US20090321688A1 - Carbon Nanotube Composition, Composite Having a Coated Film Composed of the Same, and Their Production Methods - Google Patents
Carbon Nanotube Composition, Composite Having a Coated Film Composed of the Same, and Their Production Methods Download PDFInfo
- Publication number
- US20090321688A1 US20090321688A1 US12/556,406 US55640609A US2009321688A1 US 20090321688 A1 US20090321688 A1 US 20090321688A1 US 55640609 A US55640609 A US 55640609A US 2009321688 A1 US2009321688 A1 US 2009321688A1
- Authority
- US
- United States
- Prior art keywords
- group
- ion
- carbon atoms
- cooh
- linear
- 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.)
- Abandoned
Links
- 0 [1*]C1=C(C)SC(C)=C1[2*] Chemical compound [1*]C1=C(C)SC(C)=C1[2*] 0.000 description 36
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/005—Carbon black
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/512—Hole transport
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/79—Post-treatment doping
- C08G2261/794—Post-treatment doping with polymeric dopants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
- Y10S977/745—Carbon nanotubes, CNTs having a modified surface
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
- Y10S977/745—Carbon nanotubes, CNTs having a modified surface
- Y10S977/746—Modified with biological, organic, or hydrocarbon material
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/753—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc. with polymeric or organic binder
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
Definitions
- the present invention relates to a carbon nanotube composition, a composite having a coated film composed of the same, and their production methods.
- the object of the present invention is to provide a carbon nanotube composition that does not impair the characteristics of the carbon nanotubes itself, allows the carbon nanotubes to be dispersed or solubilized in water, organic solvents, water-containing organic solvents and other solvents, does not cause separation or aggregation of the carbon nanotubes even during long-term storage, has superior electrical conductivity, film formability and moldability, can be easily coated or covered onto a base material, and the resulting coated film has superior moisture resistance, weather resistance and hardness.
- the object of the present invention is also to provide a composite having a coated film comprising the carbon nanotube composition as well as production methods of the carbon nanotube composition and the coated film.
- carbon nanotubes can be dispersed or solubilized in solvent by placing in the presence of a conducting polymer, thereby leading to completion of the present invention.
- a first aspect of the present invention is a carbon nanotube composition that contains a conducting polymer (a), a solvent (b) and carbon nanotubes (c).
- the carbon nanotubes (c) are added to the solvent (b) together with the conducting polymer (a), the carbon nanotubes (c) can be dispersed or solubilized in the solvent (b) without impairing the characteristics of the carbon nanotubes (c) itself, and there is no separation or aggregation even during long-term storage.
- the carbon nanotubes (c) are presumed to be dispersed or solubilized together with the conducting polymer (a) due to mutual adsorption by the conducting polymer (a) and the carbon nanotubes (c) due to the ⁇ - ⁇ interaction by ⁇ electrons.
- the resulting composition has superior electrical conductivity, film formability and moldability.
- the performance of the carbon nanotube composition can be improved by additionally containing a high molecular weight compound (d), a basic compound (e), a surfactant (f) and a silane coupling agent (g) and/or a colloidal silica (h).
- the conducting polymer (a) is preferably a water soluble conducting polymer, and more preferably a water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group.
- a second aspect of the present invention is a carbon nanotube composition that contains a heterocyclic compound trimer (i), a solvent (b) and carbon nanotubes (c). Similar to the carbon nanotube composition of the first aspect of the present invention, performance of the composition can be improved by additionally containing a high molecular weight compound (d), a basic compound (e), a surfactant (f), a silane coupling agent (g) and/or a colloidal silica (h).
- the carbon nanotube compositions of the first and second aspects of the present invention enable the carbon nanotubes to be dispersed or solubilized in water, an organic solvent and a water-containing organic solvent without impairing the characteristics of the carbon nanotubes itself, and there is no separation or aggregation even during long-term storage.
- a coated film having superior electrical conductivity and film formability can be obtained free of temperature dependence by coating the composition onto a base material and allowing the coated film to demonstrate the characteristics of a conducting polymer, a heterocyclic compound trimer having a sulfonic acid group and a carboxyl group or carbon nanotubes itself.
- the resulting coated film has superior moisture resistance, weather resistance and hardness.
- a third aspect of the present invention is a production method of a carbon nanotube composition
- the carbon nanotubes can be efficiently dispersed or solubilized in the solvent by this ultrasonic treatment.
- a fourth aspect of the present invention is a composite having a coated film composed of a carbon nanotube composition of the present invention on at least one surface of a base material.
- a fifth aspect of the present invention is a production method of a composite comprising coating a carbon nanotube composition of the present invention onto at least one surface of a base material, and forming a coated film by allowing to stand at an ordinary temperature or subjecting to heating treatment.
- Conducting polymer (a) is a ⁇ -conjugated polymer containing as its repeating unit phenylene vinylene, vinylene, thienylene, pyrollylene, phenylene, iminophenylene, isothianaphthene, furylene or carbazolylene and so forth.
- a so-called water soluble conducting polymer refers to a conducting polymer that has acidic groups, alkyl groups substituted with acidic groups or alkyl groups containing ether bonds on the backbone of a ⁇ -conjugated polymer or on nitrogen atoms of the polymer.
- a water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is used preferably in the present invention with respect to solubility in solvent, electrical conductivity and film formability.
- H04-268331 Japanese Unexamined Patent Application, First Publication No. H09-59376, Japanese Unexamined Patent Application, First Publication No. 2000-172384, Japanese Unexamined Patent Application, Japanese Unexamined Patent Application, First Publication No. H06-49183 and Japanese Unexamined Patent Application, First Publication No. H10-60108, are preferably used as a water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group.
- a water soluble conducting polymers having at least one of a sulfonic acid group and a carboxyl group include water soluble conducting polymers having at least one of a sulfonic acid group and a carboxyl group, an alkyl group substituted with at least one of a sulfonic acid group and a carboxyl group, or an alkyl group containing an ether bond, on the backbone of a ⁇ -conjugated polymer or nitrogen atoms of the polymer that contains as its repeating unit at least one type selected from the group consisting of non-substituted or substituted phenylene vinylene, vinylene, thienylene, pyrollylene, phenylene, iminophenylene, isothianaphthene, furylene and carbazolylene.
- a water soluble conducting polymer having a backbone that contains thienylene, pyrollylene, iminophenylene, phenylene vinylene, carbazolylene or isothianaphthene is used preferably.
- Preferable water soluble conducting polymers having at least one of a sulfonic acid group and a carboxyl group are the water soluble conducting polymers that contain 20 to 100% of at least one type of the repeating units selected from the following formulas (2) to (10) relative to the total number of repeating units throughout the entire polymer:
- R 1 and R 2 are respectively and independently selected from the group consisting of H, —SO 3 ⁇ , —SO 3 H, —R 35 SO 3 ⁇ , —R 35 SO 3 H, —OCH 3 , —CH 3 , —C 2 H 5 , —F, —Cl, —Br, —I, —N(R 35 ) 2 , —NHCOR 35 , —OH, —O ⁇ , —SR 35 , —OR 35 , —OCOR 35 , —NO 2 , —COOH, —R 35 COOH, —COOR 35 , —COR 35 , —CHO, and —CN, where R 35 represents an alkyl, aryl, or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene, or aralkylene group having 1 to 24 carbon atoms, and at least one of R 1 and R 2 is a
- R 3 and R 4 are respectively and independently selected from the group consisting of H, —SO 3 ⁇ , —SO 3 H, —R 35 SO 3 ⁇ , —R 35 SO 3 H, —OCH 3 , —CH 3 , —C 2 H 5 , —F, —Cl, —Br, —I, —N(R 35 ) 2 , —NHCOR 35 , —OH, —O ⁇ , —SR 35 , —OR 35 , —OCOR 35 , —NO 2 , —COOH, —R 35 COOH, —COOR 35 , —COR 35 , —CHO, and —CN, where R 35 represents an alkyl, aryl, or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene, or aralkylene group having 1 to 24 carbon atoms, and at least one of R 3 and R 4 is a
- R 5 to R 8 are respectively and independently selected from the group consisting of H, —SO 3 ⁇ , —SO 3 H, —R 35 SO 3 ⁇ , —R 35 SO 3 H, —OCH 3 , —CH 3 , —C 2 H 5 , —F, —Cl, —Br, —I, —N(R 35 ) 2 , —NHCOR 35 , —OH, —O ⁇ , —SR 35 , —OR 35 , —OCOR 35 , —NO 2 , —COOH, —R 35 COOH, —COOR 35 , —COR 35 , —CHO and —CN, where R 35 represents an alkyl, aryl, or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene, or aralkylene group having 1 to 24 carbon atoms, and at least one of R 5 to R 8 is a
- R 9 to R 13 are respectively and independently selected from the group consisting of H, —SO 3 ⁇ , —SO 3 H, —R 35 SO 3 ⁇ , —R 35 SO 3 H, —OCH 3 , —CH 3 , —C 2 H 5 , —F, —Cl, —Br, —I, —N(R 35 ) 2 , —NHCOR 35 , —OH, —O ⁇ , —SR 35 , —OR 35 , —OCOR 35 , —NO 2 , —COOH, —R 35 COOH, —COOR 35 , —COR 35 , —CHO, and —CN, where R 35 represents an alkyl, aryl, or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and at least one of R 9 to R 13 is a
- R 14 is selected from the group consisting of —SO 3 ⁇ , —SO 3 H, —R 42 SO 3 ⁇ , —R 42 SO 3 H, —COOH, and —R 42 COOH, where R 42 represents an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms);
- R 52 to R 57 are respectively and independently selected from the group consisting of H, —SO 3 ⁇ , —SO 3 H, —R 35 SO 3 ⁇ , —R 35 SO 3 H, —OCH 3 , —CH 3 , —C 2 H 5 , —F, —Cl, —Br, —I, —N(R 35 ) 2 , —NHCOR 35 , —OH, —O ⁇ , —SR 35 , —OR 35 , —OCOR 35 , —NO 2 , —COOH, —R 35 COOH, —COOR 35 , —COR 35 , —CHO, and —CN, where R 35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, at least one of R 52 to R 57 is a
- R 58 to R 66 are respectively and independently selected from the group consisting of H, —SO 3 ⁇ , —SO 3 H, —R 35 SO 3 ⁇ , —R 35 SO 3 H, —OCH 3 , —CH 3 , —C 2 H 5 , —F, —Cl, —Br, —I, —N(R 35 ) 2 , —NHCOR 35 , —OH, —O ⁇ , —SR 35 , —OR 35 , —OCOR 35 , —NO 2 , —COOH, —R 35 COOH, —COOR 35 , —COR 35 , —CHO, and —CN, where R 35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, at least one of R 58 to R 66 is
- R 67 to R 76 are respectively and independently selected from the group consisting of H, —SO 3 ⁇ , —SO 3 H, —R 35 SO 3 ⁇ , —R 35 SO 3 H, —OCH 3 , —CH 3 , —C 2 H 5 , —F, —Cl, —Br, —I, —N(R 35 ) 2 , —NHCOR 35 , —OH, —O ⁇ , —SR 35 , —OR 35 , —OCOR 35 , —NO 2 , —COOH, —R 35 COOH, —COOR 35 , —COR 35 , —CHO, and —CN, where R 35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, at least one of R 67 to R 76 is
- R 77 to R 81 are respectively and independently selected from the group consisting of H, —SO 3 ⁇ , —SO 3 H, —R 35 SO 3 ⁇ , —R 35 SO 3 H, —OCH 3 , —CH 3 , —C 2 H 5 , —F, —Cl, —Br, —I, —N(R 35 ) 2 , —NHCOR 35 , —OH, —O ⁇ , —SR 35 , —OR 35 , —OCOR 35 , —NO 2 , —COOH, —R 35 COOH, —COOR 35 , —COR 35 , —CHO, and —CN, where R 35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, at least one of R 77 to R 81 is
- polyethylene dioxythiophene polystyrene sulfate is also used as a preferable water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group.
- this water soluble conducting polymer does not have any sulfonic acid groups introduced into the backbone of the conducting polymer, it has a structure in which polystyrene sulfonate is added as a dopant.
- This polymer can be produced by polymerizing 3,4-ethylene dioxythiophene (Bayer, Baytron M) with an oxidizing agent such as iron toluene sulfonate (Bayer, Baytron C). In addition, this polymer can also be acquired in the form of Baytron P (Bayer).
- An even more preferable water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is a water soluble conducting polymer that contains 20 to 100% of the repeating unit represented by the following formula (11) relative to the total number of repeating units throughout the entire polymer:
- R 15 to R 32 are respectively and independently selected from the group consisting of H, —SO 3 ⁇ , —SO 3 H, —R 35 SO 3 ⁇ , —R 35 SO 3 H, —OCH 3 , —CH 3 , —C 2 H 5 , —F, —Cl, —Br, —I, —N(R 35 ) 2 , —NHCOR 35 , —OH, —O ⁇ , —SR 35 , —OR 35 , —OCOR 35 , —NO 2 , —COOH, —R 35 COOH, —COOR 35 , —COR 35 , —CHO, and —CN, where R 35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms
- a substituent added to the aromatic ring is preferably an alkyl group, alkoxy group or halogen group, from the perspective of electrical conductivity and solubility, and water soluble conducting polymers having an alkoxy group are the most preferable.
- the most preferable water soluble conducting polymer among these combinations is shown in the following formula (12):
- R 33 represents one group selected from the group consisting of a sulfonic acid group, carboxyl group, their alkaline metal salts, ammonium salts and substituted ammonium salts
- R 34 represents one group selected from the group consisting of a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, dodecyl group, tetracosyl group, methoxy group, ethoxy group, n-propoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, heptoxy group, hexoxy group, octoxy group, dodecoxy group, tetracoxy group, fluoro group, chloro group and bromo group
- X represents an arbitrary number such that 0 ⁇ x ⁇ 1
- n represents the degree of polymer
- a particularly preferable water soluble conducting polymer is a water soluble conducting polymer obtained by polymerizing at least one type of alkoxy group-substituted aminobenzene sulfonic acid, its alkaline metal salt, ammonium salt and substituted ammonium salt, with an oxidizing agent in a solution containing a basic compound.
- acidic solutions used in doping treatment include aqueous solutions containing inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as p-toluene sulfonic acid, camphasulfonic acid, benzoic acid and derivatives having these backbones; and high molecular weight acids such as polystyrene sulfonic acid, polyvinyl sulfonic acid, poly(2-acrylamide-2-methylpropane) sulfonic acid, polyvinyl sulfuric acid and derivatives having these backbones; or mixed solutions of water and an organic solvent.
- inorganic acids, organic acids and high molecular weight acids may each be used alone or they may be used as a mixture of two or more types at an arbitrary ratio.
- Ht represents a heteroatom group selected from the group consisting of NR 154 , S, O, Se and Te, and R 154 represents a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms;
- X a ⁇ represents at least one type of anion selected from the group consisting of anions having a valence of 1 to 3 consisting of a chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methane sulfonate ion, p-toluene sulfonate ion, trifluoroacetate ion and trifluoromethane sulfonate ion; a represents the ion valence of X and is an integer of 1 to 3; and m represents the doping ratio and has a value of 0 to 3.0).
- Heterocyclic compound trimer (i) is preferably a heterocyclic compound trimer represented by formula (17):
- an example of an asymmetrical heterocyclic compound trimer (i) is the indole derivative trimer oxidant represented by general formula (18):
- R 125 to R 136 are substituents respectively and independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, linear or branched alkoxy group having 1 to 24 carbon atoms, linear or branched acyl group having 2 to 24 carbon atoms, aldehyde group, carboxylic acid group and its alkaline metal salt, ammonium salt and substituted ammonium salt, linear or branched carboxylic ester group having 2 to 24 carbon atoms, sulfonic acid group and its alkaline metal salt, ammonium salt and substituted ammonium salt, linear or branched sulfonic ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, amido group, dicyanovinyl group, alkyl (linear or branched alkyl group having 1 to 8 carbon atoms) oxycarbonylcyanovinyl group, nitro
- X a ⁇ represents at least one type of anion selected from the group consisting of anions having a valence of 1 to 3 consisting of a chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogensulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-toluene sulfonate ion, trifluoroacetate ion and trifluoromethane sulfonate ion; a represents the ion valence of X and is an integer of 1 to 3; and m represents the doping ratio and has a value of 0 to 3.0).
- R 137 to R 148 are substituents respectively and independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, linear or branched alkoxy group having 1 to 24 carbon atoms, linear or branched acyl group having 2 to 24 carbon atoms, aldehyde group, carboxyl group, linear or branched carboxylic ester group having 2 to 24 carbon atoms, sulfonic acid group, linear or branched sulfonic ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, amido group, dicyanovinyl group, alkyl (linear or branched alkyl group having 1 to 8 carbon atoms) oxycarbonylcyanovinyl group, nitrophenylcyanovinyl group and halogen group;
- Ht represents a heteroatom group selected from the group consisting of NR 154 , S, O, Se and Te, and R 154 represents a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms;
- X a ⁇ represents at least one type of anion selected from the group consisting of anions having a valence of 1 to 3 consisting of a chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogensulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-toluene sulfonate ion, trifluoroacetate ion and trifluoromethane sulfonate ion; a represents the ion valence of X and is an integer of 1 to 3; and m represents the doping ratio and has a value of 0 to 3.0).
- trimers having an acidic group such as carboxyl group-substituted heterocyclic compound trimers, and sulfonic acid group-substituted heterocyclic compound trimers can be used preferably in terms of safety with respect to people and the environment since water can be used for the solvent due to their water solubility.
- indole derivatives represented by general formula (20) used in the synthesis method of the heterocyclic compound trimer (i) include carboxyl group-substituted indoles, their alkaline metal salts, ammonium salts and substituted ammonium salts such as indole-4-carboxylic acid, indole-5-carboxylic acid, indole-6-carboxylic acid and indole-7-carboxylic acid; sulfonic acid group-substituted indoles, their alkaline metal salts, ammonium salts and substituted ammonium salts such as indole-4-sulfonic acid, indole-5-sulfonic acid, indole-6-sulfonic acid and indole-7-sulfonic acid; alkyl group-substituted indoles such as 4-methylindole, 5-methylindole, 6-methylindole, 7-methylindole
- benzo[b]furans represented by general formula (20) include carboxyl group-substituted benzo[b]furans, their alkaline metal salts, ammonium salts and substituted ammonium salts such as benzo[b]furan-4-carboxylic acid, benzo[b]furan-5-carboxylic acid, benzo[b]furan-6-carboxylic acid and benzo[b]furan-7-carboxylic acid; sulfonic acid group-substituted benzo[b]furans, their alkaline metal salts, ammonium salts and substituted ammonium salts such as benzo[b]furan-4-sulfonic acid, benzo[b]furan-5-sulfonic acid, benzo[b]furan-6-sulfonic acid and benzo[b]furan-7-sulfonic acid; alkyl group-substituted benzo[b]furans such as 4-methylbenzo[b]furan, 5-
- benzo[b]selenophenes represented by general formula (20) include carboxyl group-substituted benzo[b]selenophenes, their alkaline metal salts, ammonium salts and substituted ammonium salts such as benzo[b]selenophene-4-carboxylic acid, benzo[b]selenophene-5-carboxylic acid, benzo[b]selenophene-6-carboxylic acid and benzo[b]selenophene-7-carboxylic acid; sulfonic acid group-substituted benzo[b]selenophenes, their alkaline metal salts, ammonium salts and substituted ammonium salts such as benzo[b]selenophene-4-sulfonic acid, benzo[b]selenophene-5-sulfonic acid, benzo[b]selenophene-6-sulfonic acid and benzo
- benzo[b]tellurophenes represented by general formula (20) include carboxyl group-substituted benzo[b]tellurophenes, their alkaline metal salts, ammonium salts and substituted ammonium salts such as benzo[b]tellurophene-4-carboxylic acid, benzo[b]tellurophene-5-carboxylic acid, benzo[b]tellurophene-6-carboxylic acid and benzo[b]tellurophene-7-carboxylic acid; sulfonic acid group-substituted benzo[b]tellurophenes, their alkaline metal salts, ammonium salts and substituted ammonium salts such as benzo[b]tellurophene-4-sulfonic acid, benzo[b]tellurophene-5-sulfonic acid, benzo[b]tellurophene-6-sulfonic acid and benzo[b]tellurophene-7-
- oxidizing agent used in the aforementioned synthesis method of heterocyclic compound trimer (i), and examples include ferric chloride hexahydrate, anhydrous ferric chloride, ferric nitrate nonahydrate, ferric sulfate n-hydrate, ammonium ferric sulfate dodecahydrate, ferric perchlorate n-hydrate, ferric tetrafluoroborate, cupric chloride, cupric nitrate, cupric sulfate, cupric tetrafluoroborate, nitrosonium tetrafluoroborate, hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate and potassium periodate.
- these solvents may be used alone or they may used as a mixture of two or more types at an arbitrary ratio.
- acetone, acetonitrile, 1,4-dioxane, ⁇ -butyl lactone and N,N-dimethylformamide are used preferably, while acetonitrile is used most preferably in terms of practical use.
- the reaction is particularly preferably carried out in the presence of water and the organic solvent.
- the molar ratio of the heterocyclic compound to water is 1:1000 to 1000:1 and preferably 1:100 to 100:1.
- the oxidizing agent contains crystalline water, that crystalline water is also calculated as water.
- the ratio of water is low, the reaction proceeds explosively, and simultaneous to excessive oxidation of the trimer and deterioration of its structure, X a ⁇ serving as dopant may be unable to efficiently dope the trimer, thereby resulting in decreased electrical conductivity.
- the ratio of water is excessively high, the progression of the oxidation reaction is obstructed which may cause a decrease in reaction yield.
- This anion is most preferably a monovalent anion such as chlorine ion.
- dopant X a ⁇ in the indole derivative trimer is a chlorine ion, X a ⁇ and in the case of carrying out polymerization using cupric trifluoroacetate, dopant X a ⁇ is a trifluoroacetate ion.
- the heterocyclic compound trimer (i) may have more superior electrical conductivity by having a layered structure.
- the heterocyclic compound trimer (i) preferably has a layered structure in which the interlayer interval is 0.1 to 5.0 nm, more preferably 0.1 to 2.0 nm and particularly preferably 0.1 to 1.0 nm.
- a compound having such a microlayered structure has satisfactory rigidity, strength, heat resistance and so forth. If the interlayer interval is 0.1 nm or more, the layered structure tends to become more stable, and if the interlayer interval is 2.0 nm or less, the hopping transfer of electrons between trimers becomes easier, thereby tending to improve electrical conductivity.
- acidic solutions used for doping treatment include aqueous solutions containing inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as p-toluene sulfonic acid, camphasulfonic acid, benzoic acid and derivatives having these backbones, and high molecular weight acids such as polystyrene sulfonic acid, polyvinyl sulfonic acid, poly(2-acrylamide-2-methylpropane) sulfonic acid, polyvinyl sulfuric acid and derivatives having these backbones, or mixed solutions of water and organic solvent.
- these inorganic acids, organic acids and high molecular weight acids may each be used alone or they may be used as a mixture of two or more types at an arbitrary ratio.
- the indole derivative trimer oxidant represented by general formula (18), which is an asymmetrical heterocyclic compound trimer (i) can be obtained by a production method in which an asymmetrical indole derivative trimer is subjected to oxidation treatment with a known oxidizing agent in a solvent, there are cases in which the indole derivative trimer oxidant can be obtained as a result of the oxidation reaction proceeding more efficiently without using an oxidizing agent by simply dedoping an indole derivative trimer doped with an external dopant X a ⁇ from the doped form by deacidification treatment or reduction treatment, thereby making this production method extremely suitable industrially.
- solvent (b) which is an essential component of the present invention, provided it dissolves or disperses conducting polymer (a) or the heterocyclic compound trimer (i), carbon nanotubes (c), high molecular weight compound (d), basic compound (e), surfactant (f), silane coupling agent (g) and colloidal silica (h).
