に１５０分間浸漬した後、その表面を拭い、０゜１モル
／ｌ過硫酸カリウム水溶液に３０分間浸漬した。このよ
うにして得られた黒褐色の膜は、１０−２〜１０−’Ｓ
／ｃｍの電導度を示し、その引張強度は４３Ｎ／ｍｍ”
であった。Example 1 A fluororesin membrane (Naffon membrane manufactured by DuPont) with a thickness of 0.1251 m was immersed in a saturated aqueous solution of pyrrole for 150 minutes, and then its surface was wiped and soaked in a 0.1 mol/l potassium persulfate aqueous solution. immersed in for 30 minutes. The blackish-brown film obtained in this way is 10-2 to 10-'S.
/cm, and its tensile strength is 43N/mm"
Met.
また、この膜にはポリピロールがその内部及び表面にほ
ぼ均一に形成されていた。Moreover, polypyrrole was formed almost uniformly inside and on the surface of this film.
実施例２
実施例１において、ピロールの代わりに０．１−１−ル
／ｌのチオフェンのアルコール溶液を用いて、黒褐色の
膜を得た。この膜は、１０−３〜１０−”３７ｃｍの電
導度を示し、また、引張強度は４１Ｎ／ｍｍ”であった
。Example 2 In Example 1, a dark brown film was obtained by using an alcoholic solution of thiophene at 0.1-1-l/l in place of pyrrole. The membrane exhibited a conductivity of 10-3 to 10-''37 cm and a tensile strength of 41 N/mm''.
また、この膜にはポリチオフェンがその内部及び表面に
ほぼ均一に形成されていた。Moreover, polythiophene was formed almost uniformly inside and on the surface of this film.
実施例３
厚さ０．１２５ｆｉのナフィオン膜を０．１モル／ｌ過
硫酸カリウム水溶液に１５０分間浸漬した後、その表面
を拭い、その後、ピロールの飽和水溶液に３０分間浸漬
した。このようにして得られた黒褐色の膜は、１０−＝
１０−’Ｓ／ｃａ＋の電導度を示し、その引張強度は
４５Ｎ／ｍｍ”であった。Example 3 A Nafion membrane having a thickness of 0.125 fi was immersed in a 0.1 mol/l potassium persulfate aqueous solution for 150 minutes, the surface thereof was wiped, and then immersed in a saturated aqueous solution of pyrrole for 30 minutes. The blackish-brown film thus obtained was 10−=
It exhibited an electrical conductivity of 10-'S/ca+ and a tensile strength of 45 N/mm''.
また、この膜にはポリピロールがその内部及び表面にほ
ぼ均一に形成されていた。Moreover, polypyrrole was formed almost uniformly inside and on the surface of this film.
実施例４
実施例１において、過硫酸カリウムの代わりにルテニウ
ム酸カリウムの飽和水溶液を用いて、金属光沢のある黒
褐色の膜を得た。この膜は、１０゜〜１０’Ｓ／ｃｍの
電導度を示し、また、引張強度は４ＯＮ／ｍｍ２であっ
た。Example 4 In Example 1, a saturated aqueous solution of potassium ruthenate was used instead of potassium persulfate to obtain a dark brown film with metallic luster. This film exhibited a conductivity of 10° to 10'S/cm and a tensile strength of 4ON/mm2.
また、この膜にはポリピロールがその内部及び表面にほ
ぼ均一に形成されていた。Moreover, polypyrrole was formed almost uniformly inside and on the surface of this film.
実施例５
実施例２において、過硫酸カリウムの代わりにルテニウ
ム酸カリウムの飽和水溶液を用いた。得られた膜は、１
０−′〜１０弓Ｓ／ｃＩＩ＋の電導度を示し、また、引
張強度は４ＯＮ／ｍｍ”であった。Example 5 In Example 2, a saturated aqueous solution of potassium ruthenate was used instead of potassium persulfate. The obtained film was 1
It exhibited an electrical conductivity of 0-' to 10 S/cII+, and a tensile strength of 4 ON/mm''.
また、この膜にはポリチオフェンがその内部及び表面に
ほぼ均一に形成されていた。Moreover, polythiophene was formed almost uniformly inside and on the surface of this film.