- Examples of the solvent (b) that are used preferably include water, alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol and butanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone and methyl isobutyl ketone; ethylene glycols such as ethylene glycol, ethylene glycol methyl ether and ethylene glycol mono-n-propyl ether; propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and propylene glycol propyl ether; amides such as dimethylformamide and dimethylacetoamide; pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; hydroxyesters such as dimethylsulfoxide, ⁇ -butyrolactone, methyl lactate,
- water or a water-containing organic solvent is used preferably for the solvent (b) in consideration of the solubility of the water soluble conducting polymer and dispersivity of carbon nanotubes (c).
- carbon nanotubes (c) As a more detailed explanation of the carbon nanotubes (c), an example of such a carbon nanotube is a substance in which the outer diameter is extremely small on the order of nanometers and which comprises a plurality of cylinders, in which the surfaces of graphite-like carbon atoms in layers several atoms thick are rounded, that form a nested structure.
- carbon nanohorns in which one side of a carbon nanotube is closed, or cup-shaped nanocarbon substances, in which a hole is formed in the top, can also be used.
- carbon nanotubes (c) obtained by the aforementioned production methods are single-walled carbon nanotubes, and highly purified carbon nanotubes, which are obtained by various purification methods such as washing, centrifugal separation, filtration, oxidation and chromatography, are used preferably since they adequately demonstrate various functions.
- high molecular weight compound (d) in the carbon nanotube composition of the present invention further improves the base material adhesion and strength of the coated film.
- high molecular weight compound (d) in the present invention can be dissolved or dispersed (emulsion formation) in the solvent (b) used in the present invention, specific examples of which include polyvinyl alcohols such as polyvinyl alcohol, polyvinyl formal and polyvinyl butyral; polyacrylamides such as polyacrylamide, poly(N-t-butylacrylamide and polyacrylamide methyl propane sulfonate; polyvinyl pyrrolidones; polystyrene sulfonates and their sodium salts; cellulose, alkyd resin, melamine resin, urea resin, phenol resin, epoxy resin, polybutadiene resin, acrylic resin, urethane resin, vinyl ester resin, urea resin, polyimide resin, maleic acid resin, polycarbonate resin, vinyl acetate resin, chlorinated polyethylene resin, chlorinated polypropylene resin, styrene resin, acrylic/styrene copolymer resin, vinyl
- high molecular weight compounds (d) water soluble high molecular weight compounds or high molecular weight compounds that form an emulsion in aqueous systems are used preferably in consideration of solubility in solvent, stability of the resulting composition and electrical conductivity, and high molecular weight compounds having an anion group are used particularly preferably.
- those used by mixing one or two or more types of aqueous acrylic resin, aqueous polyester resin, aqueous urethane resin and aqueous chlorinated polyolefin resin are used preferably.
- the basic compound (e) that composes a carbon nanotube composition of the present invention is effective for dedoping the water soluble conducting polymer or the heterocyclic compound trimer and improving solubility in solvent (b) as a result of being added to the carbon nanotube composition.
- basic compound (e) promotes solubilization or dispersion of the carbon nanotubes (c) in the solvent (b).
- R 45 to R 47 respectively and mutually independently represent hydrogen, alkyl group having 1 to 4 carbon atoms (C 1 to C 4 ), CH 2 OH, CH 2 CH 2 OH, CONH 2 or NH 2 ).
- R 48 to R 51 respectively and mutually independently represent hydrogen, alkyl group having 1 to 4 carbon atoms (C 1 to C 4 ), CH 2 OH, CH 2 CH 2 OH, CONH 2 or NH 2 , X ⁇ represents OH ⁇ , 1 ⁇ 2.SO 4 2 ⁇ , NO 3 ⁇ , 1 ⁇ 2.CO 3 2 ⁇ , HCO 3 ⁇ , 1 ⁇ 2.(COO) 2 2 ⁇ or R′COO ⁇ , and R′ represents an alkyl group having 1 to 3 carbon atoms (C 1 to C 3 )).
- cyclic saturated amines that are used preferably include piperidine, pyrrolidine, morpholine, piperazine, derivatives having these backbones and their ammonium hydroxide compounds.
- inorganic bases preferably include sodium hydroxide, potassium hydroxide, lithium hydroxide and other hydroxides.
- Two or more types of the basic compound (e) may be used by mixing.
- electrical conductivity can be further improved by using a mixture of an amine and an ammonium salt.
- Specific examples of such mixtures include NH 3 /(NH 4 ) 2 CO 3 , NH 3 /(NH 4 )HCO 3 , NH 3 /CH 3 COONH 4 , NH 3 /(NH 4 ) 2 SO 4 , N(CH 3 ) 3 /CH 3 COONH 4 and N(CH 3 ) 3 /(NH 4 ) 2 SO 4 .
- the ratio of amine to ammonium salt is preferably 1/10 to 10/0.
- a carbon nanotube composition of the present invention is able to form a high-performance film without undergoing separation of aggregation even when stored for a long period of time by solubilizing or dispersing carbon nanotubes (c) with the aforementioned conducting polymer (a) or heterocyclic compound trimer (i), solvent (b), carbon nanotubes (c), high molecular weight compound (d) and basic compound (e) alone, addition of surfactant (f) not only makes it possible to further promote solubilization or dispersion, but also improves flatness, coatability and electrical conductivity.
- surfactant (f) examples include anionic surfactants such as alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl carboxylic acid, alkyl naphthalene sulfonic acid, ⁇ -olefin sulfonic acid, dialkyl sulfosuccinic acid, ⁇ -sulfonated fatty acids, N-methyl-N-oleoyltaurine, petroleum sulfonic acid, alkyl sulfuric acids, sulfated oils, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene styrenated phenyl ether sulfuric acid, alkyl phosphoric acids, polyoxyethylene alkyl ether phosphoric acid, polyoxyethylene alkyl phenyl ether phosphoric acid, naphthalene sulfonic acid formaldehyde condensates and their salts; cationic surfactants such as primary to terti
- a silane coupling agent (g) can be used in the present invention in combination with the carbon nanotube composition of the present invention containing the conducting polymer (a) or the heterocyclic compound trimer (i), the solvent (b), the carbon nanotubes (c), the high molecular weight compound (d), the basic compound (e) and the surfactant (f).
- the moisture resistance of a coated film obtained from a carbon nanotube composition that uses a silane coupling agent (g) is remarkably improved.
- a silane coupling agent (g) represented by the following formula (1) is used for silane coupling agent (g):
- R 242 , R 243 and R 244 respectively and independently represent a group selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, linear or branched alkoxy group having 1 to 6 carbon atoms, amino group, acetyl group, phenyl group and halogen group, X represents the following:
- l and m represent values from 0 to 6
- Y represents a group selected from the group consisting of a hydroxyl group, thiol group, amino group, epoxy group and epoxycyclohexyl group).
- examples of silane coupling agents having an epoxy group include ⁇ -glycidyloxypropyl trimethoxysilane, ⁇ -glycidyloxypropyl methyl dimethoxysilane and ⁇ -glycidyloxypropyl triethoxysilane.
- silane coupling agents having an amino group examples include ⁇ -aminopropyl triethoxysilane, ⁇ -aminoethyl trimethoxysilane and ⁇ -aminopropoxypropyl trimethoxysilane.
- silane coupling agents having a thiol group examples include ⁇ -mercaptopropyl trimethoxysilane and ⁇ -mercaptoethyl methyl dimethoxysilane.
- silane coupling agents having a hydroxyl group examples include ⁇ -hydroxyethoxyethyl triethoxysilane and ⁇ -hydroxypropyl trimethoxysilane.
- silane coupling agents having an epoxycyclohexyl group examples include ⁇ -(3,4-epoxycyclohexyl)ethyl trimethoxysilane.
- colloidal silica (h) can also be used in a crosslinked carbon nanotube composition containing the conducting polymer (a) or the heterocyclic compound trimer (i), the solvent (b), the carbon nanotubes (c), the high molecular weight compound (d), the basic compound (e), the surfactant (f) and the silane coupling agent (g).
- a coated film obtained from a carbon nanotube composition that combines the use of colloidal silica (h) has remarkably improved surface hardness and weather resistance.
- colloidal silica having a particle diameter within the range of 1 nm to 300 nm, preferably 1 nm to 150 nm and more preferably 1 nm to 50 nm is used for the colloidal silica (h).
- the particle diameter is too large, hardness becomes inadequate or the solution stability of the colloidal silica itself ends up decreasing.
- the usage ratio between the aforementioned conducting polymer (a) or heterocyclic compound trimer (i) and the solvent (b) is preferably 0.001 to 50 parts by mass, and more preferably 0.01 to 30 parts by mass of the conducting polymer (a) or the heterocyclic compound trimer (i) relative to 100 parts by mass of the solvent (b). If the ratio of the conducting polymer (a) or the heterocyclic compound trimer (i) is less than 0.001 parts by mass, electrical conductivity deteriorates or the solubilization or dispersion efficiency of carbon nanotubes (c) decreases.
- the usage ratio between the aforementioned carbon nanotubes (c) and solvent (b) is preferably 0.0001 to 20 parts by mass, and more preferably 0.001 to 10 parts by mass of the carbon nanotubes (c) relative to 100 parts by mass of the solvent (b). If the ratio of the carbon nanotubes (c) used is less than 0.0001 parts by mass, performance such as electrical conductivity resulting from the use of carbon nanotubes (c) decreases. On the other hand, if the amount used exceeds 20 parts by mass, the solubilization or dispersion efficiency of the carbon nanotubes (c) decreases.
- the usage ratio between the aforementioned high molecular weight compound (d) and solvent (b) is preferably 0.1 to 400 parts by mass, and more preferably 0.5 to 300 parts by mass of the high molecular weight compound (d) relative to 100 parts by mass of the solvent (b). If the ratio of high molecular weight compound (d) is greater than or equal to 0.1 parts by mass, film formability, moldability and strength are further improved, while on the other hand, when the ratio of the high molecular weight compound (d) is less than or equal to 400 parts by mass, there is little decrease in the solubility of the water soluble conducting polymer (a) or the heterocyclic compound trimer (i) or the carbon nanotubes (c), and a high degree of electrical conductivity is maintained.
- the usage ratio between the aforementioned basic compound (e) and solvent (b) is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass of the basic compound (e) relative to 100 parts by mass of the solvent (b).
- the usage ratio of the basic compound (e) is within this range, the solubility of the water soluble conducting polymer improves, the solubilization or dispersion of the carbon nanotubes (c) in the solvent (b) is promoted, and electrical conductivity improves.
- the usage ratio between the aforementioned surfactant (f) and solvent (b) is preferably 0.0001 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass of the surfactant (f) relative to 100 parts by mass of the solvent (b).
- coatability improves if the usage ratio of the surfactant (f) exceeds 10 parts by mass, in addition to the occurrence of phenomena such as deterioration of electrical conductivity, the solubilization or dispersion of the carbon nanotubes (c) decreases.
- the usage ratio between the aforementioned silane coupling agent (g) and solvent (b) is preferably 0.001 to 20 parts by mass, and more preferably 0.01 to 15 parts by mass of the silane coupling agent (g) to 100 parts by mass of the solvent (b). If the usage ratio of the silane coupling agent (g) is less than 0.001 parts by mass, the amount of improvement in at least one of moisture resistance and solvent resistance becomes comparatively smaller, while on the other hand, if the usage ratio exceeds 20 parts by mass, solubility, flatness, transparency and electrical conductivity may worsen.
- the usage ratio between the aforementioned colloidal silica (h) and solvent (b) is preferably 0.001 to 100 parts by mass, and more preferably 0.01 to 50 parts by mass of the colloidal silica (h) relative to 100 parts by mass of the solvent (b). If the ratio of the colloidal silica (h) is 0.001 parts by mass or more, the amount of improvement in moisture resistance, weather resistance and hardness increases. On the other hand, if the ratio exceeds 100 parts by mass, solubility, flatness, transparency and electrical ductivity worsen.
- various types of known substances can be added to the carbon nanotube composition of the present invention as necessary, examples of which include plasticizers, dispersants, coated surface adjusters, fluidity adjusters, ultraviolet absorbers, antioxidants, preservatives, adhesion assistants and thickeners.
- an conducting substance can be incorporated in the carbon nanotube composition of the present invention in order to further improve electrical conductivity.
- the conducting substances include carbon fibers, conducting carbon black, graphite and other carbon-based substances, tin oxide, zinc oxide and other metal oxides, and metals such as silver, nickel and copper.
- a stirring or kneading device such as an ultrasonic wave device, homogenizer, spiral mixer, planetary mixer, dispenser or hybrid mixer is used when mixing these components.
- an ultrasonic wave device such as an ultrasonic wave device, homogenizer, spiral mixer, planetary mixer, dispenser or hybrid mixer is used when mixing these components.
- a homogenizer ultrasonic homogenizer
- the intensity and treatment time of the ultrasonic waves should be adequate for uniformly dispersing or dissolving the carbon nanotubes (c) in the solvent (b).
- the rated output of an ultrasonic oscillator is preferably within the range of 0.1 to 2.0 watts/cm 2 , and more preferably 0.3 to 1.5 watts/cm 2 , per unit bottom surface area of the ultrasonic oscillator, and the oscillation frequency is preferably within the range of 10 to 200 KHz and more preferably 20 to 100 KHz.
- the duration of ultrasonic irradiation treatment is preferably 1 minute to 48 hours and more preferably 5 minutes to 48 hours. Dispersion or dissolution is preferably subsequently improved by using a ball-type kneading device such as a ball mill, vibration mill, sand mill or roll mill.
- Examples of base materials that form a coated film by coating with the carbon nanotube composition in the present invention include high molecular weight compounds, plastics, wood, paper, ceramics, fibers, non-woven fabrics, carbon fibers, carbon fiber paper and their films, foams, porous films, elastomers and glass plates.
- high molecular weight compounds, plastics and films include polyethylene, polyvinyl chloride, polypropylene, polystyrene, ABS resin, AS resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, polyvinylidene fluoride, polyester, polyamide, polyimide, polyaramid, polyphenylene sulfide, polyether ethyl ketone, polyphenylene ether, polyether nitrile, polyamide imide, polyether sulfone, polysulfone, polyether imide, polybutylene terephthalate, polyurethane and their films, foams and elastomers.
- the surfaces of these films are preferably subjected to corona discharge treatment or plasma treatment for the purpose of improving adhesion of the coated film.
- a coated film in the present invention is formed on the surface of a base material by a method used for ordinary coating.
- methods used include coating methods using a gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, fountain coater, rod coater, air doctor coater, knife coater, blade coater, cast coater or screen coater, spraying methods such as air spraying or airless spraying, and immersion methods such as dipping.
- the carbon nanotube composition can be allowed to stand at normal temperatures after coating onto the surface of a base material, the coated film can also be heat-treated.
- the performing of heat treatment is preferable since the crosslinking reaction between the carbon nanotubes (c), the high molecular weight compound (d) and the basic compound (e) and the conducting polymer (a) or the heterocyclic compound trimer (i) can be further promoted, moisture resistance can be imparted in a shorter period of time, the residual amount of the solvent (b) can be further reduced and electrical conductivity can be further improved.
- the temperature of heat treatment is preferably 20 to 250° C. and particularly preferably 40 to 200° C. If the temperature of heat treatment is higher than 250° C., the conducting polymer (a) itself or the heterocyclic compound trimer (i) itself is decomposed, and electrical conductivity may be degraded.
- the film thickness of the coated film is preferably within the range of 0.01 to 100 ⁇ m, and more preferably within the range of 0.1 to 50 ⁇ m.
- the composite of the present invention has superior electrical conductivity even if used as is, electrical conductivity can be further improved by doping with acid after having formed a coated film of the carbon nanotube composition on at least one surface of the base material, and then allowing to stand at ordinary temperatures or heat treating.
- doping can be carried out by immersing a conductor in an acidic solution.
- acidic solutions include aqueous solutions containing inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as p-toluene sulfonic acid, camphasulfonic acid, benzoic acid, and derivatives having their backbones, and high molecular weight acids such as polystyrene sulfonic acid, polyvinyl sulfonic acid, poly(2-acrylamide-2-methylpropane) sulfonic acid, polyvinyl sulfuric acid and derivatives having their backbones, as well as mixed solvents of water and organic solvent.
- these inorganic acids, organic acids and high molecular weight acids may each be used alone or two or more types may be used as a mixture at an arbitrary ratio.
- Poly(2-sulfo-1,4-iminophenylene) was synthesized according to a known method (J. Am. Chem. Soc., (1991), 113, 2665-2666).
- the sulfonic acid content of the resulting polymer was 52% relative to the aromatic ring.
- the volumetric resistance of this conducting polymer (A-3) was 50 ⁇ cm.
- carbon nanotube composition 10 0.1 part by mass of carbon nanotubes and 20 parts by mass of acrylic resin in an aqueous emulsion form (Dianal MX-1845, Mitsubishi Rayon Co., Ltd.) were mixed in 100 parts by mass of water at room temperature to prepare a carbon nanotube composition 10.
- indole derivative trimers In the following production examples of indole derivative trimers, elementary analysis and measurements were carried out using the Thermoquest EA1110. Electrical conductivity was measured with the MCP-T350 conductivity gauge (Mitsubishi Chemical) (four probe method, electrode interval: 1 mm). Moreover, X-ray diffraction (XRD) was measured with the RINT-1100 (Rigaku Corporation) (tube: CuK ⁇ X-rays).
- reaction solution was aspiration filtered with a Kiriyama funnel, washed with acetonitrile and then methanol and dried to obtain 1.12 g of light green 6,11-dihydro-5H-diindolo[2,3-a:2′,3′-c]carbazole-2,9,14-tricarboxylic acid (indole-5-carboxylic acid trimer) (yield: 79%).
- compositions obtained in the aforementioned examples and comparative examples were coated onto a glass plate according to the bar coater method (using a No. 5 bar coater). After drying for 5 minutes at 80° C. to form a coated film and then observing its appearance, the surface resistance was measured. Those results are shown in Table 1.
- carbon nanotube composition 8 obtained in Example 8 the composition was coated onto a glass plate according to the bar coater method (using a No. 5 bar coater) and dried for 5 minutes at 150° C. to form a coated film followed by immersing for 5 minutes in a 1 mol/liter aqueous solution of sulfuric acid. After then drying for 5 minutes at 80° C. and observing the appearance, the surface resistance was measured.
- compositions obtained in the aforementioned examples and comparative examples were subjected to ultrasonic treatment for 1 hour (UA100, Shinmei Daiko, 36 KHz), and after visually observing the states of the compositions, the compositions were coated onto a glass plate according to the bar coater method (using a No. 5 bar coater). After drying for 5 minutes at 80° C. to form a coated film and then observing its appearance, the surface resistance was measured. Those results are shown in Table 1.
- carbon nanotube composition 8 obtained in Example 8 the composition was coated onto a glass plate according to the bar coater method (using a No. 5 bar coater) and dried for 5 minutes at 150° C. to form a coated film followed by immersing for 5 minutes in a 1 mol/liter aqueous solution of sulfuric acid. After then drying for 5 minutes at 80° C. and observing the appearance, the surface resistance was measured.
- the two probe method (electrode interval: 20 mm) was used to measure surface resistance under conditions of 25° C. and 15% RH for surface resistance values of 10 8 ⁇ or more, while the four probe method (electrode interval: 5 mm) was used for surface resistance values of 10 7 ⁇ or less. Those results are shown in Table 1.
- Example 1 No ⁇ 6.6 ⁇ 10 3 ⁇ Yes ⁇ 1.9 ⁇ 10 2 ⁇
- Example 2 No ⁇ 8.3 ⁇ 10 4 ⁇ Yes ⁇ 6.2 ⁇ 10 3 ⁇
- Example 3 No ⁇ 3.5 ⁇ 10 4 ⁇ Yes ⁇ 1.5 ⁇ 10 3 ⁇
- Example 4 No ⁇ 1.1 ⁇ 10 6 ⁇ Yes ⁇ 8.6 ⁇ 10 4 ⁇
- Example 5 No ⁇ 2.9 ⁇ 10 3 ⁇ Yes ⁇ 5.3 ⁇ 10 2 ⁇
- Example 6 No ⁇ 9.2 ⁇ 10 3 ⁇ Yes ⁇ 7.9 ⁇ 10 2 ⁇
- Example 7 No ⁇ 5.7 ⁇ 10 5 ⁇ Yes ⁇ 2.5 ⁇ 10 4 ⁇
- Example 8 No ⁇ 6.4 ⁇ 10 4 ⁇ Yes ⁇ 3.9 ⁇ 10 3 ⁇
- Example 9 No ⁇ 1.8 ⁇ 10 4 ⁇ Yes ⁇ 1.3 ⁇ 10 3 ⁇
- Example 10 No ⁇ 4.2 ⁇ 10 6 ⁇ Yes ⁇ 3.9 ⁇ 10 5
- the solutions of the carbon nanotube compositions of the present examples were uniformly dispersed or dissolved, and uniform coated films were formed.
- they also demonstrated low values of surface resistance.
- surface resistance values were able to be lowered even more by performing ultrasonic treatment.
- the carbon nanotube composition of the present invention can be used by simple coating methods such as coating, spraying, casting, and dipping for various types of antistatic agents, capacitors, batteries, fuel cells and their polymer electrolyte membranes, electrode layers, catalyst layers, gas diffusion layers, separators and other members, EMI shields, chemical sensors, display elements, non-linear materials, preservatives, adhesives, fibers, spinning materials, antistatic coatings, corrosion-resistant coatings, electrodeposition coatings, plating primers, conducting primers for electrostatic coating, electrical corrosion prevention and improvement of battery charge storage.
- simple coating methods such as coating, spraying, casting, and dipping for various types of antistatic agents, capacitors, batteries, fuel cells and their polymer electrolyte membranes, electrode layers, catalyst layers, gas diffusion layers, separators and other members, EMI shields, chemical sensors, display elements, non-linear materials, preservatives, adhesives, fibers, spinning materials, antistatic coatings, corrosion-resistant coatings, electrodeposition coatings, plating primers, conducting
- a composite of the present invention is used as an industrial packaging material for semiconductors, electrical appliance electronic components and so forth, an antistatic film of electronic photography and recording materials such as overhead projector film and slide film, for preventing accumulation of electrical charge of magnetic recording tape such as audio tape, video tape, computer tape and floppy disks, for LSI wiring of electronic devices, electron guns (sources) and electrodes of field emission displays (FED), hydrogen storage agent, for prevention of accumulation of electrical charge on the surfaces of input and display devices such as transparent touch panel, electroluminescent display, and liquid crystal displays, and as light emitting materials that form transparent electrodes and organic electroluminescent elements, buffer materials, electron transfer materials, hole transfer materials, fluorescent materials, thermal transfer sheets, transfer sheets, thermal transfer imaging sheets and imaging sheets.
- an antistatic film of electronic photography and recording materials such as overhead projector film and slide film, for preventing accumulation of electrical charge of magnetic recording tape such as audio tape, video tape, computer tape and floppy disks, for LSI wiring of electronic devices, electron guns (sources) and electrodes of field
Abstract
The object of the present invention is to provide a carbon nanotube composition that does not impair the characteristics of the carbon nanotubes itself, allows the carbon nanotubes to be dispersed or solubilized in a solvent, does not cause separation or aggregation of the carbon nanotubes even during long-term storage, has superior electrical conductivity, film formability and moldability, can be easily coated or covered onto a base material, and the resulting coated film has superior moisture resistance, weather resistance and hardness; a composite having a coated film composed thereof; and, their production methods. In order to achieve this object, the present invention provides a carbon nanotube composition that contains a conducting polymer (a) or heterocyclic compound trimer (i), a solvent (b) and carbon nanotubes (c), and may additionally contain a high molecular weight compound (d), a basic compound (e), a surfactant (f), a silane coupling agent (g) and colloidal silica (h) as necessary; a composite having a coated film composed of the composition; and, their production methods.
Description
- The present invention relates to a carbon nanotube composition, a composite having a coated film composed of the same, and their production methods.
- Ever since carbon nanotubes were first discovered by Iijima, et al. in 1991 (S. Iijima, Nature, 354, 56 (1991)), their physical properties have been evaluated and their functions have been elucidated, and extensive research and development have been conducted on their application. However, since carbon nanotubes are produced in an entangled state, they have the shortcoming of being extremely bothersome to handle. In the case of mixing into resins and solutions, there is also the problem of the carbon nanotubes becoming increasingly aggregated, thereby preventing them from demonstrating their inherent characteristics.
- Consequently, attempts have been made to uniformly disperse or solubilize carbon nanotubes in solvents or resins by subjecting them to physical treatment or chemical modification.
- For example, a method has been proposed in which single-walled carbon nanotubes are cut into short pieces and dispersed by subjecting to ultrasonic treatment in strong acid (R. E. Smalley, et al., Science, 280, 1253 (1998)). However, since treatment is carried out in strong acid, the procedure is complex and not suitable for industrial applications, while the dispersion effects cannot be said to be adequate.
- Therefore, by noticing that both ends of single-walled carbon nanotubes cut in the manner proposed above are open, and that they are terminated with oxygen-containing functional groups such as carboxylic acid groups, it was proposed that carbon nanotubes be made soluble in solvent by introducing long-chain alkyl groups by reacting with an amine compound after having converted the carboxylic acid groups into acid chloride (J. Chen, et al., Science, 282, 95 (1998)). However, in this method, since long-chain alkyl groups are introduced into single-walled carbon nanotubes by covalent bonding, there was still the problem of damage to the graphene sheet structure of the carbon nanotubes and effects on the characteristics of the carbon nanotubes itself.
- Another attempt to produce water soluble single-walled carbon nanotubes was reported that comprising introducing substituents containing ammonium ions in pyrene molecules by utilizing the fact that pyrene molecules are adsorbed onto the surfaces of carbon nanotubes by strong interaction, and subjecting these to ultrasonic treatment in water together with single-walled carbon nanotubes to non-covalently adsorb them to the single-walled carbon nanotubes (Nakajima, et al., Chem. Lett., 638 (2002)). According to this method, although damage to the graphene sheet structure is inhibited due to the non-covalent bonding chemical modification, since non-conducting pyrene compounds are present, there is the problem of a decrease in the conductivity of the resulting carbon nanotubes.
- The object of the present invention is to provide a carbon nanotube composition that does not impair the characteristics of the carbon nanotubes itself, allows the carbon nanotubes to be dispersed or solubilized in water, organic solvents, water-containing organic solvents and other solvents, does not cause separation or aggregation of the carbon nanotubes even during long-term storage, has superior electrical conductivity, film formability and moldability, can be easily coated or covered onto a base material, and the resulting coated film has superior moisture resistance, weather resistance and hardness. The object of the present invention is also to provide a composite having a coated film comprising the carbon nanotube composition as well as production methods of the carbon nanotube composition and the coated film.
- As a result of extensive research to solve these problems, the inventor of the present invention found that carbon nanotubes can be dispersed or solubilized in solvent by placing in the presence of a conducting polymer, thereby leading to completion of the present invention.
- Namely, a first aspect of the present invention is a carbon nanotube composition that contains a conducting polymer (a), a solvent (b) and carbon nanotubes (c).
- In the carbon nanotube composition of this first aspect of the present invention, since the carbon nanotubes (c) are added to the solvent (b) together with the conducting polymer (a), the carbon nanotubes (c) can be dispersed or solubilized in the solvent (b) without impairing the characteristics of the carbon nanotubes (c) itself, and there is no separation or aggregation even during long-term storage. Although the reason for this is not fully understood, the carbon nanotubes (c) are presumed to be dispersed or solubilized together with the conducting polymer (a) due to mutual adsorption by the conducting polymer (a) and the carbon nanotubes (c) due to the π-π interaction by π electrons.
- In addition, in the carbon nanotube composition of the present invention, since the conducting polymer (a) and the carbon nanotubes (c) are used in combination, the resulting composition has superior electrical conductivity, film formability and moldability.
- The performance of the carbon nanotube composition can be improved by additionally containing a high molecular weight compound (d), a basic compound (e), a surfactant (f) and a silane coupling agent (g) and/or a colloidal silica (h).
- In addition, the conducting polymer (a) is preferably a water soluble conducting polymer, and more preferably a water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group.
- Moreover, as a result of extensive research to solve the aforementioned problems, the inventor of the present invention found that a composition containing a heterocyclic compound trimer and carbon nanotubes is suitable for this purpose, thereby leading to the present invention.
- Namely, a second aspect of the present invention is a carbon nanotube composition that contains a heterocyclic compound trimer (i), a solvent (b) and carbon nanotubes (c). Similar to the carbon nanotube composition of the first aspect of the present invention, performance of the composition can be improved by additionally containing a high molecular weight compound (d), a basic compound (e), a surfactant (f), a silane coupling agent (g) and/or a colloidal silica (h).
- The carbon nanotube compositions of the first and second aspects of the present invention enable the carbon nanotubes to be dispersed or solubilized in water, an organic solvent and a water-containing organic solvent without impairing the characteristics of the carbon nanotubes itself, and there is no separation or aggregation even during long-term storage. In addition, according to the carbon nanotube composition of the present invention, a coated film having superior electrical conductivity and film formability can be obtained free of temperature dependence by coating the composition onto a base material and allowing the coated film to demonstrate the characteristics of a conducting polymer, a heterocyclic compound trimer having a sulfonic acid group and a carboxyl group or carbon nanotubes itself. Moreover, the resulting coated film has superior moisture resistance, weather resistance and hardness.
- A third aspect of the present invention is a production method of a carbon nanotube composition comprising mixing a conducting polymer (a) or a heterocyclic compound trimer (i), a solvent (b) and carbon nanotubes (c), and irradiating with ultrasonic waves. The carbon nanotubes can be efficiently dispersed or solubilized in the solvent by this ultrasonic treatment.
- A fourth aspect of the present invention is a composite having a coated film composed of a carbon nanotube composition of the present invention on at least one surface of a base material.
- In addition, a fifth aspect of the present invention is a production method of a composite comprising coating a carbon nanotube composition of the present invention onto at least one surface of a base material, and forming a coated film by allowing to stand at an ordinary temperature or subjecting to heating treatment.
- The following provides a detailed explanation of the present invention.
- <Conducting Polymer (a)>
- Conducting polymer (a) is a π-conjugated polymer containing as its repeating unit phenylene vinylene, vinylene, thienylene, pyrollylene, phenylene, iminophenylene, isothianaphthene, furylene or carbazolylene and so forth.
- With respect to solubility in solvent in particular, a so-called water soluble conducting polymer is used preferably in the present invention. Here, a water soluble conducting polymer refers to a conducting polymer that has acidic groups, alkyl groups substituted with acidic groups or alkyl groups containing ether bonds on the backbone of a π-conjugated polymer or on nitrogen atoms of the polymer.
- In addition, among these water soluble conducting polymers, a water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is used preferably in the present invention with respect to solubility in solvent, electrical conductivity and film formability.
- Water soluble conducting polymers, disclosed in, for example, Japanese Unexamined Patent Application, First Publication No. S61-197633, Japanese Unexamined Patent Application, First Publication No. S63-39916, Japanese Unexamined Patent Application, First Publication No. H01-301714, Japanese Unexamined Patent Application, First Publication No. H05-504153, Japanese Unexamined Patent Application, First Publication No. H05-503953, Japanese Unexamined Patent Application, First Publication No. H04-32848, Japanese Unexamined Patent Application, First Publication No. H04-328181, Japanese Unexamined Patent Application, First Publication No. H06-145386, Japanese Unexamined Patent Application, First Publication No. H06-56987, Japanese Unexamined Patent Application, First Publication No. H05-226238, Japanese Unexamined Patent Application, First Publication No. H05-178989, Japanese Unexamined Patent Application, First Publication No. H06-293828, Japanese Unexamined Patent Application, First Publication No. H07-118524, Japanese Unexamined Patent Application, First Publication No. H06-32845, Japanese Unexamined Patent Application, First Publication No. H06-87949, Japanese Unexamined Patent Application, First Publication No. H06-256516, Japanese Unexamined Patent Application, First Publication No. H07-41756, Japanese Unexamined Patent Application, First Publication No. H07-48436, Japanese Unexamined Patent Application, First Publication No. H04-268331, Japanese Unexamined Patent Application, First Publication No. H09-59376, Japanese Unexamined Patent Application, First Publication No. 2000-172384, Japanese Unexamined Patent Application, Japanese Unexamined Patent Application, First Publication No. H06-49183 and Japanese Unexamined Patent Application, First Publication No. H10-60108, are preferably used as a water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group.
- Specific examples of a water soluble conducting polymers having at least one of a sulfonic acid group and a carboxyl group include water soluble conducting polymers having at least one of a sulfonic acid group and a carboxyl group, an alkyl group substituted with at least one of a sulfonic acid group and a carboxyl group, or an alkyl group containing an ether bond, on the backbone of a π-conjugated polymer or nitrogen atoms of the polymer that contains as its repeating unit at least one type selected from the group consisting of non-substituted or substituted phenylene vinylene, vinylene, thienylene, pyrollylene, phenylene, iminophenylene, isothianaphthene, furylene and carbazolylene. In particular, among these, a water soluble conducting polymer having a backbone that contains thienylene, pyrollylene, iminophenylene, phenylene vinylene, carbazolylene or isothianaphthene is used preferably.
- Preferable water soluble conducting polymers having at least one of a sulfonic acid group and a carboxyl group are the water soluble conducting polymers that contain 20 to 100% of at least one type of the repeating units selected from the following formulas (2) to (10) relative to the total number of repeating units throughout the entire polymer:
- (in the structural formula (2), wherein R1 and R2 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, —R35COOH, —COOR35, —COR35, —CHO, and —CN, where R35 represents an alkyl, aryl, or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene, or aralkylene group having 1 to 24 carbon atoms, and at least one of R1 and R2 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH);
- (in the structural formula (3), wherein R3 and R4 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, —R35COOH, —COOR35, —COR35, —CHO, and —CN, where R35 represents an alkyl, aryl, or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene, or aralkylene group having 1 to 24 carbon atoms, and at least one of R3 and R4 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH);
- (in the structural formula (4), wherein R5 to R8 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, —R35COOH, —COOR35, —COR35, —CHO and —CN, where R35 represents an alkyl, aryl, or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene, or aralkylene group having 1 to 24 carbon atoms, and at least one of R5 to R8 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH);
- (in the structural formula (5), wherein R9 to R13 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, —R35COOH, —COOR35, —COR35, —CHO, and —CN, where R35 represents an alkyl, aryl, or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and at least one of R9 to R13 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH);
- (in the structural formula (6), wherein R14 is selected from the group consisting of —SO3 −, —SO3H, —R42SO3 −, —R42SO3H, —COOH, and —R42COOH, where R42 represents an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms);
- (in the structural formula (7), wherein R52 to R57 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, —R35COOH, —COOR35, —COR35, —CHO, and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, at least one of R52 to R57 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH, and —R35COOH, Ht represents a heteroatom group selected from the group consisting of NR82, S, O, Se, and Te, where R82 represents hydrogen or a linear or branched alkyl group having 1 to 24 carbon atoms or substituted or non-substituted aryl group having 1 to 24 carbon atoms, the hydrocarbon chains of R52 to R57 mutually bond at arbitrary locations and may form a bivalent chain that forms at least one cyclic structure of saturated or unsaturated hydrocarbons of a 3 to 7-member ring together with the carbon atoms substituted by the groups, the cyclic bonded chain formed in this manner may contain a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl or imino bond at arbitrary locations, and n represents the number of condensed rings sandwiched between a hetero ring and a benzene ring having substituents R53 to R56, and is 0 or an integer of 1 to 3);
- (in the structural formula (8), wherein R58 to R66 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, —R35COOH, —COOR35, —COR35, —CHO, and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, at least one of R58 to R66 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH, and —R35COOH, and n represents the number of condensed rings sandwiched between a benzene ring having substituents R58 and R59 and a benzene ring having substituents R61 to R64, and is 0 or an integer of 1 to 3);
- (in the structural formula (9), wherein R67 to R76 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, —R35COOH, —COOR35, —COR35, —CHO, and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, at least one of R67 to R76 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH, and —R35COOH, and n represents the number of condensed rings sandwiched between a benzene ring having substituents R67 to R69 and a benzoquinone ring, and is 0 or an integer of 1 to 3); and,
- (in the structural formula (10), wherein R77 to R81 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, —R35COOH, —COOR35, —COR35, —CHO, and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, at least one of R77 to R81 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH, and —R35COOH, Xa− is at least one type of anion selected from the group of anions having a valence of 1 to 3 consisting of a chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogensulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methane sulfonate ion, p-toluene sulfonate ion, trifluoroacetate ion, and trifluoromethane sulfonate ion, a represents the ion valence of X and is an integer of 1 to 3, and p represents the doping ratio and has a value of 0.001 to 1).
- In addition, polyethylene dioxythiophene polystyrene sulfate is also used as a preferable water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group. Although this water soluble conducting polymer does not have any sulfonic acid groups introduced into the backbone of the conducting polymer, it has a structure in which polystyrene sulfonate is added as a dopant. This polymer can be produced by polymerizing 3,4-ethylene dioxythiophene (Bayer, Baytron M) with an oxidizing agent such as iron toluene sulfonate (Bayer, Baytron C). In addition, this polymer can also be acquired in the form of Baytron P (Bayer).
- An even more preferable water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is a water soluble conducting polymer that contains 20 to 100% of the repeating unit represented by the following formula (11) relative to the total number of repeating units throughout the entire polymer:
- (in the structural formula (11), wherein y represents an arbitrary number such that 0<y<1, R15 to R32 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, —R35COOH, —COOR35, —COR35, —CHO, and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and at least one of R15 to R32 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH).
- Here, a water soluble conducting polymer in which the content of repeating units having at least one of a sulfonic acid group and a carboxyl group is 50% or more relative to the total number of repeating units of the polymer is used preferably since it has extremely favorable solubility in solvents such as water and water-containing organic solvents. The content of repeating units having at least one of a sulfonic acid group and a carboxyl group is more preferably 70% or more, even more preferably 90% or more, and particularly preferably 100%.
- In addition, a substituent added to the aromatic ring is preferably an alkyl group, alkoxy group or halogen group, from the perspective of electrical conductivity and solubility, and water soluble conducting polymers having an alkoxy group are the most preferable. The most preferable water soluble conducting polymer among these combinations is shown in the following formula (12):
- (in the structural formula (12), wherein R33 represents one group selected from the group consisting of a sulfonic acid group, carboxyl group, their alkaline metal salts, ammonium salts and substituted ammonium salts, R34 represents one group selected from the group consisting of a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, dodecyl group, tetracosyl group, methoxy group, ethoxy group, n-propoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, heptoxy group, hexoxy group, octoxy group, dodecoxy group, tetracoxy group, fluoro group, chloro group and bromo group, X represents an arbitrary number such that 0<x<1, and n represents the degree of polymerization and has a value of 3 or more).
- Here, at least a portion of R33 is preferably at least one of a sulfonic acid group and a carboxyl group of a free acid from the perspective of improving electrical conductivity.
- Polymers obtained by various types of synthesis methods such as chemical polymerization or electrolytic polymerization can be used for a water soluble conducting polymer in the present invention. For example, synthesis methods described in Japanese Unexamined Patent Application, First Publication No. H7-196791 and Japanese Unexamined Patent Application, First Publication No. H7-324132 proposed by the inventors of the present invention can be applied. Namely, this refers to water soluble conducting polymers obtained by polymerizing at least one of the acidic group-substituted aniline represented by the following formula (13), its alkaline metal salt, ammonium salt and substituted ammonium salt, with an oxidizing agent in a solution containing a basic compound:
- (in the structural formula (13), wherein R36 to R41 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, —R35COOH, —COOR35, —COR35, —CHO, and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and at least one of R36 to R41 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH).
- A particularly preferable water soluble conducting polymer is a water soluble conducting polymer obtained by polymerizing at least one type of alkoxy group-substituted aminobenzene sulfonic acid, its alkaline metal salt, ammonium salt and substituted ammonium salt, with an oxidizing agent in a solution containing a basic compound.
- At least a portion of the acidic groups contained in a water soluble conducting polymer in the present invention are preferably in the form of free acid from the viewpoint of improving electrical conductivity. In addition, a water soluble conducting polymer in the present invention having a mass average molecular weight as GPC polyethylene of 2,000 to 3,000,000 is used preferably due to its superior electrical conductivity, film formability and film strength, while that having a mass average molecular weight of 3,000 to 1,000,000 is more preferable, and that having a mass average molecular weight of 5,000 to 500,000 is the most preferable.
- Although the conducting polymer (a) can be used as is, the conducting polymer (a) to which an external dopant has been imparted by doping treatment using acid according to known methods can also be used. Doping treatment can be carried out by, for example, immersing a conductor containing conducting polymer (a) in an acidic solution. Specific examples of acidic solutions used in doping treatment include aqueous solutions containing inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as p-toluene sulfonic acid, camphasulfonic acid, benzoic acid and derivatives having these backbones; and high molecular weight acids such as polystyrene sulfonic acid, polyvinyl sulfonic acid, poly(2-acrylamide-2-methylpropane) sulfonic acid, polyvinyl sulfuric acid and derivatives having these backbones; or mixed solutions of water and an organic solvent. These inorganic acids, organic acids and high molecular weight acids may each be used alone or they may be used as a mixture of two or more types at an arbitrary ratio.
- <Heterocyclic Compound Trimer (i)>
- An example of heterocyclic compound trimer (i) is the asymmetrical heterocyclic compound trimer represented by formula (16) in which heterocyclic compounds are bonded asymmetrically:
- (in the structural formula (16), wherein R101 to R112 are substituents respectively and independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, linear or branched alkoxy group having 1 to 24 carbon atoms, linear or branched acyl group having 2 to 24 carbon atoms, aldehyde group, carboxyl group, linear or branched carboxylic ester group having 2 to 24 carbon atoms, sulfonic acid group, linear or branched sulfonic ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, amido group, dicyanovinyl group, alkyl (linear or branched alkyl group having 1 to 8 carbon atoms) oxycarbonylcyanovinyl group, nitrophenylcyanovinyl group and halogen group;
- Ht represents a heteroatom group selected from the group consisting of NR154, S, O, Se and Te, and R154 represents a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms;
- Xa− represents at least one type of anion selected from the group consisting of anions having a valence of 1 to 3 consisting of a chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methane sulfonate ion, p-toluene sulfonate ion, trifluoroacetate ion and trifluoromethane sulfonate ion; a represents the ion valence of X and is an integer of 1 to 3; and m represents the doping ratio and has a value of 0 to 3.0).
- Heterocyclic compound trimer (i) is preferably a heterocyclic compound trimer represented by formula (17):
- (in the structural formula (17), wherein R113 to R124 represent substituents respectively and independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, linear or branched alkoxy group having 1 to 24 carbon atoms, linear or branched acyl group having 2 to 24 carbon atoms, aldehyde group, carboxyl group, linear or branched carboxylic ester group having 2 to 24 carbon atoms, sulfonic acid group, linear or branched sulfonic ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, amido group, dicyanovinyl group, alkyl (linear or branched alkyl group having 1 to 8 carbon atoms) oxycarbonylcyanovinyl group, nitrophenylcyanovinyl group and halogen group; at least one of R113 to R124 is a cyano group, nitro group, amide group, halogen group, sulfonic acid group, and carboxyl group;
- Ht represents a heteroatom group selected from the group consisting of NR154, S, O, Se and Te, and R154 represents a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms;
- Xa− represents at least one type of anion selected from the group consisting of anions having a valence of 1 to 3 consisting of a chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-toluene sulfonate ion, trifluoroacetate ion and trifluoromethane sulfonate ion; a represents the ion valence of X and is an integer of 1 to 3; and m represents the doping ratio and has a value of 0 to 3.0).
- In addition, an example of an asymmetrical heterocyclic compound trimer (i) is the indole derivative trimer oxidant represented by general formula (18):
- (in the structural formula (18), wherein R125 to R136 are substituents respectively and independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, linear or branched alkoxy group having 1 to 24 carbon atoms, linear or branched acyl group having 2 to 24 carbon atoms, aldehyde group, carboxylic acid group and its alkaline metal salt, ammonium salt and substituted ammonium salt, linear or branched carboxylic ester group having 2 to 24 carbon atoms, sulfonic acid group and its alkaline metal salt, ammonium salt and substituted ammonium salt, linear or branched sulfonic ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, amido group, dicyanovinyl group, alkyl (linear or branched alkyl group having 1 to 8 carbon atoms) oxycarbonylcyanovinyl group, nitrophenylcyanovinyl group and halogen group;
- Xa− represents at least one type of anion selected from the group consisting of anions having a valence of 1 to 3 consisting of a chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogensulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-toluene sulfonate ion, trifluoroacetate ion and trifluoromethane sulfonate ion; a represents the ion valence of X and is an integer of 1 to 3; and m represents the doping ratio and has a value of 0 to 3.0).
- On the other hand, an example of heterocyclic compound trimer (i) used in the present invention is a symmetrical heterocyclic compound trimer represented by general formula (19) in which heterocyclic compounds are bonded symmetrically:
- (in the structural formula (19), wherein R137 to R148 are substituents respectively and independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, linear or branched alkoxy group having 1 to 24 carbon atoms, linear or branched acyl group having 2 to 24 carbon atoms, aldehyde group, carboxyl group, linear or branched carboxylic ester group having 2 to 24 carbon atoms, sulfonic acid group, linear or branched sulfonic ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, amido group, dicyanovinyl group, alkyl (linear or branched alkyl group having 1 to 8 carbon atoms) oxycarbonylcyanovinyl group, nitrophenylcyanovinyl group and halogen group;
- Ht represents a heteroatom group selected from the group consisting of NR154, S, O, Se and Te, and R154 represents a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms;
- Xa− represents at least one type of anion selected from the group consisting of anions having a valence of 1 to 3 consisting of a chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogensulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-toluene sulfonate ion, trifluoroacetate ion and trifluoromethane sulfonate ion; a represents the ion valence of X and is an integer of 1 to 3; and m represents the doping ratio and has a value of 0 to 3.0).
- Among these heterocyclic compound trimers (i), carboxyl group-substituted heterocyclic compound trimers, sulfonic acid group-substituted heterocyclic compound trimers, cyano group-substituted heterocyclic compound trimers, nitro group-substituted heterocyclic compound trimers, amido group-substituted heterocyclic compound trimers, and halogen group-substituted heterocyclic compound trimers are preferable in terms of practical use. In particular, trimers having an acidic group such as carboxyl group-substituted heterocyclic compound trimers, and sulfonic acid group-substituted heterocyclic compound trimers can be used preferably in terms of safety with respect to people and the environment since water can be used for the solvent due to their water solubility.
- In addition, among these heterocyclic compound trimers (i), an indole derivative trimer in which the heterocyclic compound is an indole derivative (namely, a compound in which Ht is represented by NR154) is used particularly preferably due to its high electrical conductivity and high solubility.
- Heterocyclic compound trimers (i) obtained by various synthesis methods such as chemical synthesis and electrochemical synthesis can be used for a heterocyclic compound trimer (i) used in the present invention.
- In the present invention, a heterocyclic compound trimer obtained by reacting at least one type of heterocyclic compound represented by the following general formula (20) in a reaction mixture containing at least one type of oxidizing agent and at least one type of solvent is used particularly preferably due to its high electrical conductivity and high solubility.
- (in the formula (20), wherein R150 to R153 are substituents respectively and independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, linear or branched alkoxy group having 1 to 24 carbon atoms, linear or branched acyl group having 2 to 24 carbon atoms, aldehyde group, carboxyl group, linear or branched carboxylic ester group having 2 to 24 carbon atoms, sulfonic acid group, linear or branched sulfonic ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, amido group, dicyanovinyl group, alkyl (linear or branched alkyl group having 1 to 8 carbon atoms) oxycarbonylcyanovinyl group, nitrophenylcyanovinyl group and halogen group; and,
- Ht represents a heteroatom group selected from the group consisting of NR154, S, O, Se and Te, and R154 represents a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms).