実施例６
１．０体積％のピロールを含む厚さ０． Ｉ ｎ＋の均
質なポリアクリロニトリル膜を調製し、これを０．１モ
ル／ｌ過硫酸カリウム水溶液に浸漬した。６時間後に得
られた黒褐色の膜は異方性導電性膜であって、表面型導
度が１０−”〜ｌ Ｏ−’Ｓ／ｃｍであり、垂直方向の
電導度は１０づ〜１０−’Ｓ／ｃｍであった。また、膜
の引張強度は３８Ｎ／ｍｍ２であった。Example 6 Thickness: 0.000 mm containing 1.0% by volume of pyrrole. A homogeneous polyacrylonitrile film of I n+ was prepared and immersed in a 0.1 mol/l potassium persulfate aqueous solution. The blackish-brown film obtained after 6 hours is an anisotropic conductive film, with a surface conductivity of 10-" to 1 O-'S/cm, and a vertical conductivity of 10 to 10-"'S/cm.Furthermore, the tensile strength of the membrane was 38 N/mm2.
また、上記と同じポリアクリロニトリル膜を０゜１モル
／ｌ過硫酸カリウム水溶液に１２時間浸漬したときは、
表面型導度は上記膜と同じであるが、垂直方向の電導度
は１０−２〜１０−’Ｓ／ｃｍであった。Furthermore, when the same polyacrylonitrile membrane as above was immersed in a 0.1 mol/l potassium persulfate aqueous solution for 12 hours,
The surface type conductivity was the same as the above film, but the vertical conductivity was 10-2 to 10-'S/cm.
実施例７
０．５体積％の過硫酸カリウム微粉末をブレンドした厚
さ０．０５ ＊＊＊のポリアクリロニトリル膜を調製し
、これをピロールに１０時間浸漬した。得られた黒褐色
の膜は、表面型導度がｌｏ−２〜工０−１３ ／ ｃｍ
であり、垂直方向の電４度が１０−３〜１０− ’ Ｓ
／ ａｍであった。膜の引張強度は３７Ｎ／ｍｍ２で
あった。Example 7 A polyacrylonitrile film with a thickness of 0.05 *** blended with 0.5% by volume of potassium persulfate fine powder was prepared and immersed in pyrrole for 10 hours. The obtained dark brown film has a surface conductivity of lo-2 to 0-13/cm.
, and the electric fourth degree in the vertical direction is 10-3 to 10-' S
/ am. The tensile strength of the membrane was 37 N/mm2.
実施例８
ピロール及びスピロピランをそれぞれ１．０体積％ブレ
ンドしたポリスチレン膜を調製し、これを０．１モル／
ｌ過硫酸カリウム水溶液に３時間浸漬した。得られた暗
褐色の膜は、近紫外光の照射によって黒褐色となるホト
クロミズムを示した。Example 8 A polystyrene film containing 1.0% by volume of each of pyrrole and spiropyran was prepared, and 0.1 mol/% of this was blended.
It was immersed in a potassium persulfate aqueous solution for 3 hours. The obtained dark brown film showed photochromism, turning blackish brown when irradiated with near-ultraviolet light.
また、この膜の電導度は１０−２〜１０刊Ｓ ／ ｃｍ
、引張強度は６２ Ｎ ／ｍｍ２であった。Also, the electrical conductivity of this film is 10-2 to 10 S/cm
, the tensile strength was 62 N/mm2.
実施例９
実施例８において、スピロピランの代すりに、亜鉛テト
ラスルホフェニルポルフィリン錯体を用いて、実施例８
と同様にして、暗紫色の膜を得た。Example 9 In Example 8, a zinc tetrasulfophenylporphyrin complex was used in place of spiropyran.
A dark purple film was obtained in the same manner as above.
この膜の電窩度は１Ｏ−２〜１０−’Ｓ／ａｍであった
。The degree of electric porosity of this film was 10-2 to 10-'S/am.
また、膜の引張強度は６３Ｎ／ｍｍ２であった。Further, the tensile strength of the membrane was 63 N/mm2.