- Specific examples of the most typical indole derivatives represented by general formula (20) used in the synthesis method of the heterocyclic compound trimer (i) include carboxyl group-substituted indoles, their alkaline metal salts, ammonium salts and substituted ammonium salts such as indole-4-carboxylic acid, indole-5-carboxylic acid, indole-6-carboxylic acid and indole-7-carboxylic acid; sulfonic acid group-substituted indoles, their alkaline metal salts, ammonium salts and substituted ammonium salts such as indole-4-sulfonic acid, indole-5-sulfonic acid, indole-6-sulfonic acid and indole-7-sulfonic acid; alkyl group-substituted indoles such as 4-methylindole, 5-methylindole, 6-methylindole, 7-methylindole, 4-ethylindole, 5-ethylindole, 6-ethylindole, 7-ethylindole, 4-n-propylindole, 5-n-propylindole, 6-n-propylindole, 7-n-propylindole, 4-iso-propylindole, 5-iso-propylindole, 6-iso-propylindole, 7-iso-propylindole, 4-n-butylindole, 5-n-butylindole, 6-n-butylindole, 7-n-butylindole, 4-sec-butylindole, 5-sec-butylindole, 6-sec-butylindole, 7-sec-butylindole, 4-t-butylindole, 5-t-butylindole, 6-t-butylindole and 7-t-butylindole; alkoxy group-substituted indoles such as 4-methoxyindole, 5-methoxyindole, 6-methoxyindole, 7-methoxyindole, 4-ethoxyindole, 5-ethoxyindole, 6-ethoxyindole, 7-ethoxyindole, 4-n-propoxyindole, 5-n-propoxyindole, 6-n-propoxyindole, 7-n-propoxyindole, 4-iso-propoxyindole, 5-iso-propoxyindole, 6-iso-propoxyindole, 7-iso-propoxyindole, 4-n-butoxyindole, 5-n-butoxyindole, 6-n-butoxyindole, 7-n-butoxyindole, 4-sec-butoxyindole, 5-sec-butoxyindole, 6-sec-butoxyindole, 7-sec-butoxyindole, 4-t-butoxyindole, 5-t-butoxyindole, 6-t-butoxyindole and 7-t-butoxyindole; acyl group-substituted indoles such as 4-acetylindole, 5-acetylindole, 6-acetylindole and 7-acetylindole; aldehyde group-substituted indoles such as indole-4-carbaldehyde, indole-5-carbaldehyde, indole-6-carbaldehyde and indole-7-carbaldehyde; carboxylic ester group-substituted indoles such as methyl indole-4-carboxylate, methyl indole-5-carboxylate, methyl indole-6-carboxylate and methyl indole-7-carboxylate; sulfonic ester group-substituted indoles such as methyl indole-4-sulfonate, methyl indole-5-sulfonate, methyl indole-6-sulfonate and methyl indole-7-sulfonate; cyano group-substituted indoles such as indole-4-carbonitrile, indole-5-carbonitrile, indole-6-carbonitrile and indole-7-carbonitrile; hydroxyl group-substituted indoles such as 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole; nitro group-substituted indoles such as 4-nitroindole, 5-nitroindole, 6-nitroindole and 7-nitroindole; amino group-substituted indoles such as 4-aminoindole, 5-aminoindole, 6-aminoindole and 7-aminoindole; amido group-substituted indoles such as 4-carbamoylindole, 5-carbamoylindole, 6-carbamoylindole and 7-carbamoylindole; halogen group-substituted indoles such as 4-fluoroindole, 5-fluoroindole, 6-fluoroindole, 7-fluoroindole, 4-chloroindole, 5-chloroindole, 6-chloroindole, 7-chloroindole, 4-bromoindole, 5-bromoindole, 6-bromoindole, 7-bromoindole, 4-iodoindole, 5-iodoindole, 6-iodoindole and 7-iodoindole; dicyanovinyl group-substituted indoles such as 4-dicyanovinylindole, 5-dicyanovinylindole, 6-dicyanovinylindole and 7-dicyanovinylindole; and N-alkyl group-substituted indoles such as N-methylindole, N-ethylindole, N-n-propylindole, N-iso-propylindole, N-n-butylindole, N-sec-butylindole and N-t-butylindole.
- Specific examples of the most typical benzo[b]furans represented by general formula (20) include carboxyl group-substituted benzo[b]furans, their alkaline metal salts, ammonium salts and substituted ammonium salts such as benzo[b]furan-4-carboxylic acid, benzo[b]furan-5-carboxylic acid, benzo[b]furan-6-carboxylic acid and benzo[b]furan-7-carboxylic acid; sulfonic acid group-substituted benzo[b]furans, their alkaline metal salts, ammonium salts and substituted ammonium salts such as benzo[b]furan-4-sulfonic acid, benzo[b]furan-5-sulfonic acid, benzo[b]furan-6-sulfonic acid and benzo[b]furan-7-sulfonic acid; alkyl group-substituted benzo[b]furans such as 4-methylbenzo[b]furan, 5-methylbenzo[b]furan, 6-methylbenzo[b]furan, 7-methylbenzo[b]furan, 4-ethylbenzo[b]furan, 5-ethylbenzo[b]furan, 6-ethylbenzo[b]furan, 7-ethylbenzo[b]furan, 4-n-propylbenzo[b]furan, 5-n-propylbenzo[b]furan, 6-n-propylbenzo[b]furan, 7-n-propylbenzo[b]furan, 4-iso-propylbenzo[b]furan, 5-iso-propylbenzo[b]furan, 6-iso-propylbenzo[b]furan, 7-iso-propylbenzo[b]furan, 4-n-butylbenzo[b]furan, 5-n-butylbenzo[b]furan, 6-n-butylbenzo[b]furan, 7-n-butylbenzo[b]furan, 4-sec-butylbenzo[b]furan, 5-sec-butylbenzo[b]furan, 6-sec-butylbenzo[b]furan, 7-sec-butylbenzo[b]furan, 4-t-butylbenzo[b]furan, 5-t-butylbenzo[b]furan, 6-t-butylbenzo[b]furan and 7-t-butylbenzo[b]furan; alkoxy group-substituted benzo[b]furans such as 4-methoxybenzo[b]furan, 5-methoxybenzo[b]furan, 6-methoxybenzo[b]furan, 7-methoxybenzo[b]furan, 4-ethoxybenzo[b]furan, 5-ethoxybenzo[b]furan, 6-ethoxybenzo[b]furan, 7-ethoxybenzo[b]furan, 4-n-propoxybenzo[b]furan, 5-n-propoxybenzo[b]furan, 6-n-propoxybenzo[b]furan, 7-n-propoxybenzo[b]furan, 4-iso-propoxybenzo[b]furan, 5-iso-propoxybenzo[b]furan, 6-iso-propoxybenzo[b]furan, 7-iso-propoxybenzo[b]furan, 4-n-butoxybenzo[b]furan, 5-n-butoxybenzo[b]furan, 6-n-butoxybenzo[b]furan, 7-n-butoxybenzo[b]furan, 4-sec-butoxybenzo[b]furan, 5-sec-butoxybenzo[b]furan, 6-sec-butoxybenzo[b]furan, 7-sec-butoxybenzo[b]furan, 4-t-butyoxybenzo[b]furan, 5-t-butoxybenzo[b]furan, 6-t-butoxybenzo[b]furan and 7-t-butoxybenzo[b]furan; acyl group-substituted benzo[b]furans such as 4-acetylbenzo[b]furan, 5-acetylbenzo[b]furan, 6-acetylbenzo[b]furan and 7-acetylbenzo[b]furan; aldehyde group-substituted benzo[b]furans such as benzo[b]furan 4-carbaldehyde, benzo[b]furan 5-carbaldehyde, benzo[b]furan 6-carbaldehyde and benzo[b]furan 7-carbaldehyde; carboxylic ester-group substituted benzo[b]furans such as methyl benzo[b]furan-4-carboxylate, methyl benzo[b]furan-5-carboxylate, methyl benzo[b]furan-6-carboxylate and methyl benzo[b]furan-7-carboxylate; sulfonic ester-group substituted benzo[b]furans such as methyl benzo[b]furan-4-sulfonate, methyl benzo[b]furan-5-sulfonate, methyl benzo[b]furan-6-sulfonate and methyl benzo[b]furan-7-sulfonate; cyano group-substituted benzo[b]furans such as benzo[b]furan-4-carbonitrile, benzo[b]furan-5-carbonitrile, benzo[b]furan-6-carbonitrile and benzo[b]furan-7-carbonitrile; hydroxyl group-substituted benzo[b]furans such as 4-hydroxybenzo[b]furan, 5-hydroxybenzo[b]furan, 6-hydroxybenzo[b]furan and 7-hydroxybenzo[b]furan; nitro group-substituted benzo[b]furans such as 4-nitrobenzo[b]furan, 5-nitrobenzo[b]furan, 6-nitrobenzo[b]furan and 7-nitrobenzo[b]furan; amino group-substituted benzo[b]furans such as 4-aminobenzo[b]furan, 5-aminobenzo[b]furan, 6-aminobenzo[b]furan and 7-aminobenzo[b]furan; amido group-substituted benzo[b]furans such as 4-carbamoylbenzo[b]furan, 5-carbamoylbenzo[b]furan, 6-carbamoylbenzo[b]furan and 7-carbamoylbenzo[b]furan; halogen group-substituted benzo[b]furans such as 4-fluorobenzo[b]furan, 5-fluorobenzo[b]furan, 6-fluorobenzo[b]furan, 7-fluorobenzo[b]furan, 4-chlorobenzo[b]furan, 5-chlorobenzo[b]furan, 6-chlorobenzo[b]furan, 7-chlorobenzo[b]furan, 4-bromobenzo[b]furan, 5-bromobenzo[b]furan, 6-bromobenzo[b]furan, 7-bromobenzo[b]furan, 4-iodobenzo[b]furan, 5-iodobenzo[b]furan, 6-iodobenzo[b]furan and 7-iodobenzo[b]furan; dicyanovinyl group-substituted benzo[b]furans such as 4-dicyanovinylbenzo[b]furan, 5-dicyanovinylbenzo[b]furan, 6-dicyanovinylbenzo[b]furan and 7-dicyanovinylbenzo[b]furan; and N-alkyl group-substituted benzo[b]furans such as N-methylbenzo[b]furan, N-ethylbenzo[b]furan, N-n-propylbenzo[b]furan, N-iso-propylbenzo[b]furan, N-n-butylbenzo[b]furan, N-sec-butylbenzo[b]furan and N-t-butylbenzo[b]furan.
- Specific examples of the most typical benzo[b]thiophenes represented by general formula (20) include carboxyl group-substituted benzo[b]thiophenes, their alkaline metal salts, ammonium salts and substituted ammonium salts such as benzo[b]thiophene-4-carboxylic acid, benzo[b]thiophene-5-carboxylic acid, benzo[b]thiophene-6-carboxylic acid and benzo[b]thiophene-7-carboxylic acid; sulfonic acid group-substituted benzo[b]thiophenes, their alkaline metal salts, ammonium salts and substituted ammonium salts such as benzo[b]thiophene-4-sulfonic acid, benzo[b]thiophene-5-sulfonic acid, benzo[b]thiophene-6-sulfonic acid and benzo[b]thiophene-7-sulfonic acid; alkyl group-substituted benzo[b]thiophenes such as 4-methylbenzo[b]thiophene, 5-methylbenzo[b]thiophene, 6-methylbenzo[b]thiophene, 7-methylbenzo[b]thiophene, 4-ethylbenzo[b]thiophene, 5-ethylbenzo[b]thiophene, 6-ethylbenzo[b]thiophene, 7-ethylbenzo[b]thiophene, 4-n-propylbenzo[b]thiophene, 5-n-propylbenzo[b]thiophene, 6-n-propylbenzo[b]thiophene, 7-n-propylbenzo[b]thiophene, 4-iso-propylbenzo[b]thiophene, 5-iso-propylbenzo[b]thiophene, 6-iso-propylbenzo[b]thiophene, 7-iso-propylbenzo[b]thiophene, 4-n-butylbenzo[b]thiophene, 5-n-butylbenzo[b]thiophene, 6-n-butylbenzo[b]thiophene, 7-n-butylbenzo[b]thiophene, 4-sec-butylbenzo[b]thiophene, 5-sec-butylbenzo[b]thiophene, 6-sec-butylbenzo[b]thiophene, 7-sec-butylbenzo[b]thiophene, 4-t-butylbenzo[b]thiophene, 5-t-butylbenzo[b]thiophene, 6-t-butylbenzo[b]thiophene and 7-t-butylbenzo[b]thiophene; alkoxy group-substituted benzo[b]thiophenes such as 4-methoxybenzo[b]thiophene, 5-methoxybenzo[b]thiophene, 6-methoxybenzo[b]thiophene, 7-methoxybenzo[b]thiophene, 4-ethoxybenzo[b]thiophene, 5-ethoxybenzo[b]thiophene, 6-ethoxybenzo[b]thiophene, 7-ethoxybenzo[b]thiophene, 4-n-propoxybenzo[b]thiophene, 5-n-propoxybenzo[b]thiophene, 6-n-propoxybenzo[b]thiophene, 7-n-propoxybenzo[b]thiophene, 4-iso-propoxybenzo[b]thiophene, 5-iso-propoxybenzo[b]thiophene, 6-iso-propoxybenzo[b]thiophene, 7-iso-propoxybenzo[b]thiophene, 4-n-butoxybenzo[b]thiophene, 5-n-butoxybenzo[b]thiophene, 6-n-butoxybenzo[b]thiophene, 7-n-butoxybenzo[b]thiophene, 4-sec-butoxybenzo[b]thiophene, 5-sec-butoxybenzo[b]thiophene, 6-sec-butoxybenzo[b]thiophene, 7-sec-butoxybenzo[b]thiophene, 4-t-butyoxybenzo[b]thiophene, 5-t-butoxybenzo[b]thiophene, 6-t-butoxybenzo[b]thiophene and 7-t-butoxybenzo[b]thiophene; acyl group-substituted benzo[b]thiophenes such as 4-acetylbenzo[b]thiophene, 5-acetylbenzo[b]thiophene, 6-acetylbenzo[b]thiophene and 7-acetylbenzo[b]thiophene; aldehyde group-substituted benzo[b]thiophenes such as benzo[b]thiophene 4-carbaldehyde, benzo[b]thiophene 5-carbaldehyde, benzo[b]thiophene 6-carbaldehyde and benzo[b]thiophene 7-carbaldehyde; carboxylic ester-group substituted benzo[b]thiophenes such as methyl benzo[b]thiophene-4-carboxylate, methyl benzo[b]thiophene-5-carboxylate, methyl benzo[b]thiophene-6-carboxylate and methyl benzo[b]thiophene-7-carboxylate; sulfonic ester-group substituted benzo[b]thiophenes such as methyl benzo[b]thiophene-4-sulfonate, methyl benzo[b]thiophene-5-sulfonate, methyl benzo[b]thiophene-6-sulfonate and methyl benzo[b]thiophene-7-sulfonate; cyano group-substituted benzo[b]thiophenes such as benzo[b]thiophene-4-carbonitrile, benzo[b]thiophene-5-carbonitrile, benzo[b]thiophene-6-carbonitrile and benzo[b]thiophene-7-carbonitrile; hydroxyl group-substituted benzo[b]thiophenes such as 4-hydroxybenzo[b]thiophene, 5-hydroxybenzo[b]thiophene, 6-hydroxybenzo[b]thiophene and 7-hydroxybenzo[b]thiophene; nitro group-substituted benzo[b]thiophenes such as 4-nitrobenzo[b]thiophene, 5-nitrobenzo[b]thiophene, 6-nitrobenzo[b]thiophene and 7-nitrobenzo[b]thiophene; amino group-substituted benzo[b]thiophenes such as 4-aminobenzo[b]thiophene, 5-aminobenzo[b]thiophene, 6-aminobenzo[b]thiophene and 7-aminobenzo[b]thiophene; amido group-substituted benzo[b]thiophenes such as 4-carbamoylbenzo[b]thiophene, 5-carbamoylbenzo[b]thiophene, 6-carbamoylbenzo[b]thiophene and 7-carbamoylbenzo[b]thiophene; halogen group-substituted benzo[b]thiophenes such as 4-fluorobenzo[b]thiophene, 5-fluorobenzo[b]thiophene, 6-fluorobenzo[b]thiophene, 7-fluorobenzo[b]thiophene, 4-chlorobenzo[b]thiophene, 5-chlorobenzo[b]thiophene, 6-chlorobenzo[b]thiophene, 7-chlorobenzo[b]thiophene, 4-bromobenzo[b]thiophene, 5-bromobenzo[b]thiophene, 6-bromobenzo[b]thiophene, 7-bromobenzo[b]thiophene, 4-iodobenzo[b]thiophene, 5-iodobenzo[b]thiophene, 6-iodobenzo[b]thiophene and 7-iodobenzo[b]thiophene; dicyanovinyl group-substituted benzo[b]thiophenes such as 4-dicyanovinylbenzo[b]thiophene, 5-dicyanovinylbenzo[b]thiophene, 6-dicyanovinylbenzo[b]thiophene and 7-dicyanovinylbenzo[b]thiophene; and, N-alkyl group-substituted benzo[b]thiophenes such as N-methylbenzo[b]thiophene, N-ethylbenzo[b]thiophene, N-n-propylbenzo[b]thiophene, N-iso-propylbenzo[b]thiophene, N-n-butylbenzo[b]thiophene, N-sec-butylbenzo[b]thiophene and N-t-butylbenzo[b]thiophene.
- Specific examples of the most typical benzo[b]selenophenes represented by general formula (20) include carboxyl group-substituted benzo[b]selenophenes, their alkaline metal salts, ammonium salts and substituted ammonium salts such as benzo[b]selenophene-4-carboxylic acid, benzo[b]selenophene-5-carboxylic acid, benzo[b]selenophene-6-carboxylic acid and benzo[b]selenophene-7-carboxylic acid; sulfonic acid group-substituted benzo[b]selenophenes, their alkaline metal salts, ammonium salts and substituted ammonium salts such as benzo[b]selenophene-4-sulfonic acid, benzo[b]selenophene-5-sulfonic acid, benzo[b]selenophene-6-sulfonic acid and benzo[b]selenophene-7-sulfonic acid; alkyl group-substituted benzo[b]selenophenes such as 4-methylbenzo[b]selenophene, 5-methylbenzo[b]selenophene, 6-methylbenzo[b]selenophene, 7-methylbenzo[b]selenophene, 4-ethylbenzo[b]selenophene, 5-ethylbenzo[b]selenophene, 6-ethylbenzo[b]selenophene, 7-ethylbenzo[b]selenophene, 4-n-propylbenzo[b]selenophene, 5-n-propylbenzo[b]selenophene, 6-n-propylbenzo[b]selenophene, 7-n-propylbenzo[b]selenophene, 4-iso-propylbenzo[b]selenophene, 5-iso-propylbenzo[b]selenophene, 6-iso-propylbenzo[b]selenophene, 7-iso-propylbenzo[b]selenophene, 4-n-butylbenzo[b]selenophene, 5-n-butylbenzo[b]selenophene, 6-n-butylbenzo[b]selenophene, 7-n-butylbenzo[b]selenophene, 4-sec-butylbenzo[b]selenophene, 5-sec-butylbenzo[b]selenophene, 6-sec-butylbenzo[b]selenophene, 7-sec-butylbenzo[b]selenophene, 4-t-butylbenzo[b]selenophene, 5-t-butylbenzo[b]selenophene, 6-t-butylbenzo[b]selenophene and 7-t-butylbenzo[b]selenophene; alkoxy group-substituted benzo[b]selenophenes such as 4-methoxybenzo[b]selenophene, 5-methoxybenzo[b]selenophene, 6-methoxybenzo[b]selenophene, 7-methoxybenzo[b]selenophene, 4-ethoxybenzo[b]selenophene, 5-ethoxybenzo[b]selenophene, 6-ethoxybenzo[b]selenophene, 7-ethoxybenzo[b]selenophene, 4-n-propoxybenzo[b]selenophene, 5-n-propoxybenzo[b]selenophene, 6-n-propoxybenzo[b]selenophene, 7-n-propoxybenzo[b]selenophene, 4-iso-propoxybenzo[b]selenophene, 5-iso-propoxybenzo[b]selenophene, 6-iso-propoxybenzo[b]selenophene, 7-iso-propoxybenzo[b]selenophene, 4-n-butoxybenzo[b]selenophene, 5-n-butoxybenzo[b]selenophene, 6-n-butoxybenzo[b]selenophene, 7-n-butoxybenzo[b]selenophene, 4-sec-butoxybenzo[b]selenophene, 5-sec-butoxybenzo[b]selenophene, 6-sec-butoxybenzo[b]selenophene, 7-sec-butoxybenzo[b]selenophene, 4-t-butyoxybenzo[b]selenophene, 5-t-butoxybenzo[b]selenophene, 6-t-butoxybenzo[b]selenophene and 7-t-butoxybenzo[b]selenophene; acyl group-substituted benzo[b]selenophenes such as 4-acetylbenzo[b]selenophene, 5-acetylbenzo[b]selenophene, 6-acetylbenzo[b]selenophene and 7-acetylbenzo[b]selenophene; aldehyde group-substituted benzo[b]selenophenes such as benzo[b]selenophene 4-carbaldehyde, benzo[b]selenophene 5-carbaldehyde, benzo[b]selenophene 6-carbaldehyde and benzo[b]selenophene 7-carbaldehyde; carboxylic ester-group substituted benzo[b]selenophenes such as methyl benzo[b]selenophene-4-carboxylate, methyl benzo[b]selenophene-5-carboxylate, methyl benzo[b]selenophene-6-carboxylate and methyl benzo[b]selenophene-7-carboxylate; sulfonic ester-group substituted benzo[b]selenophenes such as methyl benzo[b]selenophene-4-sulfonate, methyl benzo[b]selenophene-5-sulfonate, methyl benzo[b]selenophene-6-sulfonate and methyl benzo[b]selenophene-7-sulfonate; cyano group-substituted benzo[b]selenophenes such as benzo[b]selenophene-4-carbonitrile, benzo[b]selenophene-5-carbonitrile, benzo[b]selenophene-6-carbonitrile and benzo[b]selenophene-7-carbonitrile; hydroxyl group-substituted benzo[b]selenophenes such as 4-hydroxybenzo[b]selenophene, 5-hydroxybenzo[b]selenophene, 6-hydroxybenzo[b]selenophene and 7-hydroxybenzo[b]selenophene; nitro group-substituted benzo[b]selenophenes such as 4-nitrobenzo[b]selenophene, 5-nitrobenzo[b]selenophene, 6-nitrobenzo[b]selenophene and 7-nitrobenzo[b]selenophene; amino group-substituted benzo[b]selenophenes such as 4-aminobenzo[b]selenophene, 5-aminobenzo[b]selenophene, 6-aminobenzo[b]selenophene and 7-aminobenzo[b]selenophene; amido group-substituted benzo[b]selenophenes such as 4-carbamoylbenzo[b]selenophene, 5-carbamoylbenzo[b]selenophene, 6-carbamoylbenzo[b]selenophene and 7-carbamoylbenzo[b]selenophene; halogen group-substituted benzo[b]selenophenes such as 4-fluorobenzo[b]selenophene, 5-fluorobenzo[b]selenophene, 6-fluorobenzo[b]selenophene, 7-fluorobenzo[b]selenophene, 4-chlorobenzo[b]selenophene, 5-chlorobenzo[b]selenophene, 6-chlorobenzo[b]selenophene, 7-chlorobenzo[b]selenophene, 4-bromobenzo[b]selenophene, 5-bromobenzo[b]selenophene, 6-bromobenzo[b]selenophene, 7-bromobenzo[b]selenophene, 4-iodobenzo[b]selenophene, 5-iodobenzo[b]selenophene, 6-iodobenzo[b]selenophene and 7-iodobenzo[b]selenophene; dicyanovinyl group-substituted benzo[b]selenophenes such as 4-dicyanovinylbenzo[b]selenophene, 5-dicyanovinylbenzo[b]selenophene, 6-dicyanovinylbenzo[b]selenophene and 7-dicyanovinylbenzo[b]selenophene; and, N-alkyl group-substituted benzo[b]selenophenes such as N-methylbenzo[b]selenophene, N-ethylbenzo[b]selenophene, N-n-propylbenzo[b]selenophene, N-iso-propylbenzo[b]selenophene, N-n-butylbenzo[b]selenophene, N-sec-butylbenzo[b]selenophene and N-t-butylbenzo[b]selenophene.
- Specific examples of the most typical benzo[b]tellurophenes represented by general formula (20) include carboxyl group-substituted benzo[b]tellurophenes, their alkaline metal salts, ammonium salts and substituted ammonium salts such as benzo[b]tellurophene-4-carboxylic acid, benzo[b]tellurophene-5-carboxylic acid, benzo[b]tellurophene-6-carboxylic acid and benzo[b]tellurophene-7-carboxylic acid; sulfonic acid group-substituted benzo[b]tellurophenes, their alkaline metal salts, ammonium salts and substituted ammonium salts such as benzo[b]tellurophene-4-sulfonic acid, benzo[b]tellurophene-5-sulfonic acid, benzo[b]tellurophene-6-sulfonic acid and benzo[b]tellurophene-7-sulfonic acid; alkyl group-substituted benzo[b]tellurophenes such as 4-methylbenzo[b]tellurophene, 5-methylbenzo[b]tellurophene, 6-methylbenzo[b]tellurophene, 7-methylbenzo[b]tellurophene, 4-ethylbenzo[b]tellurophene, 5-ethylbenzo[b]tellurophene, 6-ethylbenzo[b]tellurophene, 7-ethylbenzo[b]tellurophene, 4-n-propylbenzo[b]tellurophene, 5-n-propylbenzo[b]tellurophene, 6-n-propylbenzo[b]tellurophene, 7-n-propylbenzo[b]tellurophene, 4-iso-propylbenzo[b]tellurophene, 5-iso-propylbenzo[b]tellurophene, 6-iso-propylbenzo[b]tellurophene, 7-iso-propylbenzo[b]tellurophene, 4-n-butylbenzo[b]tellurophene, 5-n-butylbenzo[b]tellurophene, 6-n-butylbenzo[b]tellurophene, 7-n-butylbenzo[b]tellurophene, 4-sec-butylbenzo[b]tellurophene, 5-sec-butylbenzo[b]tellurophene, 6-sec-butylbenzo[b]tellurophene, 7-sec-butylbenzo[b]tellurophene, 4-t-butylbenzo[b]tellurophene, 5-t-butylbenzo[b]tellurophene, 6-t-butylbenzo[b]tellurophene and 7-t-butylbenzo[b]tellurophene; alkoxy group-substituted benzo[b]tellurophenes such as 4-methoxybenzo[b]tellurophene, 5-methoxybenzo[b]tellurophene, 6-methoxybenzo[b]tellurophene, 7-methoxybenzo[b]tellurophene, 4-ethoxybenzo[b]tellurophene, 5-ethoxybenzo[b]tellurophene, 6-ethoxybenzo[b]tellurophene, 7-ethoxybenzo[b]tellurophene, 4-n-propoxybenzo[b]tellurophene, 5-n-propoxybenzo[b]tellurophene, 6-n-propoxybenzo[b]tellurophene, 7-n-propoxybenzo[b]tellurophene, 4-iso-propoxybenzo[b]tellurophene, 5-iso-propoxybenzo[b]tellurophene, 6-iso-propoxybenzo[b]tellurophene, 7-iso-propoxybenzo[b]tellurophene, 4-n-butoxybenzo[b]tellurophene, 5-n-butoxybenzo[b]tellurophene, 6-n-butoxybenzo[b]tellurophene, 7-n-butoxybenzo[b]tellurophene, 4-sec-butoxybenzo[b]tellurophene, 5-sec-butoxybenzo[b]tellurophene, 6-sec-butoxybenzo[b]tellurophene, 7-sec-butoxybenzo[b]tellurophene, 4-t-butyoxybenzo[b]tellurophene, 5-t-butoxybenzo[b]tellurophene, 6-t-butoxybenzo[b]tellurophene and 7-t-butoxybenzo[b]tellurophene; acyl group-substituted benzo[b]tellurophenes such as 4-acetylbenzo[b]tellurophene, 5-acetylbenzo[b]tellurophene, 6-acetylbenzo[b]tellurophene and 7-acetylbenzo[b]tellurophene; aldehyde group-substituted benzo[b]tellurophenes such as benzo[b]tellurophene 4-carbaldehyde, benzo[b]tellurophene 5-carbaldehyde, benzo[b]tellurophene 6-carbaldehyde and benzo[b]tellurophene 7-carbaldehyde; carboxylic ester-group substituted benzo[b]tellurophenes such as methyl benzo[b]tellurophene-4-carboxylate, methyl benzo[b]tellurophene-5-carboxylate, methyl benzo[b]tellurophene-6-carboxylate and methyl benzo[b]tellurophene-7-carboxylate; sulfonic ester-group substituted benzo[b]tellurophenes such as methyl benzo[b]tellurophene-4-sulfonate, methyl benzo[b]tellurophene-5-sulfonate, methyl benzo[b]tellurophene-6-sulfonate and methyl benzo[b]tellurophene-7-sulfonate; cyano group-substituted benzo[b]tellurophenes such as benzo[b]tellurophene-4-carbonitrile, benzo[b]tellurophene-5-carbonitrile, benzo[b]tellurophene-6-carbonitrile and benzo[b]tellurophene-7-carbonitrile; hydroxyl group-substituted benzo[b]tellurophenes such as 4-hydroxybenzo[b]tellurophene, 5-hydroxybenzo[b]tellurophene, 6-hydroxybenzo[b]tellurophene and 7-hydroxybenzo[b]tellurophene; nitro group-substituted benzo[b]tellurophenes such as 4-nitrobenzo[b]tellurophene, 5-nitrobenzo[b]tellurophene, 6-nitrobenzo[b]tellurophene and 7-nitrobenzo[b]tellurophene; amino group-substituted benzo[b]tellurophenes such as 4-aminobenzo[b]tellurophene, 5-aminobenzo[b]tellurophene, 6-aminobenzo[b]tellurophene and 7-aminobenzo[b]tellurophene; amido group-substituted benzo[b]tellurophenes such as 4-carbamoylbenzo[b]tellurophene, 5-carbamoylbenzo[b]tellurophene, 6-carbamoylbenzo[b]tellurophene and 7-carbamoylbenzo[b]tellurophene; halogen group-substituted benzo[b]tellurophenes such as 4-fluorobenzo[b]tellurophene, 5-fluorobenzo[b]tellurophene, 6-fluorobenzo[b]tellurophene, 7-fluorobenzo[b]tellurophene, 4-chlorobenzo[b]tellurophene, 5-chlorobenzo[b]tellurophene, 6-chlorobenzo[b]tellurophene, 7-chlorobenzo[b]tellurophene, 4-bromobenzo[b]tellurophene, 5-bromobenzo[b]tellurophene, 6-bromobenzo[b]tellurophene, 7-bromobenzo[b]tellurophene, 4-iodobenzo[b]tellurophene, 5-iodobenzo[b]tellurophene, 6-iodobenzo[b]tellurophene and 7-iodobenzo[b]tellurophene; dicyanovinyl group-substituted benzo[b]tellurophenes such as 4-dicyanovinylbenzo[b]tellurophene, 5-dicyanovinylbenzo[b]tellurophene, 6-dicyanovinylbenzo[b]tellurophene and 7-dicyanovinylbenzo[b]tellurophene; and, N-alkyl group-substituted benzo[b]tellurophenes such as N-methylbenzo[b]tellurophene, N-ethylbenzo[b]tellurophene, N-n-propylbenzo[b]tellurophene, N-iso-propylbenzo[b]tellurophene, N-n-butylbenzo[b]tellurophene, N-sec-butylbenzo[b]tellurophene and N-t-butylbenzo[b]tellurophene.
- Among these, carboxyl group-substituted heterocyclic compounds, sulfonic acid group-substituted heterocyclic compounds, cyano group-substituted heterocyclic compounds, nitro group-substituted heterocyclic compounds, amido group-substituted heterocyclic compounds, halogen group-substituted heterocyclic compounds and so forth are used preferably in terms of practical use. In particular, carboxyl group-substituted heterocyclic compounds and sulfonic acid group-substituted heterocyclic compounds are used preferably.
- Among these heterocyclic compounds, indole derivatives are used preferably.
- There are no particular limitations on the oxidizing agent used in the aforementioned synthesis method of heterocyclic compound trimer (i), and examples include ferric chloride hexahydrate, anhydrous ferric chloride, ferric nitrate nonahydrate, ferric sulfate n-hydrate, ammonium ferric sulfate dodecahydrate, ferric perchlorate n-hydrate, ferric tetrafluoroborate, cupric chloride, cupric nitrate, cupric sulfate, cupric tetrafluoroborate, nitrosonium tetrafluoroborate, hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate and potassium periodate. Among these, ferric chloride hexahydrate, anhydrous ferric chloride, cupric chloride, cupric tetrafluoroborate and ammonium persulfate are used preferably in terms of practical use, while ferric chloride hexahydrate and anhydrous ferric chloride are used most preferably in terms of practical use. Furthermore, these oxidizing agents may be used alone or two or more types may be combined at an arbitrary ratio.
- The molar ratio of heterocyclic compound to oxidizing agent used in the aforementioned synthesis method of heterocyclic compound trimer (i) (heterocyclic compound:oxidizing agent) is 1:0.5 to 100, and preferably 1:1 to 50. Here, if the ratio of the oxidizing agent is low, reactivity decreases and raw materials remain. Conversely, if the ratio of the oxidizing agent is high, the trimer that is formed is oxidized excessively causing deterioration of the product.
- Water or an inorganic solvent can be used for the solvent used in the aforementioned synthesis method of the heterocyclic compound trimer (i). There are no particular limitations on the organic solvent, and examples of organic solvents that are used include methanol, ethanol, isopropanol, acetone, acetonitrile, propionitrile, tetrahydrofuran, 1,4-dioxane, methyl isobutyl ketone, methyl ethyl ketone, γ-butyl lactone, propylene carbonate, sulfolane, nitromethane, N,N-dimethylformamide, N-methylacetamide, dimethylsulfoxide, dimethylsulfone, N-methylpyrrolidone, benzene, toluene, xylene, methylene chloride, chloroform and dichloroethane. Furthermore, these solvents may be used alone or they may used as a mixture of two or more types at an arbitrary ratio. Among these solvents, acetone, acetonitrile, 1,4-dioxane, γ-butyl lactone and N,N-dimethylformamide are used preferably, while acetonitrile is used most preferably in terms of practical use.
- In addition, in the aforementioned synthesis method of the heterocyclic compound trimer (i), the reaction is particularly preferably carried out in the presence of water and the organic solvent. The molar ratio of the heterocyclic compound to water (heterocyclic compound:water) is 1:1000 to 1000:1 and preferably 1:100 to 100:1. However, in the case the oxidizing agent contains crystalline water, that crystalline water is also calculated as water. Here, if the ratio of water is low, the reaction proceeds explosively, and simultaneous to excessive oxidation of the trimer and deterioration of its structure, Xa− serving as dopant may be unable to efficiently dope the trimer, thereby resulting in decreased electrical conductivity. Conversely, if the ratio of water is excessively high, the progression of the oxidation reaction is obstructed which may cause a decrease in reaction yield.
- In the aforementioned synthesis method of the heterocyclic compound trimer (i), the concentration of the heterocyclic compound during the reaction is 0.01% by mass or more, preferably 0.1 to 50% by mass, and more preferably within the range of 1 to 30% by mass relative to the solvent.
- The Xa− in the heterocyclic compound trimers used in the present invention represented by general formulas (16) to (19) represents a dopant, and is an anion of a protonic acid originating in the oxidizing agent and so forth during polymerization. More specifically, this anion is an anion having a valence of 1 to 3 such as chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, p-toluene sulfonate ion, trifluoroacetate ion and trifluoromethane sulfonate ion, and is preferably an anion having a valence of 1 to 2 such as a chlorine ion, sulfate ion or borofluoride ion. This anion is most preferably a monovalent anion such as chlorine ion. In the case of carrying out polymerization by selecting anhydrous ferric chloride for the oxidizing agent, for example, dopant Xa− in the indole derivative trimer is a chlorine ion, Xa− and in the case of carrying out polymerization using cupric trifluoroacetate, dopant Xa− is a trifluoroacetate ion.
- The heterocyclic compound trimer (i) obtained in the aforementioned synthesis method of the heterocyclic compound trimer (i) is a doped heterocyclic compound trimer (i) except for when hydrogen peroxide or ozone is used for the oxidizing agent, and the molar ratio (doping ratio) of the dopant Xa− relative to its repeating unit is 0.001 to 0.5. The value of m becomes 0 when hydrogen peroxide or ozone is used for the oxidizing agent.
- A heterocyclic compound trimer that is dedoped for the purpose of improving solubility in solvent (b) can be used for the heterocyclic compound trimer (i). Although there are no particular limitations on dedoping method, methods known as dedoping steps of various types of conducting polymers and charge transfer complexes in the prior art can be used. Namely, examples of these methods include a method in which indole derivative trimer (I) is suspended in an alkaline solution of aqueous ammonia, sodium hydroxide, potassium hydroxide or lithium hydroxide to remove dopant Xa−, or a method in which a dedoped indole derivative trimer (namely, doping ratio m=0) is obtained by reduction treatment.
- The heterocyclic compound trimer (i) may have more superior electrical conductivity by having a layered structure. The heterocyclic compound trimer (i) preferably has a layered structure in which the interlayer interval is 0.1 to 5.0 nm, more preferably 0.1 to 2.0 nm and particularly preferably 0.1 to 1.0 nm. A compound having such a microlayered structure has satisfactory rigidity, strength, heat resistance and so forth. If the interlayer interval is 0.1 nm or more, the layered structure tends to become more stable, and if the interlayer interval is 2.0 nm or less, the hopping transfer of electrons between trimers becomes easier, thereby tending to improve electrical conductivity.
- Furthermore, although the heterocyclic compound trimer (i) can be used as is, that imparted with an external dopant can be used by carrying out doping treatment by acid using a known method. For example, doping treatment can be carried out by immersing the heterocyclic compound trimer in an acidic solution. Specific examples of acidic solutions used for doping treatment include aqueous solutions containing inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as p-toluene sulfonic acid, camphasulfonic acid, benzoic acid and derivatives having these backbones, and high molecular weight acids such as polystyrene sulfonic acid, polyvinyl sulfonic acid, poly(2-acrylamide-2-methylpropane) sulfonic acid, polyvinyl sulfuric acid and derivatives having these backbones, or mixed solutions of water and organic solvent. Furthermore, these inorganic acids, organic acids and high molecular weight acids may each be used alone or they may be used as a mixture of two or more types at an arbitrary ratio.
- In addition, although the indole derivative trimer oxidant represented by general formula (18), which is an asymmetrical heterocyclic compound trimer (i), can be obtained by a production method in which an asymmetrical indole derivative trimer is subjected to oxidation treatment with a known oxidizing agent in a solvent, there are cases in which the indole derivative trimer oxidant can be obtained as a result of the oxidation reaction proceeding more efficiently without using an oxidizing agent by simply dedoping an indole derivative trimer doped with an external dopant Xa− from the doped form by deacidification treatment or reduction treatment, thereby making this production method extremely suitable industrially.
- On the other hand, the heterocyclic compound oxidant represented by general formula (19), which is the symmetrical heterocyclic compound trimer (i), can be obtained by a known production method. For example, a symmetrical indole derivative trimer can be produced according to the method described in Japanese Unexamined Patent Application, First Publication No. 2001-261680.
- The performance of these heterocyclic compound trimers (i) can be improved by using after increasing their purity by using a purification method such as recrystallization, reprecipitation purification or sublimation purification and so forth following their synthesis.
- In the present invention, electrical conductivity, film formability and moldability are improved as a result of containing this heterocyclic compound trimer.
- <Solvent (b)>
- There are no particular limitations on solvent (b), which is an essential component of the present invention, provided it dissolves or disperses conducting polymer (a) or the heterocyclic compound trimer (i), carbon nanotubes (c), high molecular weight compound (d), basic compound (e), surfactant (f), silane coupling agent (g) and colloidal silica (h). Examples of the solvent (b) that are used preferably include water, alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol and butanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone and methyl isobutyl ketone; ethylene glycols such as ethylene glycol, ethylene glycol methyl ether and ethylene glycol mono-n-propyl ether; propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and propylene glycol propyl ether; amides such as dimethylformamide and dimethylacetoamide; pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; hydroxyesters such as dimethylsulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate, methyl β-methoxyisobutyrate and methyl α-hydroxyisobutyrate; and anilines such as aniline and N-methylaniline.
- In the case of using a water soluble conducting polymer for the conducting polymer (a), water or a water-containing organic solvent is used preferably for the solvent (b) in consideration of the solubility of the water soluble conducting polymer and dispersivity of carbon nanotubes (c).
- <Carbon Nanotubes (c)>
- There are no particular limitations on carbon nanotubes (c), which are an essential component of the carbon nanotube composition of the present invention, and single-walled carbon nanotubes, multi-walled carbon nanotubes in which multiple walls are layered concentrically and their coiled forms can be used for the carbon nanotubes (c).
- As a more detailed explanation of the carbon nanotubes (c), an example of such a carbon nanotube is a substance in which the outer diameter is extremely small on the order of nanometers and which comprises a plurality of cylinders, in which the surfaces of graphite-like carbon atoms in layers several atoms thick are rounded, that form a nested structure. In addition, carbon nanohorns, in which one side of a carbon nanotube is closed, or cup-shaped nanocarbon substances, in which a hole is formed in the top, can also be used.
- There are no particular limitations on the production method of the carbon nanotubes (c) in the present invention. Specific examples of production methods include catalytic hydrogen reduction of carbon dioxide, arc discharge, laser vaporization, CVD, vapor phase growth and HiPco (high-pressure carbon monoxide process), in which carbon monoxide is reacted with an iron catalyst at high temperature and high pressure to grow carbon nanotubes in the vapor phase.
- Preferable examples of carbon nanotubes (c) obtained by the aforementioned production methods are single-walled carbon nanotubes, and highly purified carbon nanotubes, which are obtained by various purification methods such as washing, centrifugal separation, filtration, oxidation and chromatography, are used preferably since they adequately demonstrate various functions.
- In addition, crushed carbon nanotubes obtained by crushing using a ball mill, vibration mill, sand mill, roll mill or other ball-type kneading device, as well as shortly cut carbon nanotubes obtained by chemical or physical treatment, can also be used.
- <High Molecular Weight Compound (d)>
- The use of high molecular weight compound (d) in the carbon nanotube composition of the present invention further improves the base material adhesion and strength of the coated film.
- There are no particular limitations on high molecular weight compound (d) in the present invention provided it can be dissolved or dispersed (emulsion formation) in the solvent (b) used in the present invention, specific examples of which include polyvinyl alcohols such as polyvinyl alcohol, polyvinyl formal and polyvinyl butyral; polyacrylamides such as polyacrylamide, poly(N-t-butylacrylamide and polyacrylamide methyl propane sulfonate; polyvinyl pyrrolidones; polystyrene sulfonates and their sodium salts; cellulose, alkyd resin, melamine resin, urea resin, phenol resin, epoxy resin, polybutadiene resin, acrylic resin, urethane resin, vinyl ester resin, urea resin, polyimide resin, maleic acid resin, polycarbonate resin, vinyl acetate resin, chlorinated polyethylene resin, chlorinated polypropylene resin, styrene resin, acrylic/styrene copolymer resin, vinyl acetate/acrylic copolymer resin, polyester resin, styrene/maleic acid copolymer resin, fluororesin and their copolymers. In addition, these high molecular weight compounds (d) may be used as a mixture of two or more types at an arbitrary ratio.
- Among these high molecular weight compounds (d), water soluble high molecular weight compounds or high molecular weight compounds that form an emulsion in aqueous systems are used preferably in consideration of solubility in solvent, stability of the resulting composition and electrical conductivity, and high molecular weight compounds having an anion group are used particularly preferably. In addition, among these, those used by mixing one or two or more types of aqueous acrylic resin, aqueous polyester resin, aqueous urethane resin and aqueous chlorinated polyolefin resin are used preferably.
- <Basic Compound (e)>
- The basic compound (e) that composes a carbon nanotube composition of the present invention is effective for dedoping the water soluble conducting polymer or the heterocyclic compound trimer and improving solubility in solvent (b) as a result of being added to the carbon nanotube composition. In addition, together with considerably improving solubility in water by forming salts with sulfonic acid groups and carboxyl groups, basic compound (e) promotes solubilization or dispersion of the carbon nanotubes (c) in the solvent (b).
- Although there are no particular limitations on the basic compound (e), examples of the basic compounds that are used preferably include ammonia, aliphatic amines, cyclic saturated amines, cyclic unsaturated amines and ammonium salts, and inorganic bases.
- The structural formula of amines used for the basic compound (e) is shown in the following formula (14):
- (in the formula (14), wherein R45 to R47 respectively and mutually independently represent hydrogen, alkyl group having 1 to 4 carbon atoms (C1 to C4), CH2OH, CH2CH2OH, CONH2 or NH2).
- The structural formula of ammonium salts used for basic compound (e) is shown in the following formula (15):
- (in the formula (15), wherein R48 to R51 respectively and mutually independently represent hydrogen, alkyl group having 1 to 4 carbon atoms (C1 to C4), CH2OH, CH2CH2OH, CONH2 or NH2, X− represents OH−, ½.SO4 2−, NO3 −, ½.CO3 2−, HCO3 −, ½.(COO)2 2− or R′COO−, and R′ represents an alkyl group having 1 to 3 carbon atoms (C1 to C3)).
- Examples of cyclic saturated amines that are used preferably include piperidine, pyrrolidine, morpholine, piperazine, derivatives having these backbones and their ammonium hydroxide compounds.
- Examples of cyclic unsaturated amines that are used preferably include pyridine, α-picoline, β-picoline, γ-picoline, quinoline, isoquinoline, pyrroline, derivatives having their backbones and their ammonium hydroxide compounds.
- Examples of inorganic bases that are used preferably include sodium hydroxide, potassium hydroxide, lithium hydroxide and other hydroxides.
- Two or more types of the basic compound (e) may be used by mixing. For example, electrical conductivity can be further improved by using a mixture of an amine and an ammonium salt. Specific examples of such mixtures include NH3/(NH4)2CO3, NH3/(NH4)HCO3, NH3/CH3COONH4, NH3/(NH4)2SO4, N(CH3)3/CH3COONH4 and N(CH3)3/(NH4)2SO4. In addition, although these mixtures can be used in arbitrary mixing ratios, the ratio of amine to ammonium salt (amine/ammonium salt) is preferably 1/10 to 10/0.
- <Surfactant (f)>
- Although a carbon nanotube composition of the present invention is able to form a high-performance film without undergoing separation of aggregation even when stored for a long period of time by solubilizing or dispersing carbon nanotubes (c) with the aforementioned conducting polymer (a) or heterocyclic compound trimer (i), solvent (b), carbon nanotubes (c), high molecular weight compound (d) and basic compound (e) alone, addition of surfactant (f) not only makes it possible to further promote solubilization or dispersion, but also improves flatness, coatability and electrical conductivity.