この膜と白金をそれぞれ電極とし、支持電解質として１
モル／ｌ塩化カリウム水溶液を用いて電池を形成したと
ころ、可視光照射によって光電池としての機能を示した
。This membrane and platinum are used as electrodes, and 1 as a supporting electrolyte.
When a battery was formed using a mol/l potassium chloride aqueous solution, it exhibited a function as a photovoltaic cell upon irradiation with visible light.
Claims (2)
内部及び／又は表面で化学的に酸化重合させて導電性重
合体を形成させることを特徴とする導電性複合材料の製
造方法。(1) A method for producing a conductive composite material, which comprises chemically oxidatively polymerizing a polymerizable heterocyclic compound monomer inside and/or on the surface of a support to form a conductive polymer. .
らの誘導体から選ばれる複素環式化合物であることを特
徴とする特許請求の範囲第１項記載の導電性複合材料の
製造方法。(2) The method for producing a conductive composite material according to claim 1, wherein the monomer is a heterocyclic compound selected from pyrrole, thiophene, furan, or a derivative thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3952085A JPS61197636A (en) | 1985-02-27 | 1985-02-27 | Production of electrically conductive composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3952085A JPS61197636A (en) | 1985-02-27 | 1985-02-27 | Production of electrically conductive composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61197636A true JPS61197636A (en) | 1986-09-01 |
Family
ID=12555316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3952085A Pending JPS61197636A (en) | 1985-02-27 | 1985-02-27 | Production of electrically conductive composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61197636A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62275137A (en) * | 1985-11-05 | 1987-11-30 | Achilles Corp | Preparation of conductive composite |
| WO1990008792A1 (en) * | 1989-01-31 | 1990-08-09 | Nippon Oil And Fats Co., Ltd. | Fluoroalkylated heteroaromatic polymer |
| JPH07124332A (en) * | 1993-10-29 | 1995-05-16 | Konami Kk | Brake unit mechanism for video driving game machine |
| JP2006215104A (en) * | 2005-02-01 | 2006-08-17 | Nitto Denko Corp | Adhesive optical film and image display unit |
| WO2018084820A2 (en) | 2016-09-07 | 2018-05-11 | Istanbul Teknik Universitesi | METHOD OF PRODUCING POWDER-FORM POLYMER USING 1-(p-OLYLSULFONYL) PYRROLE MONOMER |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61111336A (en) * | 1984-11-06 | 1986-05-29 | Toray Ind Inc | Preparation of composite material |
| JPS61127736A (en) * | 1984-11-26 | 1986-06-16 | Mitsui Toatsu Chem Inc | Production of electrically conductive resin composite |
| JPS61157522A (en) * | 1984-12-28 | 1986-07-17 | Hoechst Gosei Kk | Production of molded article of electrically conductive composite high polymer |
-
1985
- 1985-02-27 JP JP3952085A patent/JPS61197636A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61111336A (en) * | 1984-11-06 | 1986-05-29 | Toray Ind Inc | Preparation of composite material |
| JPS61127736A (en) * | 1984-11-26 | 1986-06-16 | Mitsui Toatsu Chem Inc | Production of electrically conductive resin composite |
| JPS61157522A (en) * | 1984-12-28 | 1986-07-17 | Hoechst Gosei Kk | Production of molded article of electrically conductive composite high polymer |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62275137A (en) * | 1985-11-05 | 1987-11-30 | Achilles Corp | Preparation of conductive composite |
| WO1990008792A1 (en) * | 1989-01-31 | 1990-08-09 | Nippon Oil And Fats Co., Ltd. | Fluoroalkylated heteroaromatic polymer |
| JPH07124332A (en) * | 1993-10-29 | 1995-05-16 | Konami Kk | Brake unit mechanism for video driving game machine |
| JP2006215104A (en) * | 2005-02-01 | 2006-08-17 | Nitto Denko Corp | Adhesive optical film and image display unit |
| JP4582704B2 (en) * | 2005-02-01 | 2010-11-17 | 日東電工株式会社 | Adhesive optical film and image display device |
| WO2018084820A2 (en) | 2016-09-07 | 2018-05-11 | Istanbul Teknik Universitesi | METHOD OF PRODUCING POWDER-FORM POLYMER USING 1-(p-OLYLSULFONYL) PYRROLE MONOMER |
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