- Specific examples of the surfactant (f) that are used include anionic surfactants such as alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl carboxylic acid, alkyl naphthalene sulfonic acid, α-olefin sulfonic acid, dialkyl sulfosuccinic acid, α-sulfonated fatty acids, N-methyl-N-oleoyltaurine, petroleum sulfonic acid, alkyl sulfuric acids, sulfated oils, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene styrenated phenyl ether sulfuric acid, alkyl phosphoric acids, polyoxyethylene alkyl ether phosphoric acid, polyoxyethylene alkyl phenyl ether phosphoric acid, naphthalene sulfonic acid formaldehyde condensates and their salts; cationic surfactants such as primary to tertiary fatty amines, quaternary ammonium, tetraalkyl ammonium, trialkyl benzyl ammonium alkyl pyridinium, 2-alkyl-1-alkyl-1-hydroxyethyl imidazolinium, N,N-dialkylmorpholinium, polyethylene polyamine fatty acid amides, urea condensates of polyethylene polyamine fatty acid amides, quaternary ammonium of urea condensates of polyethylene polyamine fatty acid amides and their salts; betaines such as N,N-dimethyl-N-alkyl-N-carboxymethyl ammonium betaines, N,N,N-trialkyl-N-sulfoalkylene ammonium betaines, N,N-dialkyl-N,N-bispolyoxyethylene ammonium sulfuric acid ester betaines and 2-alkyl-1-carboxymethyl-1-hydroxyethylimidazolinium betaines; amphoteric surfactants such as N,N-dialkylaminoalkylene carbonates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene-polyoxypropylene glycols, polyoxyethylene-polyoxypropylene alkyl ethers, polyvalent alcohol fatty acid partial esters, polyoxyethylene polyvalent alcohol fatty acid partial esters, polyoxyethylene fatty acid esters, polyglycerin fatty acid esters, polyoxyethylenated castor oil, fatty acid diethanol amides, polyoxyethylene alkyl amines, triethanol amine fatty acid partial esters and trialkylamine oxides; and fluorine-based surfactants such as fluoroalkyl carboxylic acid, perfluoroalkyl carboxylic acid, perfluoroalkyl benzene sulfonic acid and perfluoroalkyl polyoxyethylene ethanol. Here, alkyl groups preferably have 1 to 24 carbon atoms and more preferably 3 to 18 carbon atoms. Furthermore, two or more types of surfactants may be used.
- <Silane Coupling Agent (g)>
- A silane coupling agent (g) can be used in the present invention in combination with the carbon nanotube composition of the present invention containing the conducting polymer (a) or the heterocyclic compound trimer (i), the solvent (b), the carbon nanotubes (c), the high molecular weight compound (d), the basic compound (e) and the surfactant (f). The moisture resistance of a coated film obtained from a carbon nanotube composition that uses a silane coupling agent (g) is remarkably improved. A silane coupling agent (g) represented by the following formula (1) is used for silane coupling agent (g):
- (in the formula (1) wherein, R242, R243 and R244 respectively and independently represent a group selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, linear or branched alkoxy group having 1 to 6 carbon atoms, amino group, acetyl group, phenyl group and halogen group, X represents the following:
-
CH2l or CH2lOCH2m - l and m represent values from 0 to 6, and Y represents a group selected from the group consisting of a hydroxyl group, thiol group, amino group, epoxy group and epoxycyclohexyl group).
- More specifically, examples of silane coupling agents having an epoxy group include γ-glycidyloxypropyl trimethoxysilane, γ-glycidyloxypropyl methyl dimethoxysilane and γ-glycidyloxypropyl triethoxysilane.
- Examples of silane coupling agents having an amino group include γ-aminopropyl triethoxysilane, β-aminoethyl trimethoxysilane and γ-aminopropoxypropyl trimethoxysilane.
- Examples of silane coupling agents having a thiol group include γ-mercaptopropyl trimethoxysilane and β-mercaptoethyl methyl dimethoxysilane.
- Examples of silane coupling agents having a hydroxyl group include β-hydroxyethoxyethyl triethoxysilane and γ-hydroxypropyl trimethoxysilane.
- Examples of silane coupling agents having an epoxycyclohexyl group include β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane.
- <Colloidal Silica (h)>
- In the present invention, colloidal silica (h) can also be used in a crosslinked carbon nanotube composition containing the conducting polymer (a) or the heterocyclic compound trimer (i), the solvent (b), the carbon nanotubes (c), the high molecular weight compound (d), the basic compound (e), the surfactant (f) and the silane coupling agent (g). A coated film obtained from a carbon nanotube composition that combines the use of colloidal silica (h) has remarkably improved surface hardness and weather resistance.
- Although there are no particular limitations on the colloidal silica (h) in the present invention, that which is dispersed in water, organic solvent, or a mixed solvent of water and organic solvent is used preferably. Although there are no particular limitations on the organic solvent, examples of organic solvents that are used preferably include alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol and pentanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone and methyl isobutyl ketone; ethylene glycols such as ethylene glycol, ethylene glycol methyl ether and ethylene glycol mono-n-propyl ether, and propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and propylene glycol propyl ether.
- In addition, colloidal silica having a particle diameter within the range of 1 nm to 300 nm, preferably 1 nm to 150 nm and more preferably 1 nm to 50 nm is used for the colloidal silica (h). Here, if the particle diameter is too large, hardness becomes inadequate or the solution stability of the colloidal silica itself ends up decreasing.
- The usage ratio between the aforementioned conducting polymer (a) or heterocyclic compound trimer (i) and the solvent (b) is preferably 0.001 to 50 parts by mass, and more preferably 0.01 to 30 parts by mass of the conducting polymer (a) or the heterocyclic compound trimer (i) relative to 100 parts by mass of the solvent (b). If the ratio of the conducting polymer (a) or the heterocyclic compound trimer (i) is less than 0.001 parts by mass, electrical conductivity deteriorates or the solubilization or dispersion efficiency of carbon nanotubes (c) decreases. On the other hand, if the ratio exceeds 50 parts by mass, electrical conductivity reaches a peak and does not increase further and viscosity becomes excessively high thereby causing a decrease in the solubilization or dispersion efficiency of the carbon nanotubes (c).
- The usage ratio between the aforementioned carbon nanotubes (c) and solvent (b) is preferably 0.0001 to 20 parts by mass, and more preferably 0.001 to 10 parts by mass of the carbon nanotubes (c) relative to 100 parts by mass of the solvent (b). If the ratio of the carbon nanotubes (c) used is less than 0.0001 parts by mass, performance such as electrical conductivity resulting from the use of carbon nanotubes (c) decreases. On the other hand, if the amount used exceeds 20 parts by mass, the solubilization or dispersion efficiency of the carbon nanotubes (c) decreases.
- The usage ratio between the aforementioned high molecular weight compound (d) and solvent (b) is preferably 0.1 to 400 parts by mass, and more preferably 0.5 to 300 parts by mass of the high molecular weight compound (d) relative to 100 parts by mass of the solvent (b). If the ratio of high molecular weight compound (d) is greater than or equal to 0.1 parts by mass, film formability, moldability and strength are further improved, while on the other hand, when the ratio of the high molecular weight compound (d) is less than or equal to 400 parts by mass, there is little decrease in the solubility of the water soluble conducting polymer (a) or the heterocyclic compound trimer (i) or the carbon nanotubes (c), and a high degree of electrical conductivity is maintained.
- The usage ratio between the aforementioned basic compound (e) and solvent (b) is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass of the basic compound (e) relative to 100 parts by mass of the solvent (b). When the usage ratio of the basic compound (e) is within this range, the solubility of the water soluble conducting polymer improves, the solubilization or dispersion of the carbon nanotubes (c) in the solvent (b) is promoted, and electrical conductivity improves.
- The usage ratio between the aforementioned surfactant (f) and solvent (b) is preferably 0.0001 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass of the surfactant (f) relative to 100 parts by mass of the solvent (b). Although coatability improves if the usage ratio of the surfactant (f) exceeds 10 parts by mass, in addition to the occurrence of phenomena such as deterioration of electrical conductivity, the solubilization or dispersion of the carbon nanotubes (c) decreases.
- The usage ratio between the aforementioned silane coupling agent (g) and solvent (b) is preferably 0.001 to 20 parts by mass, and more preferably 0.01 to 15 parts by mass of the silane coupling agent (g) to 100 parts by mass of the solvent (b). If the usage ratio of the silane coupling agent (g) is less than 0.001 parts by mass, the amount of improvement in at least one of moisture resistance and solvent resistance becomes comparatively smaller, while on the other hand, if the usage ratio exceeds 20 parts by mass, solubility, flatness, transparency and electrical conductivity may worsen.
- The usage ratio between the aforementioned colloidal silica (h) and solvent (b) is preferably 0.001 to 100 parts by mass, and more preferably 0.01 to 50 parts by mass of the colloidal silica (h) relative to 100 parts by mass of the solvent (b). If the ratio of the colloidal silica (h) is 0.001 parts by mass or more, the amount of improvement in moisture resistance, weather resistance and hardness increases. On the other hand, if the ratio exceeds 100 parts by mass, solubility, flatness, transparency and electrical ductivity worsen.
- Moreover, various types of known substances can be added to the carbon nanotube composition of the present invention as necessary, examples of which include plasticizers, dispersants, coated surface adjusters, fluidity adjusters, ultraviolet absorbers, antioxidants, preservatives, adhesion assistants and thickeners.
- In addition, an conducting substance can be incorporated in the carbon nanotube composition of the present invention in order to further improve electrical conductivity. Examples of the conducting substances include carbon fibers, conducting carbon black, graphite and other carbon-based substances, tin oxide, zinc oxide and other metal oxides, and metals such as silver, nickel and copper.
- A stirring or kneading device such as an ultrasonic wave device, homogenizer, spiral mixer, planetary mixer, dispenser or hybrid mixer is used when mixing these components. In particular, it is preferable to mix the conducting polymer (a) or the heterocyclic compound trimer (i), the solvent (b), the carbon nanotubes (c) and other components and irradiate them with ultrasonic waves. At that time, it is preferable to use irradiation of ultrasonic waves in combination with a homogenizer (ultrasonic homogenizer).
- Although there are no particular limitations on the conditions of irradiation with ultrasonic waves, the intensity and treatment time of the ultrasonic waves should be adequate for uniformly dispersing or dissolving the carbon nanotubes (c) in the solvent (b). For example, the rated output of an ultrasonic oscillator is preferably within the range of 0.1 to 2.0 watts/cm2, and more preferably 0.3 to 1.5 watts/cm2, per unit bottom surface area of the ultrasonic oscillator, and the oscillation frequency is preferably within the range of 10 to 200 KHz and more preferably 20 to 100 KHz. In addition, the duration of ultrasonic irradiation treatment is preferably 1 minute to 48 hours and more preferably 5 minutes to 48 hours. Dispersion or dissolution is preferably subsequently improved by using a ball-type kneading device such as a ball mill, vibration mill, sand mill or roll mill.
- Examples of base materials that form a coated film by coating with the carbon nanotube composition in the present invention include high molecular weight compounds, plastics, wood, paper, ceramics, fibers, non-woven fabrics, carbon fibers, carbon fiber paper and their films, foams, porous films, elastomers and glass plates.
- Examples of high molecular weight compounds, plastics and films include polyethylene, polyvinyl chloride, polypropylene, polystyrene, ABS resin, AS resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, polyvinylidene fluoride, polyester, polyamide, polyimide, polyaramid, polyphenylene sulfide, polyether ethyl ketone, polyphenylene ether, polyether nitrile, polyamide imide, polyether sulfone, polysulfone, polyether imide, polybutylene terephthalate, polyurethane and their films, foams and elastomers. In order to form a coated film on at least one of their surfaces, the surfaces of these films are preferably subjected to corona discharge treatment or plasma treatment for the purpose of improving adhesion of the coated film.
- A coated film in the present invention is formed on the surface of a base material by a method used for ordinary coating. Examples of methods used include coating methods using a gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, fountain coater, rod coater, air doctor coater, knife coater, blade coater, cast coater or screen coater, spraying methods such as air spraying or airless spraying, and immersion methods such as dipping.
- Although the carbon nanotube composition can be allowed to stand at normal temperatures after coating onto the surface of a base material, the coated film can also be heat-treated. The performing of heat treatment is preferable since the crosslinking reaction between the carbon nanotubes (c), the high molecular weight compound (d) and the basic compound (e) and the conducting polymer (a) or the heterocyclic compound trimer (i) can be further promoted, moisture resistance can be imparted in a shorter period of time, the residual amount of the solvent (b) can be further reduced and electrical conductivity can be further improved. The temperature of heat treatment is preferably 20 to 250° C. and particularly preferably 40 to 200° C. If the temperature of heat treatment is higher than 250° C., the conducting polymer (a) itself or the heterocyclic compound trimer (i) itself is decomposed, and electrical conductivity may be degraded.
- The film thickness of the coated film is preferably within the range of 0.01 to 100 μm, and more preferably within the range of 0.1 to 50 μm.
- Although the composite of the present invention has superior electrical conductivity even if used as is, electrical conductivity can be further improved by doping with acid after having formed a coated film of the carbon nanotube composition on at least one surface of the base material, and then allowing to stand at ordinary temperatures or heat treating.
- There are no particular limitations on the method used for acid doping and known methods can be used. For example, doping can be carried out by immersing a conductor in an acidic solution. Specific examples of acidic solutions include aqueous solutions containing inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as p-toluene sulfonic acid, camphasulfonic acid, benzoic acid, and derivatives having their backbones, and high molecular weight acids such as polystyrene sulfonic acid, polyvinyl sulfonic acid, poly(2-acrylamide-2-methylpropane) sulfonic acid, polyvinyl sulfuric acid and derivatives having their backbones, as well as mixed solvents of water and organic solvent. Furthermore, these inorganic acids, organic acids and high molecular weight acids may each be used alone or two or more types may be used as a mixture at an arbitrary ratio.
- Although the following provides a more detailed explanation of the present invention through its examples, the following examples are not intended to limit the scope of the present invention in any way.
- Synthesis of Poly(2-sulfo-5-methoxy-1,4-iminophenylene)
- 100 mmol of 2-aminoanisol-4-benzene sulfonic acid were stirred and dissolved in a 4 mol/liter aqueous solution of triethylamine at 25° C., then a 100 mmol aqueous solution of ammonium peroxodisulfate was dropped in the mixture. Following completion of dropping and stirring for an additional 12 hours at 25° C., the reaction product was filtered, washed and then dried to obtain 15 g of a polymer powder. The volumetric resistance of this conducting polymer (A-1) was 9.0 Ω·cm.
- Synthesis of Poly(2-sulfo-1,4-iminophenylene)
- 100 mmol of m-aminobenzene sulfonic acid were stirred and dissolved in a 4 mol/liter aqueous solution of trimethylamine at 25° C., then a 100 mmol aqueous solution of ammonium peroxodisulfate was dropped in the mixture. Following completion of dropping and stirring for an additional 12 hours at 25° C., the reaction product was filtered, washed and then dried to obtain 10 g of a polymer powder. The volumetric resistance of this conducting polymer (A-2) was 12.0 Ω·cm.
- Poly(2-sulfo-1,4-iminophenylene) was synthesized according to a known method (J. Am. Chem. Soc., (1991), 113, 2665-2666). The sulfonic acid content of the resulting polymer was 52% relative to the aromatic ring. In addition, the volumetric resistance of this conducting polymer (A-3) was 50 Ω·cm.
- 100 mmol of aniline were stirred and dissolved in a 1 mol/liter aqueous solution of sulfuric acid at 25° C., followed by dropping in a 100 mmol aqueous solution of ammonium peroxodisulfate. Following completion of dropping and stirring for an additional 12 hours at 25° C., the reaction product was filtered, washed and then dried to obtain 8 g of a polymer powder. The resulting doped polymer was press molded with a tablet molding machine and cut to a diameter of 10 mm and thickness of 1 mm. When the conductivity was measured with the four probe method, it was found to be 1.0 S/cm or less. After dispersing and stirring this polymer in 1 mol/liter aqueous ammonia for 1 hour at 25° C., it was filtered, washed and then dried to obtain 5 g of dedoped polymer powder.
- 5 parts by mass of the aforementioned conducting polymer (A-1) of Production Example 1 and 0.4 parts by mass of carbon nanotubes (Iljin, multi-walled carbon nanotubes produced by CVD) were mixed in 100 parts by mass of water at room temperature to prepare a carbon nanotube composition 1.
- 5 parts by mass of the aforementioned conducting polymer (A-1) of Production Example 1, 0.1 parts by mass of carbon nanotubes and 20 parts by mass of acrylic resin in an aqueous emulsion form (Dianal MX-1845, Mitsubishi Rayon Co., Ltd., resin content: 40% by mass) were mixed in 100 parts of water at room temperature to prepare a carbon nanotube composition 2.
- 3 parts by mass of the aforementioned conducting polymer (A-2) of Production Example 2, 0.1 parts by mass of carbon nanotubes and 1 part by mass of ammonia were mixed in 100 parts by mass of water at room temperature to prepare a carbon nanotube composition 3.
- 1 part by mass of the aforementioned conducting polymer (A-1) of Production Example 1, 0.2 parts by mass of carbon nanotubes, 1 part by mass of triethylamine and 20 parts by mass of acrylic resin in an aqueous emulsion form (Dianal MX-1845, Mitsubishi Rayon Co., Ltd.) were mixed in 100 parts by mass of water at room temperature to a prepare carbon nanotube composition 4.
- 1 part by mass of the aforementioned conducting polymer (A-3) of Production Example 3, 0.4 parts by mass of carbon nanotubes and 0.5 parts by mass of dodecylbenzene sulfonate were mixed in 100 parts by mass of a water/methanol mixed solvent (weight ratio: 9/1) at room temperature to prepare a carbon nanotube composition 5.
- 1 part by mass of the aforementioned conducting polymer (A-1) of Production Example 1, 0.4 parts by mass of carbon nanotubes and 0.5 parts by mass of γ-glycidoxypropyl trimethoxysilane were mixed in 100 parts by mass of water at room temperature to prepare a carbon nanotube composition 6.
- 1 part by mass of the aforementioned conducting polymer (A-1) of Production Example 1, 0.4 parts by mass of carbon nanotubes, 0.5 parts by mass of γ-glycidoxypropyl trimethoxysilane, 5 parts by mass of colloidal silica (particle diameter: 10 nm) and 10 parts by mass of acrylic resin in an aqueous emulsion form (Dianal MX-1845, Mitsubishi Rayon Co., Ltd.) were mixed in 100 parts of water at room temperature to prepare a carbon nanotube composition 7.
- 0.5 parts by mass of the aforementioned conducting polymer (A-4) of Production Example 4 and 0.1 parts by mass of carbon nanotubes were mixed in 100 parts by mass of N-methylpyrrolidone at room temperature to prepare a carbon nanotube composition 8.
- 0.1 part by mass of carbon nanotubes were mixed in 100 parts by mass of water at room temperature to prepare a carbon nanotube composition 8.
- 0.1 part by mass of carbon nanotubes and 1 part by mass of ammonia were mixed in 100 parts by mass of water at room temperature to prepare a carbon nanotube composition 9.
- 0.1 part by mass of carbon nanotubes and 20 parts by mass of acrylic resin in an aqueous emulsion form (Dianal MX-1845, Mitsubishi Rayon Co., Ltd.) were mixed in 100 parts by mass of water at room temperature to prepare a carbon nanotube composition 10.
- 5 parts by mass of the aforementioned conducting polymer (A-1) of Production Example 1 were mixed in 100 parts by mass of water at room temperature to prepare a conducting composition 1.
- In the following production examples of indole derivative trimers, elementary analysis and measurements were carried out using the Thermoquest EA1110. Electrical conductivity was measured with the MCP-T350 conductivity gauge (Mitsubishi Chemical) (four probe method, electrode interval: 1 mm). Moreover, X-ray diffraction (XRD) was measured with the RINT-1100 (Rigaku Corporation) (tube: CuKα X-rays).
- 10 ml of acetonitrile were placed in a 200 ml three-mouth flask followed by dissolving 1.42 g of indole-5-carboxylic acid. On the other hand, preparation of the oxidizing agent solution was carried out by dissolving 16.2 g of anhydrous ferric chloride and 5.4 g of water in 40 ml of acetonitrile and stirring for 10 minutes. Next, after dropping in the prepared oxidizing agent solution into the aqueous indole-5-carboxylic acid solution over the course of 30 minutes, the solution was stirred for 10 hours at 60° C. The reaction solution changed from a pale yellow color to a light green color while generating a small amount of heat, and its pH was 1 or less. Following completion of the reaction, the reaction solution was aspiration filtered with a Kiriyama funnel, washed with acetonitrile and then methanol and dried to obtain 1.12 g of light green 6,11-dihydro-5H-diindolo[2,3-a:2′,3′-c]carbazole-2,9,14-tricarboxylic acid (indole-5-carboxylic acid trimer) (yield: 79%).
- When the resulting trimer was press molded with a tablet molding machine and cut to a diameter of 10 mm and thickness of 1 mm followed by measurement of electrical conductivity using the four probe method, it was 0.41 S/cm. The result of elementary analysis was (C9.00H4.90N1.09O1.98Cl0.11)3. In addition, the result of X-ray diffraction crystal analysis was an interlayer interval of 0.48 nm.
- With the exception of using indole-5-sulfonic acid instead of indole-5-carboxylic acid in Production Example 5, polymerization was carried out in the same manner as Production Example 5 to obtain 1.01 g of green 6,11-dihydro-5H-diindolo[2,3-a:2′,3′-c]carbazole-2,9,14-trisulfonic acid (indole-5-sulfonic acid trimer) (yield: 71%).
- When the resulting trimer was press molded with a tablet molding machine and cut to a diameter of 10 mm and thickness of 1 mm followed by measurement of electrical conductivity using the four probe method, it was 0.56 S/cm. The result of elementary analysis was (C8.00H4.85N1.06O3.01S1.06Cl0.11)3.
- With the exception of using indole-5-carbonitrile instead of indole-5-carboxylic acid in Production Example 5, polymerization was carried out in the same manner as Production Example 5 to obtain 1.22 g of green 6,11-dihydro-5H-diindolo[2,3-a:2′,3′-c]carbazole-2,9,14-tricarbonitrile (indole-5-carbonitrile trimer) (yield: 86%).
- When the resulting trimer was press molded with a tablet molding machine and cut to a diameter of 10 mm and thickness of 1 mm followed by measurement of electrical conductivity using the four probe method, it was 0.50 S/cm. The result of elementary analysis was (C9.00H4.03N1.97Cl0.10)3. In addition, the result of X-ray diffraction crystal analysis was an interlayer interval of 0.44 nm.
- 1.00 g of the indole-5-carboxylic acid trimer synthesized in Production Example 5 was dissolved in 50 ml of 1 M aqueous ammonia and stirred for 1 hour. After stirring, it was re-precipitated in 50 ml of acetonitrile and the resulting precipitate was suction filtered with a Kiriyama funnel, washed with water and then acetonitrile and dried to obtain 0.92 g of the black oxidant of indole-5-carboxylic acid trimer. The result of elementary analysis was (C9.00H4.34N1.07O1.99)3.
- 50.0 g of oxyindole were stirred for 10 hours at 100° C. in air using 100 ml of phosphorous oxychloride as solvent in a 300 ml three-mouth flask. After slowly pouring the reaction liquid into ice water and crushing the excess phosphorous oxychloride, the liquid was neutralized with aqueous sodium hydroxide. The target compound was then extracted from this solution with chloroform and dried with magnesium sulfate. The solvent was distilled off from the filtrate and purified by column chromatography to obtain 32.5 g of indole trimer (symmetrical form).
- 5 parts by mass of the aforementioned indole-5-carboxylic acid trimer of Production Example 5 and 0.4 parts by mass of carbon nanotubes (Iljin, multi-walled carbon nanotubes produced by CVD) were mixed in 100 parts by mass of water at room temperature to prepare a carbon nanotube composition.
- 3 parts by mass of the aforementioned indole-5-carboxylic acid trimer of Production Example 5, 0.1 parts by mass of carbon nanotubes and 20 parts by mass of acrylic resin in an aqueous emulsion form (Dianal MX-1845, Mitsubishi Rayon Co., Ltd.) were mixed in 100 parts by mass of water at room temperature to prepare a carbon nanotube composition.
- 3 parts by mass of the aforementioned indole-5-sulfonic acid trimer of Production Example 6, 0.1 parts by mass of carbon nanotubes and 1 part by mass of ammonia were mixed in 100 parts by mass of water at room temperature to prepare a carbon nanotube composition.
- 3 parts by mass of the aforementioned indole-5-sulfonic acid trimer of Production Example 6, 0.2 parts by mass of carbon nanotubes, 1 part by mass of triethylamine and 20 parts by mass of acrylic resin in an aqueous emulsion form (Dianal MX-1845, Mitsubishi Rayon Co., Ltd.) were mixed in 100 parts by mass of water at room temperature to prepare a carbon nanotube composition.
- 1 part by mass of the aforementioned indole-5-carbonitrile trimer of Production Example 7, 0.4 parts by mass of carbon nanotubes and 0.5 parts by mass of dodecylbenzene sulfonate were mixed in 100 parts by mass of dimethylsulfoxide at room temperature to prepare a carbon nanotube composition.
- 3 parts by mass of the aforementioned indole-5-carboxylic acid trimer oxidant of Production Example 8, 0.4 parts by mass of carbon nanotubes and 0.5 parts by mass of γ-glycidoxypropyl trimethoxysilane were mixed in 100 parts by mass of water at room temperature to prepare a carbon nanotube composition.
- 3 parts by mass of the aforementioned symmetrical indole trimer of Production Example 9, 0.4 parts by mass of carbon nanotubes and 10 parts by mass of acrylic resin in an aqueous emulsion form (Dianal MX-1845, Mitsubishi Rayon Co., Ltd.) were mixed in 100 parts by mass of water at room temperature to prepare a carbon nanotube composition.
- 1 part by mass of the aforementioned indole-5-carbonitrile trimer of Production Example 7 and 0.5 parts by mass of dodecylbenzene sulfonate were mixed in 100 parts by mass of dimethylsulfoxide at room temperature to prepare a conducting composition.
- After visually observing the states of the compositions obtained in the aforementioned examples and comparative examples, the compositions were coated onto a glass plate according to the bar coater method (using a No. 5 bar coater). After drying for 5 minutes at 80° C. to form a coated film and then observing its appearance, the surface resistance was measured. Those results are shown in Table 1.
- However, in the case of carbon nanotube composition 8 obtained in Example 8, the composition was coated onto a glass plate according to the bar coater method (using a No. 5 bar coater) and dried for 5 minutes at 150° C. to form a coated film followed by immersing for 5 minutes in a 1 mol/liter aqueous solution of sulfuric acid. After then drying for 5 minutes at 80° C. and observing the appearance, the surface resistance was measured.
- The compositions obtained in the aforementioned examples and comparative examples were subjected to ultrasonic treatment for 1 hour (UA100, Shinmei Daiko, 36 KHz), and after visually observing the states of the compositions, the compositions were coated onto a glass plate according to the bar coater method (using a No. 5 bar coater). After drying for 5 minutes at 80° C. to form a coated film and then observing its appearance, the surface resistance was measured. Those results are shown in Table 1.
- However, in the case of carbon nanotube composition 8 obtained in Example 8, the composition was coated onto a glass plate according to the bar coater method (using a No. 5 bar coater) and dried for 5 minutes at 150° C. to form a coated film followed by immersing for 5 minutes in a 1 mol/liter aqueous solution of sulfuric acid. After then drying for 5 minutes at 80° C. and observing the appearance, the surface resistance was measured.
- The solution state was observed visually 24 hours after having prepared the carbon nanotube compositions. Those results are shown in Table 1.
- ∘: Uniformly dispersed or dissolved
- X: Non-uniformly dispersed
- The two probe method (electrode interval: 20 mm) was used to measure surface resistance under conditions of 25° C. and 15% RH for surface resistance values of 108Ω or more, while the four probe method (electrode interval: 5 mm) was used for surface resistance values of 107Ω or less. Those results are shown in Table 1.
- The state of the coated film was observed visually. Those results are shown in Table 1.
- ∘: Uniform coated film formed
- X: Coated film observed in which carbon nanotubes are not present uniformly
-
TABLE 1 Ultrasonic Surface Coated Film Treatment Solution State Resistance Appearance Example 1 No ◯ 6.6 × 103 ◯ Yes ◯ 1.9 × 102 ◯ Example 2 No ◯ 8.3 × 104 ◯ Yes ◯ 6.2 × 103 ◯ Example 3 No ◯ 3.5 × 104 ◯ Yes ◯ 1.5 × 103 ◯ Example 4 No ◯ 1.1 × 106 ◯ Yes ◯ 8.6 × 104 ◯ Example 5 No ◯ 2.9 × 103 ◯ Yes ◯ 5.3 × 102 ◯ Example 6 No ◯ 9.2 × 103 ◯ Yes ◯ 7.9 × 102 ◯ Example 7 No ◯ 5.7 × 105 ◯ Yes ◯ 2.5 × 104 ◯ Example 8 No ◯ 6.4 × 104 ◯ Yes ◯ 3.9 × 103 ◯ Example 9 No ◯ 1.8 × 104 ◯ Yes ◯ 1.3 × 103 ◯ Example 10 No ◯ 4.2 × 106 ◯ Yes ◯ 3.9 × 105 ◯ Example 11 No ◯ 1.1 × 106 ◯ Yes ◯ 2.1 × 105 ◯ Example 12 No ◯ 3.2 × 106 ◯ Yes ◯ 1.3 × 105 ◯ Example 13 No ◯ 6.4 × 106 ◯ Yes ◯ 6.9 × 105 ◯ Example 14 No ◯ 9.1 × 105 ◯ Yes ◯ 1.5 × 105 ◯ Example 15 No ◯ 5.2 × 105 ◯ Yes ◯ 8.4 × 104 ◯ Comp. Ex. 1 No X >1 × 1012 X Yes X >1 × 1012 X Comp. Ex. 2 No X >1 × 1012 X Yes X >1 × 1012 X Comp. Ex. 3 No X >1 × 1012 X No X >1 × 1012 X Comp. Ex. 4 No ◯ 1.5 × 106 ◯ Yes ◯ 1.7 × 106 ◯ Comp. Ex. 5 No ◯ 4.2 × 107 ◯ Yes ◯ 4.2 × 107 ◯ - As is clear from Table 1, the solutions of the carbon nanotube compositions of the present examples were uniformly dispersed or dissolved, and uniform coated films were formed. In addition, they also demonstrated low values of surface resistance. In particular, surface resistance values were able to be lowered even more by performing ultrasonic treatment.
- On the other hand, the carbon nanotube compositions of Comparative Examples 1 to 3 demonstrated inferior surface resistance values and coated film appearance. The electrical conductivity of Comparative Examples 4 and 5 that used conducting composition 1 was not adequate.
- The carbon nanotube composition of the present invention can be used by simple coating methods such as coating, spraying, casting, and dipping for various types of antistatic agents, capacitors, batteries, fuel cells and their polymer electrolyte membranes, electrode layers, catalyst layers, gas diffusion layers, separators and other members, EMI shields, chemical sensors, display elements, non-linear materials, preservatives, adhesives, fibers, spinning materials, antistatic coatings, corrosion-resistant coatings, electrodeposition coatings, plating primers, conducting primers for electrostatic coating, electrical corrosion prevention and improvement of battery charge storage.
- In addition, a composite of the present invention is used as an industrial packaging material for semiconductors, electrical appliance electronic components and so forth, an antistatic film of electronic photography and recording materials such as overhead projector film and slide film, for preventing accumulation of electrical charge of magnetic recording tape such as audio tape, video tape, computer tape and floppy disks, for LSI wiring of electronic devices, electron guns (sources) and electrodes of field emission displays (FED), hydrogen storage agent, for prevention of accumulation of electrical charge on the surfaces of input and display devices such as transparent touch panel, electroluminescent display, and liquid crystal displays, and as light emitting materials that form transparent electrodes and organic electroluminescent elements, buffer materials, electron transfer materials, hole transfer materials, fluorescent materials, thermal transfer sheets, transfer sheets, thermal transfer imaging sheets and imaging sheets.
Claims (25)
1. A carbon nanotube composition that contains a conducting polymer (a), a solvent (b) and carbon nanotubes (c).
2. A carbon nanotube composition that contains a heterocyclic compound trimer (i), a solvent (b) and carbon nanotubes (c).
3. A carbon nanotube composition according to claim 1 , wherein the carbon nanotube composition additionally contains a high molecular weight compound (d).
4. A carbon nanotube composition according to claim 1 , wherein the carbon nanotube composition additionally contains a basic compound (e).
5. A carbon nanotube composition according to claim 1 , wherein the carbon nanotube composition additionally contains a surfactant (f).
6. (canceled)
7. A carbon nanotube composition according to claim 1 , wherein the carbon nanotube composition additionally contains a colloidal silica (h).
8. A carbon nanotube composition according to claim 1 , wherein the conducting polymer (a) is a water soluble conducting polymer.
9. A carbon nanotube composition according to claim 8 , wherein the water soluble conducting polymer has at least one of a sulfonic acid group and a carboxyl group.
10. A carbon nanotube composition according to claim 9 , wherein the water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is a water soluble conducting polymer that contains 20 to 100% of at least one type of the repeating units selected from the following formulas (2) to (10) relative to the total number of repeating units throughout the entire polymer:
wherein in the formula (2) R1 and R2 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR3, —OCOR35, —NO2, —COOH, R35COOH, —COOR35, —COR35, —CHO and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and at least one of R1 and R2 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH;
wherein in the formula (3) R3 and R4 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, —R35COOH, —COOR35, —COR35, —CHO and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and at least one of R3 and R4 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH;
wherein in the formula (4) R5 to R8 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH R35COOH, —COOR35, —COR35, —CHO and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and at least one of R5 to R8 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH;
wherein in the formula (5) R9 to R13 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, R35COOH, —COOR35, —COR35, —CHO and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and at least one of R9 to R13 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH;
wherein in the formula (6) R14 is selected from the group consisting of —SO3 −, —SO3H, —R42SO3 −, —R42SO3H, —COOH and —R42COOH, where R42 represents an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms;
wherein in the formula (7) R52 to R57 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, R35COOH, —COOR35, —COR35, —CHO and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, at least one of R52 to R57 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH, Ht represents a heteroatom group selected from the group consisting of NR82, S, O, Se and Te, where R82 represents hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, or a substituted or non-substituted aryl group having 1 to 24 carbon atoms, the hydrocarbon chains of R52 to R57 mutually bond at arbitrary locations and may form a bivalent chain that forms at least one cyclic structure of saturated or unsaturated hydrocarbons of a 3 to 7-member ring together with the carbon atoms substituted by the groups, the cyclic bonded chain formed in this manner may contain a carbonyl ether, ester, amide, sulfide, sulfinyl, sulfonyl or imino bond at arbitrary locations, and n represents the number of condensed rings sandwiched between a hetero ring and a benzene ring having substituents R53 to R56, and is 0 or an integer of 1 to 3;
wherein in the formula (8) R58 to R66 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, —R35COOH, —COOR35, —COR35, —CHO and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, at least one of R58 to R66 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH, and n represents the number of condensed rings sandwiched between a benzene ring having substituents R58 and R59 and a benzene ring having substituents R61 to R64, and is 0 or an integer of 1 to 3;
wherein in the formula (9) R67 to R76 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH R35COOH, —COOR35, —COR35, —CHO and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, at least one of R67 to R76 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH, and n represents the number of condensed rings sandwiched between a benzene ring having substituents R67 to R69 and a benzoquinone ring, and is 0 or an integer of 1 to 3; and,
wherein in the formula (10) R77 to R81 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, R35COOH, —COOR35, —COR35, —CHO and —CN, where R35 represents an alkyl, aryl or aralkyl group or alkylene, arylene having 1 to 24 carbon atoms or an aralkylene group having 1 to 24 carbon atoms, at least one of R77 to R81 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH, Xa− is at least one type of anion selected from the group of anions having a valence of 1 to 3 consisting of a chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogensulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methane sulfonate ion, p-toluene sulfonate ion, trifluoroacetate ion and trifluoromethane sulfonate ion, a represents the ion valence of X and is an integer of 1 to 3, and p represents the doping ratio and has a value of 0.001 to 1.
11. A carbon nanotube composition according to claim 9 , wherein the water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is a water soluble conducting polymer that contains 20 to 100% of the repeating unit represented by the following formula (11) relative to the total number of repeating units throughout the entire polymer:
wherein in the formula (1) y represents an arbitrary number such that 0<y<1, R15 to R32 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR35, —OR35, —OCOR35, —NO2, —COOH, —R35COOH, —COOR35, —COR35, —CHO and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and at least one of R15 to R32 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH.
12. A carbon nanotube composition according to claim 9 , wherein the water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is represented by the following formula (12):
wherein in the formula (12) R33 represents one group selected from the group consisting of a sulfonic acid group, carboxyl group, their alkaline metal salts, ammonium salts and substituted ammonium salts, R34 represents one group selected from the group consisting of a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, dodecyl group, tetracosyl group, methoxy group, ethoxy group, n-propoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, heptoxy group, hexoxy group, octoxy group, dodecoxy group, tetracoxy group, fluoro group, chloro group and bromo group, X represents an arbitrary number such that 0<X<1, and n represents the degree of polymerization and has a value of 3 or more.
13. A carbon nanotube composition according to claim 9 , wherein the water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is a water soluble conducting polymer obtained by polymerizing at least one of type of acidic group-substituted aniline represented by the following formula (13), its alkaline metal salt, ammonium salt and substituted ammonium salt, with an oxidizing agent in a solution containing a basic compound:
wherein in the formula (13) R36 to R41 are respectively and independently selected from the group consisting of H, —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —OCH3, —CH3, —C2H5, —F, —Cl, —Br, —I, —N(R35)2, —NHCOR35, —OH, —O−, —SR3, —OR3, —OCOR35, —NO2, —COOH, —R35COOH, —COOR35, —COR35, —CHO and —CN, where R35 represents an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and at least one of R36 to R41 is a group selected from the group consisting of —SO3 −, —SO3H, —R35SO3 −, —R35SO3H, —COOH and —R35COOH.
14. A carbon nanotube composition according to claim 9 , wherein the water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is a water soluble conducting polymer obtained by polymerizing at least one type of alkoxy group-substituted aminobenzene sulfonic acid, its alkaline metal salt, ammonium salt and substituted ammonium salt, with an oxidizing agent in a solution containing a basic compound.
15. A carbon nanotube composition according to claim 9 , wherein the water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is polyethylene dioxythiophene polystyrene sulfate.
16. A carbon nanotube composition according to claim 2 , wherein the composition contains a heterocyclic compound trimer (i) that is a heterocyclic compound trimer represented by the following formula (16):
wherein in the formula (16) R101 to R112 are substituents respectively and independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, linear or branched acyl group having 2 to 24 carbon atoms, aldehyde group, carboxyl group, linear or branched carboxylic ester group having 2 to 24 carbon atoms, sulfonic acid group, linear or branched sulfonic ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, amido group, dicyanovinyl group, alkyl (linear or branched alkyl group having 1 to 8 carbon atoms) oxycarbonylcyanovinyl group, nitrophenylcyanovinyl group and halogen group;
Ht represents a heteroatom group selected from the group consisting of NR154, S, O, Se and Te, and R154 represents a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms;
Xa− represents at least one type of anion selected from the group consisting of anions having a valence of 1 to 3 consisting of a chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogensulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methane sulfonate ion, p-toluene sulfonate ion, trifluoroacetate ion and trifluoromethane sulfonate ion; a represents the ion valence of X and is an integer of 1 to 3; and, m represents the doping ratio and has a value of 0 to 3.0.
17. A carbon nanotube composition according to claim 2 , wherein the composition contains a heterocyclic compound trimer (i) that is a heterocyclic compound trimer represented by the following general formula (17):
wherein in the formula (17) R113 to R124 represent substituents respectively and independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, linear or branched alkoxy group having 1 to 24 carbon atoms, linear or branched acyl group having 2 to 24 carbon atoms, aldehyde group, carboxyl group, linear or branched carboxylic ester group having 2 to 24 carbon atoms, sulfonic acid group, linear or branched sulfonic ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, amido group, dicyanovinyl group, alkyl (linear or branched alkyl group having 1 to 8 carbon atoms) oxycarbonylcyanovinyl group, nitrophenylcyanovinyl group and halogen group; at least one of R113 to R124 is a cyano group, nitro group, amide group, halogen group, sulfonic acid group, and carboxyl group;
Ht represents a heteroatom group selected from the group consisting of NR154, S, O, Se and Te, and R154 represents a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms;
Xa− represents at least one type of anion selected from the group consisting of anions having a valence of 1 to 3 consisting of a chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methane sulfonate ion, p-toluene sulfonate ion, trifluoroacetate ion and trifluoromethane sulfonate ion; a represents the ion valence of X and is an integer of 1 to 3; and, m represents the doping ratio and has a value of 0 to 3.0.
18. A carbon nanotube composition according to claim 2 , wherein the composition contains a heterocyclic compound trimer (i) that is a heterocyclic compound trimer represented by the following general formula (18):
wherein in the formula (18) R125 to R136 are substituents respectively and independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, linear or branched alkoxy group having 1 to 24 carbon atoms, linear or branched acyl group having 2 to 24 carbon atoms, aldehyde group, carboxylic acid group and its alkaline metal salt, ammonium salt and substituted ammonium salt, linear or branched carboxylic ester group having 2 to 24 carbon atoms, sulfonic acid group and its alkaline metal salt, ammonium salt and substituted ammonium salt, linear or branched sulfonic ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, amido group, dicyanovinyl group, alkyl (linear or branched alkyl group having 1 to 8 carbon atoms)oxycarbonylcyanovinyl group, nitrophenylcyanovinyl group and halogen group;
Xa− represents at least one type of anion selected from the group consisting of anions having a valence of 1 to 3 consisting of a chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methane sulfonate ion, p-toluene sulfonate ion, trifluoroacetate ion and trifluoromethane sulfonate ion; a represents the ion valence of X and is an integer of 1 to 3; and, m represents the doping ratio and has a value of 0 to 3.0.
19. A carbon nanotube composition according to claim 2 , wherein the composition contains a heterocyclic compound trimer (i) that is a heterocyclic compound trimer represented by the following general formula (19):
wherein in the formula (19) R137 to R148 are substituents respectively and independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, linear or branched alkoxy group having 1 to 24 carbon atoms, linear or branched acyl group having 2 to 24 carbon atoms, aldehyde group, carboxyl group, linear or branched carboxylic ester group having 2 to 24 carbon atoms, sulfonic acid group, linear or branched sulfonic ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, amido group, dicyanovinyl group, alkyl (linear or branched alkyl group having 1 to 8 carbon atoms)oxycarbonylcyanovinyl group, nitrophenylcyanovinyl group and halogen group;
Ht represents a heteroatom group selected from the group consisting of NR154, S, O, Se and Te, and R154 represents a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms;
Xa− represents at least one type of anion selected from the group consisting of anions having a valence of 1 to 3 consisting of a chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methane sulfonate ion, p-toluene sulfonate ion, trifluoroacetate ion and trifluoromethane sulfonate ion; a represents the ion valence of X and is an integer of 1 to 3; and, m represents the doping ratio and has a value of 0 to 3.0.
20. A carbon nanotube composition according to claim 2 , wherein the composition contains a heterocyclic compound trimer (i) that is a heterocyclic compound trimer obtained by reacting at least one type of heterocyclic compound represented by the following general formula (20) in a reaction mixture containing at least one type of oxidizing agent and at least one type of solvent:
wherein in the formula (20) R150 to R153 are substituents respectively and independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, linear or branched alkoxy group having 1 to 24 carbon atoms, linear or branched acyl group having 2 to 24 carbon atoms, aldehyde group, carboxyl group, linear or branched carboxylic ester group having 2 to 24 carbon atoms, sulfonic acid group, linear or branched sulfonic ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, amido group, dicyanovinyl group, alkyl (linear or branched alkyl group having 1 to 8 carbon atoms)oxycarbonylcyanovinyl group, nitrophenylcyanovinyl group and halogen group; and,
Ht represents a heteroatom group selected from the group consisting of NR154, S, O, Se and Te, and R154 represents a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms.
21. A carbon nanotube composition according to claim 2 , wherein said carbon nanotube composition includes a the heterocyclic compound trimer (i) having a layered structure.
22. A production method of a carbon nanotube composition comprising: irradiating a carbon nanotube composition according to claim 1 with ultrasonic waves and mixing.
23. A composite comprising a base material, and a coated film composed of the carbon nanotube composition according to claim 1 on at least one surface of the base material.
24. A method of producing a composite comprising: coating the carbon nanotube composition according to claim 1 onto at least one surface of a base material, and forming a coated film by allowing the coated carbon nanotube to stand at room temperature or subjecting it to heat treatment.
25. A production method of a composite according to claim 24 , wherein the heat treatment is carried out within a temperature range of normal temperature to 250° C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/556,406 US20090321688A1 (en) | 2002-11-01 | 2009-09-09 | Carbon Nanotube Composition, Composite Having a Coated Film Composed of the Same, and Their Production Methods |
Applications Claiming Priority (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002-319551 | 2002-11-01 | ||
JP2002-319552 | 2002-11-01 | ||
JP2002319552 | 2002-11-01 | ||
JP2002319551 | 2002-11-01 | ||
JP2003-311927 | 2003-09-03 | ||
JP2003-311926 | 2003-09-03 | ||
JP2003311927 | 2003-09-03 | ||
JP2003311926A JP4266752B2 (en) | 2002-11-01 | 2003-09-03 | Carbon nanotube-containing composition and method for preparing the same, composite using the same, and method for producing the same |
JP2003367533A JP3913208B2 (en) | 2002-11-01 | 2003-10-28 | Carbon nanotube-containing composition, composite having coating film made thereof, and method for producing them |
JP2003-367533 | 2003-10-28 | ||
US10/532,685 US7645400B2 (en) | 2002-11-01 | 2003-10-31 | Composition containing carbon nanotubes having a coating |
PCT/JP2003/014027 WO2004039893A1 (en) | 2002-11-01 | 2003-10-31 | Composition containing carbon nanotubes, composite having coating thereof and process for producing them |
US12/556,406 US20090321688A1 (en) | 2002-11-01 | 2009-09-09 | Carbon Nanotube Composition, Composite Having a Coated Film Composed of the Same, and Their Production Methods |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/532,685 Division US7645400B2 (en) | 2002-11-01 | 2003-10-31 | Composition containing carbon nanotubes having a coating |
PCT/JP2003/014027 Division WO2004039893A1 (en) | 2002-11-01 | 2003-10-31 | Composition containing carbon nanotubes, composite having coating thereof and process for producing them |
Publications (1)
Publication Number | Publication Date |
---|---|
US20090321688A1 true US20090321688A1 (en) | 2009-12-31 |
Family
ID=32234426
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/532,685 Expired - Lifetime US7645400B2 (en) | 2002-11-01 | 2003-10-31 | Composition containing carbon nanotubes having a coating |
US12/556,406 Abandoned US20090321688A1 (en) | 2002-11-01 | 2009-09-09 | Carbon Nanotube Composition, Composite Having a Coated Film Composed of the Same, and Their Production Methods |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/532,685 Expired - Lifetime US7645400B2 (en) | 2002-11-01 | 2003-10-31 | Composition containing carbon nanotubes having a coating |
Country Status (3)
Country | Link |
---|---|
US (2) | US7645400B2 (en) |
KR (2) | KR100720628B1 (en) |
WO (1) | WO2004039893A1 (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090078914A1 (en) * | 2007-09-20 | 2009-03-26 | Xintek, Inc. | Methods and devices for electrophoretic deposition of a uniform carbon nanotube composite film |
US20100273263A1 (en) * | 2007-12-14 | 2010-10-28 | Meijo Nano Carbon Co., Ltd. | Cell culture vessel and method of production thereof |
US20100270513A1 (en) * | 2009-04-03 | 2010-10-28 | Luke Haylock | Conductive solid film material |
US20100330358A1 (en) * | 2008-02-08 | 2010-12-30 | Meijo Nano Carbon Co., Ltd. | Carbon nanotube dispersion and utilization of same |
WO2012068424A2 (en) | 2010-11-17 | 2012-05-24 | Battelle Memorial Institute | Carbon nanotube thin film laminate resistive heater |
CN103101899A (en) * | 2011-11-15 | 2013-05-15 | 北京化工大学 | Preparation method of nano-material thin-film based on complex micelle system |
WO2013074710A1 (en) * | 2011-11-14 | 2013-05-23 | Vorbeck Materials | Graphene compositions |
US8455583B2 (en) | 2004-08-02 | 2013-06-04 | University Of Houston | Carbon nanotube reinforced polymer nanocomposites |
US20130168012A1 (en) * | 2011-12-28 | 2013-07-04 | Hon Hai Precision Industry Co., Ltd. | Method for making lithium ion battery electrode |
US8709539B2 (en) | 2009-02-17 | 2014-04-29 | Meijo University | Process and apparatus for producing composite material that includes carbon nanotubes |
US20140332728A1 (en) * | 2011-10-19 | 2014-11-13 | Environment energy nano technical research institute | Porous material including carbon nanohorns and use thereof |
US10813257B2 (en) * | 2016-09-05 | 2020-10-20 | Nec Corporation | Electromagnetic wave absorbing material |
Families Citing this family (138)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7259410B2 (en) * | 2001-07-25 | 2007-08-21 | Nantero, Inc. | Devices having horizontally-disposed nanofabric articles and methods of making the same |
US6706402B2 (en) * | 2001-07-25 | 2004-03-16 | Nantero, Inc. | Nanotube films and articles |
US6924538B2 (en) * | 2001-07-25 | 2005-08-02 | Nantero, Inc. | Devices having vertically-disposed nanofabric articles and methods of making the same |
US6835591B2 (en) * | 2001-07-25 | 2004-12-28 | Nantero, Inc. | Methods of nanotube films and articles |
US7335395B2 (en) * | 2002-04-23 | 2008-02-26 | Nantero, Inc. | Methods of using pre-formed nanotubes to make carbon nanotube films, layers, fabrics, ribbons, elements and articles |
US7858185B2 (en) | 2003-09-08 | 2010-12-28 | Nantero, Inc. | High purity nanotube fabrics and films |
US7560136B2 (en) * | 2003-01-13 | 2009-07-14 | Nantero, Inc. | Methods of using thin metal layers to make carbon nanotube films, layers, fabrics, ribbons, elements and articles |
WO2005019793A2 (en) * | 2003-05-14 | 2005-03-03 | Nantero, Inc. | Sensor platform using a horizontally oriented nanotube element |
US7375369B2 (en) * | 2003-09-08 | 2008-05-20 | Nantero, Inc. | Spin-coatable liquid for formation of high purity nanotube films |
US7504051B2 (en) * | 2003-09-08 | 2009-03-17 | Nantero, Inc. | Applicator liquid for use in electronic manufacturing processes |
US20070128440A1 (en) * | 2003-12-11 | 2007-06-07 | The Trustees Of The University Of Pennsylvania | Cellular probes |
US20070189953A1 (en) * | 2004-01-30 | 2007-08-16 | Centre National De La Recherche Scientifique (Cnrs) | Method for obtaining carbon nanotubes on supports and composites comprising same |
JP2005290292A (en) * | 2004-04-02 | 2005-10-20 | National Institute Of Advanced Industrial & Technology | Saturable absorber of carbon nanotube-dispersed polyimide |
US7556746B2 (en) * | 2004-06-03 | 2009-07-07 | Nantero, Inc. | Method of making an applicator liquid for electronics fabrication process |
US7658869B2 (en) * | 2004-06-03 | 2010-02-09 | Nantero, Inc. | Applicator liquid containing ethyl lactate for preparation of nanotube films |
KR100880280B1 (en) * | 2004-06-03 | 2009-01-28 | 난테로 인크. | Applicator liquid for use in electronic fabrication processes |
CN1296436C (en) * | 2004-06-07 | 2007-01-24 | 清华大学 | Prepn process of composite material based on carbon nanotube |
US20060006367A1 (en) * | 2004-07-06 | 2006-01-12 | Chun-Yen Hsiao | Carbon nanotube suspension |
JP4807817B2 (en) * | 2004-08-05 | 2011-11-02 | 三菱レイヨン株式会社 | Method for producing conductive molded body and conductive molded body |
US7804238B2 (en) * | 2004-08-31 | 2010-09-28 | Nissan Motor Co., Ltd. | Functional thin-film element, producing method thereof, and article using functional thin-film element |
US20080281014A1 (en) * | 2004-09-09 | 2008-11-13 | Mitsubishi Rayon Co., Ltd. | Nanosubstance-Containing Composition, Process for Producing the Same, and Composite Made With the Same |
WO2006121461A2 (en) * | 2004-09-16 | 2006-11-16 | Nantero, Inc. | Light emitters using nanotubes and methods of making same |
US20080132584A1 (en) * | 2004-12-02 | 2008-06-05 | The Trustees Of The University Of Pennsylvania | Biofunctional Nanoprobes |
WO2006065937A2 (en) * | 2004-12-16 | 2006-06-22 | Nantero, Inc. | Aqueous carbon nanotube applicator liquids and methods for producing applicator liquids thereof |
FR2883879B1 (en) * | 2005-04-04 | 2007-05-25 | Arkema Sa | POLYMER MATERIALS CONTAINING IMPROVED DISPERSION CARBON NANOTUBES AND PROCESS FOR THEIR PREPARATION |
US7479654B2 (en) * | 2005-05-09 | 2009-01-20 | Nantero, Inc. | Memory arrays using nanotube articles with reprogrammable resistance |
TWI264271B (en) * | 2005-05-13 | 2006-10-11 | Delta Electronics Inc | Heat sink |
US7915122B2 (en) * | 2005-06-08 | 2011-03-29 | Nantero, Inc. | Self-aligned cell integration scheme |
KR101121203B1 (en) * | 2005-07-27 | 2012-03-23 | 삼성전자주식회사 | Dispersant for high-concentrated carbon nanotube solution and composition comprising the same |
CA2621103C (en) * | 2005-09-06 | 2015-11-03 | Nantero, Inc. | Nanotube fabric-based sensor systems and methods of making same |
KR100815028B1 (en) * | 2005-10-05 | 2008-03-18 | 삼성전자주식회사 | Dispersant for carbon nanotube and composition comprising the same |
DE102005053646A1 (en) * | 2005-11-10 | 2007-05-16 | Starck H C Gmbh Co Kg | Polymer coatings with improved solvent resistance |
WO2007066649A1 (en) * | 2005-12-06 | 2007-06-14 | Mitsubishi Rayon Co., Ltd. | Carbon nanotube-containing composition, composite body, and their production methods |
WO2008048313A2 (en) | 2005-12-19 | 2008-04-24 | Advanced Technology Materials, Inc. | Production of carbon nanotubes |
US20070158619A1 (en) * | 2006-01-12 | 2007-07-12 | Yucong Wang | Electroplated composite coating |
CN101466598B (en) * | 2006-03-10 | 2013-02-27 | 豪富公司 | Low density lightning strike protection for use in airplanes |
KR100773551B1 (en) * | 2006-04-14 | 2007-11-07 | 삼성전자주식회사 | Carbon Nanotube dispersion solution and method for preparing the same |
CN101484628A (en) * | 2006-05-02 | 2009-07-15 | 罗尔股份有限公司 | Modification of reinforcing fiber tows used in composite materials by using nanoreinforcements |
US7768050B2 (en) * | 2006-07-07 | 2010-08-03 | The Trustees Of The University Of Pennsylvania | Ferroelectric thin films |
US8545962B2 (en) * | 2006-08-07 | 2013-10-01 | Paradigm Energy Research Corporation | Nano-fiber arrayed surfaces |
US8323789B2 (en) | 2006-08-31 | 2012-12-04 | Cambridge Enterprise Limited | Nanomaterial polymer compositions and uses thereof |
CN100434478C (en) * | 2006-09-28 | 2008-11-19 | 同济大学 | Medium temperature proton conductive mateiral basedon hydrophilic carbon nano tube and its preparing method |
US8961830B2 (en) * | 2006-10-11 | 2015-02-24 | University Of Florida Research Foundation, Inc. | Electroactive polymers containing pendant pi-interacting/binding substituents, their carbon nanotube composites, and processes to form the same |
KR100801595B1 (en) * | 2006-11-09 | 2008-02-05 | 제일모직주식회사 | Composition of carbon nano tube and transparent and conductive film |
KR100828477B1 (en) * | 2006-12-19 | 2008-05-13 | 재단법인서울대학교산학협력재단 | Method of conductive multilayered nanomembranes, and mems sensor and method of using the same |
US8158217B2 (en) * | 2007-01-03 | 2012-04-17 | Applied Nanostructured Solutions, Llc | CNT-infused fiber and method therefor |
US20100279569A1 (en) * | 2007-01-03 | 2010-11-04 | Lockheed Martin Corporation | Cnt-infused glass fiber materials and process therefor |
US20120189846A1 (en) * | 2007-01-03 | 2012-07-26 | Lockheed Martin Corporation | Cnt-infused ceramic fiber materials and process therefor |
US9005755B2 (en) | 2007-01-03 | 2015-04-14 | Applied Nanostructured Solutions, Llc | CNS-infused carbon nanomaterials and process therefor |
US8951632B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
US8951631B2 (en) * | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused metal fiber materials and process therefor |
US20080166563A1 (en) * | 2007-01-04 | 2008-07-10 | Goodrich Corporation | Electrothermal heater made from thermally conducting electrically insulating polymer material |
KR100913700B1 (en) * | 2007-06-12 | 2009-08-24 | 삼성전자주식회사 | Carbon nano-tubeCNT thin film comprising an amine compound, and a manufacturing method thereof |
KR100869161B1 (en) * | 2007-07-13 | 2008-11-19 | 한국전기연구원 | Polymer binder composition for transparent conductive films containing carbon nanotubes |
KR100926699B1 (en) | 2007-07-25 | 2009-11-17 | 연세대학교 산학협력단 | Method for controlling porosity of carbon nanotube thin film and manufacturing method thereof |
US20090081383A1 (en) * | 2007-09-20 | 2009-03-26 | Lockheed Martin Corporation | Carbon Nanotube Infused Composites via Plasma Processing |
US20090081441A1 (en) * | 2007-09-20 | 2009-03-26 | Lockheed Martin Corporation | Fiber Tow Comprising Carbon-Nanotube-Infused Fibers |
CN101394712B (en) * | 2007-09-21 | 2010-08-25 | 清华大学 | Hole blackening solution and preparation thereof |
FR2922369B1 (en) * | 2007-10-11 | 2010-01-08 | Commissariat Energie Atomique | ELECTRODE COMPRISING POLY (3,4-ETHYLENEDIOXYTHIOPHENE) POLY (STYRENESULFONATE) |
KR101213787B1 (en) * | 2007-11-14 | 2012-12-18 | 성균관대학교산학협력단 | Conductivity enhanced transparent conductive film and fabrication method thereof |
WO2009064133A2 (en) * | 2007-11-14 | 2009-05-22 | Cheil Industries Inc. | Conductivity enhanced transparent conductive film and fabrication method thereof |
US20090169870A1 (en) * | 2007-12-27 | 2009-07-02 | Essilor International (Compagnie Generale D'optique) | Carbon Nanotube-Based Curable Coating Composition Providing Antistatic Abrasion-Resistant Coated Articles |
CN101960047A (en) * | 2007-12-27 | 2011-01-26 | Posco公司 | Chrome-free coating compositions for surface-treating steel sheet including carbon nanotube, methods for surface-treating steel sheet and surface-treated steel sheets using the same |
US8597547B2 (en) * | 2008-01-28 | 2013-12-03 | Yazaki Corporation | Electrically conductive polymer composites |
KR100965106B1 (en) * | 2008-01-29 | 2010-06-22 | 웅진케미칼 주식회사 | Conductive coating composition, unstretched conductive sheet using them and anti-static packing material thereby |
JP2009203118A (en) * | 2008-02-28 | 2009-09-10 | Fujifilm Corp | Nanocarbon film, electrode using it, and its manufacturing method |
JP5370151B2 (en) * | 2008-02-29 | 2013-12-18 | 東レ株式会社 | Substrate with transparent conductive film, method for producing the same, and touch panel using the same |
WO2009123371A1 (en) * | 2008-04-03 | 2009-10-08 | Seoul National University Industry Foundation | The conductive nanomembrane, and mems sensor of using the same |
US8390580B2 (en) * | 2008-07-09 | 2013-03-05 | Tsinghua University | Touch panel, liquid crystal display screen using the same, and methods for making the touch panel and the liquid crystal display screen |
KR101091196B1 (en) * | 2008-08-14 | 2011-12-09 | 한국전기연구원 | transparent conductive films containing carbon nanotubes and the touch panel |
US8557345B2 (en) * | 2008-08-26 | 2013-10-15 | Xerox Corporation | Process for making CNT/PFA composite coatings for fuser applications |
US9441131B2 (en) * | 2008-08-26 | 2016-09-13 | Xerox Corporation | CNT/fluoropolymer coating composition |
CN101659789B (en) * | 2008-08-29 | 2012-07-18 | 清华大学 | Preparation method for carbon nano tube/conducting polymer composite material |
JP5557992B2 (en) * | 2008-09-02 | 2014-07-23 | 国立大学法人北海道大学 | Conductive fiber, conductive yarn, fiber structure having carbon nanotubes attached thereto, and manufacturing method thereof |
ITTO20080734A1 (en) * | 2008-10-07 | 2010-04-08 | Techfab S R L | MICROWAVE RETICULABLE COATING COMPOSITION AND RELATED COVERING PROCEDURE FOR MICROWOOD COVERINGS |
US20100099011A1 (en) * | 2008-10-21 | 2010-04-22 | Gm Global Technology Operations, Inc. | Electrode morphology via use of high boiling point co-solvents in electrode inks |
CA2750484A1 (en) * | 2009-02-17 | 2010-12-16 | Applied Nanostructured Solutions, Llc | Composites comprising carbon nanotubes on fiber |
WO2010141130A1 (en) * | 2009-02-27 | 2010-12-09 | Lockheed Martin Corporation | Low temperature cnt growth using gas-preheat method |
US20100224129A1 (en) * | 2009-03-03 | 2010-09-09 | Lockheed Martin Corporation | System and method for surface treatment and barrier coating of fibers for in situ cnt growth |
WO2010112680A1 (en) * | 2009-03-31 | 2010-10-07 | Hutchinson | Transparent conductive films or coatings |
AU2010233113A1 (en) * | 2009-04-10 | 2011-10-13 | Applied Nanostructured Solutions Llc | Method and apparatus for using a vertical furnace to infuse carbon nanotubes to fiber |
US20100260998A1 (en) * | 2009-04-10 | 2010-10-14 | Lockheed Martin Corporation | Fiber sizing comprising nanoparticles |
US20100272891A1 (en) * | 2009-04-10 | 2010-10-28 | Lockheed Martin Corporation | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
BRPI1010288A2 (en) * | 2009-04-10 | 2016-03-22 | Applied Nanostructured Sols | apparatus and method for producing carbon nanotubes on a continuously moving substrate |
CA2758570A1 (en) * | 2009-04-24 | 2010-12-16 | Applied Nanostructured Solutions, Llc | Cnt-based signature control material |
US9111658B2 (en) | 2009-04-24 | 2015-08-18 | Applied Nanostructured Solutions, Llc | CNS-shielded wires |
JP5744008B2 (en) * | 2009-04-27 | 2015-07-01 | アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニーApplied Nanostructuredsolutions, Llc | CNT-based resistive heating for deicing composite structures |
CA2760447A1 (en) * | 2009-04-30 | 2010-11-04 | Applied Nanostructured Solutions, Llc | Method and system for close proximity catalysis for carbon nanotube synthesis |
US9242897B2 (en) * | 2009-05-18 | 2016-01-26 | Ppg Industries Ohio, Inc. | Aqueous dispersions and methods of making same |
JP5377120B2 (en) * | 2009-07-02 | 2013-12-25 | 三菱レイヨン株式会社 | Photoelectric conversion element and manufacturing method thereof |
US8574673B2 (en) | 2009-07-31 | 2013-11-05 | Nantero Inc. | Anisotropic nanotube fabric layers and films and methods of forming same |
US8128993B2 (en) * | 2009-07-31 | 2012-03-06 | Nantero Inc. | Anisotropic nanotube fabric layers and films and methods of forming same |
WO2011017200A1 (en) * | 2009-08-03 | 2011-02-10 | Lockheed Martin Corporation | Incorporation of nanoparticles in composite fibers |
US20110048508A1 (en) * | 2009-08-26 | 2011-03-03 | International Business Machines Corporation | Doping of Carbon Nanotube Films for the Fabrication of Transparent Electrodes |
US8561934B2 (en) * | 2009-08-28 | 2013-10-22 | Teresa M. Kruckenberg | Lightning strike protection |
WO2011053811A1 (en) * | 2009-10-30 | 2011-05-05 | The Board Of Trustees Of The Leland Stanford Junior University | Conductive fibrous materials |
KR20120099690A (en) * | 2009-11-02 | 2012-09-11 | 어플라이드 나노스트럭처드 솔루션스, 엘엘씨. | Cnt-infused aramid fiber materials and process therefor |
JP5643835B2 (en) * | 2009-11-23 | 2014-12-17 | アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニーApplied Nanostructuredsolutions, Llc | CNT-adapted sea-based composite structure |
US20110123735A1 (en) * | 2009-11-23 | 2011-05-26 | Applied Nanostructured Solutions, Llc | Cnt-infused fibers in thermoset matrices |
EP2504164A4 (en) * | 2009-11-23 | 2013-07-17 | Applied Nanostructured Sols | Ceramic composite materials containing carbon nanotube-infused fiber materials and methods for production thereof |
US8545963B2 (en) * | 2009-12-14 | 2013-10-01 | Applied Nanostructured Solutions, Llc | Flame-resistant composite materials and articles containing carbon nanotube-infused fiber materials |
DE102009054718A1 (en) * | 2009-12-16 | 2011-06-22 | Evonik Litarion GmbH, 01917 | Use of N-ethyl pyrrolidone in the manufacture of electrodes for double-layer capacitors |
US20110168018A1 (en) * | 2010-01-14 | 2011-07-14 | Research Institute Of Petroleum Industry (Ripi) | Hybrid nano sorbent |
US9167736B2 (en) * | 2010-01-15 | 2015-10-20 | Applied Nanostructured Solutions, Llc | CNT-infused fiber as a self shielding wire for enhanced power transmission line |
CA2785803A1 (en) * | 2010-02-02 | 2011-11-24 | Applied Nanostructured Solutions, Llc | Carbon nanotube-infused fiber materials containing parallel-aligned carbon nanotubes, methods for production thereof, and composite materials derived therefrom |
WO2011100661A1 (en) | 2010-02-12 | 2011-08-18 | Nantero, Inc. | Methods for controlling density, porosity, and/or gap size within nanotube fabric layers and films |
CN102934267A (en) | 2010-03-02 | 2013-02-13 | 应用奈米结构公司 | Spiral wound electrical devices containing carbon nanotube-infused electrode materials and methods and apparatuses for production thereof |
BR112012021634A2 (en) * | 2010-03-02 | 2019-09-24 | Applied Nanostructured Sols | electrical devices containing infused carbon nanotube fibers and methods for reproducing them. |
US8780526B2 (en) | 2010-06-15 | 2014-07-15 | Applied Nanostructured Solutions, Llc | Electrical devices containing carbon nanotube-infused fibers and methods for production thereof |
US9017854B2 (en) | 2010-08-30 | 2015-04-28 | Applied Nanostructured Solutions, Llc | Structural energy storage assemblies and methods for production thereof |
CA2808242A1 (en) | 2010-09-14 | 2012-03-22 | Applied Nanostructured Solutions, Llc | Glass substrates having carbon nanotubes grown thereon and methods for production thereof |
US10069072B2 (en) | 2010-09-20 | 2018-09-04 | Nantero, Inc. | Nanotube solutions with high concentration and low contamination and methods for purifiying nanotube solutions |
CN103118975A (en) | 2010-09-22 | 2013-05-22 | 应用奈米结构公司 | Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof |
CA2782976A1 (en) | 2010-09-23 | 2012-03-29 | Applied Nanostructured Solutions, Llc | Cnt-infused fiber as a self shielding wire for enhanced power transmission line |
JP6162693B2 (en) * | 2011-06-24 | 2017-07-12 | ブルーワー サイエンス アイ エヌ シー. | Highly soluble carbon nanotubes with improved conductivity |
FI20110232L (en) * | 2011-07-05 | 2013-01-11 | Hafmex Oy | Heated wind turbine rotor |
ITTO20110699A1 (en) * | 2011-07-29 | 2013-01-30 | Tecnocarbon Ant S R L | COATING WITH CARBON NANOTUBES FOR PHOTOVOLTAIC MODULES AND ITS APPLICATION PROCEDURE |
US8925736B2 (en) * | 2011-09-12 | 2015-01-06 | University Of Houston | Nanocomposite polymer-carbon based nanomaterial filters for the simultaneous removal of bacteria and heavy metals |
KR101182723B1 (en) * | 2012-01-27 | 2012-09-13 | 한국신발피혁연구소 | Method for manufacturing conductive polyurethane resin composite in which carbon nano tube is uniformly dispersed |
US9634251B2 (en) | 2012-02-27 | 2017-04-25 | Nantero Inc. | Nanotube solution treated with molecular additive, nanotube film having enhanced adhesion property, and methods for forming the nanotube solution and the nanotube film |
US9085464B2 (en) | 2012-03-07 | 2015-07-21 | Applied Nanostructured Solutions, Llc | Resistance measurement system and method of using the same |
CN102702892A (en) * | 2012-06-14 | 2012-10-03 | 天长市银狐漆业有限公司 | Conducting paint composition and preparation method thereof |
JP2014048165A (en) * | 2012-08-31 | 2014-03-17 | Nitto Denko Corp | Destaticizer for analysis |
EP2990380B1 (en) * | 2013-04-24 | 2018-09-19 | Nitta Corporation | Composite material and molded article |
US9650732B2 (en) | 2013-05-01 | 2017-05-16 | Nantero Inc. | Low defect nanotube application solutions and fabrics and methods for making same |
WO2015005204A1 (en) | 2013-07-08 | 2015-01-15 | 東洋紡株式会社 | Electrically conductive paste |
US10654718B2 (en) | 2013-09-20 | 2020-05-19 | Nantero, Inc. | Scalable nanotube fabrics and methods for making same |
WO2015047605A1 (en) | 2013-09-24 | 2015-04-02 | Henkel IP & Holding GmbH | Pyrolized organic layers and conductive prepregs made therewith |
US9545042B2 (en) * | 2014-03-14 | 2017-01-10 | Ppg Industries Ohio, Inc. | P-static charge drain layer including carbon nanotubes |
US10442549B2 (en) | 2015-04-02 | 2019-10-15 | Ppg Industries Ohio, Inc. | Liner-type, antistatic topcoat system for aircraft canopies and windshields |
US11382181B2 (en) * | 2016-12-02 | 2022-07-05 | Goodrich Corporation | Method to create carbon nanotube heaters with varying resistance |
US10221288B1 (en) | 2017-08-08 | 2019-03-05 | International Business Machines Corporation | Matrix bonding abrasion resistant CNTs (MBARCs) and employing same in fiber reinforced polymer composites |
US11525209B2 (en) * | 2017-09-13 | 2022-12-13 | The Board Of Regents For Oklahoma State University | Preparation and characterization of organic conductive threads as non-metallic electrodes and interconnects |
US11344241B2 (en) * | 2017-09-13 | 2022-05-31 | Allegheny Singer Research Institute | Conductive fiber with polythiophene coating |
CN109294423B (en) * | 2018-08-29 | 2021-02-02 | 湖北启利新材料股份有限公司 | Water-based nano polyaniline-polyurethane conductive anticorrosive paint and preparation method thereof |
US11633881B1 (en) | 2018-12-20 | 2023-04-25 | General Nano Llc | Heated composite tool and method for building and use |
CN111440179A (en) * | 2020-04-07 | 2020-07-24 | 曲靖师范学院 | Conjugated organic lithium ion battery electrode material and preparation method and application thereof |
CN111620885B (en) * | 2020-06-30 | 2023-05-30 | 华东理工大学 | Poly R-indole blue light absorber and preparation method and application thereof |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002072682A1 (en) * | 2001-03-08 | 2002-09-19 | The Board Of Governors For Higher Education, State Of Rhode Island And Providence Plantations | Conductive polymer-inorganic hybrid composites |
US20030134236A1 (en) * | 2001-12-26 | 2003-07-17 | Debasis Majumdar | Composition for antistat layer |
US20030134212A1 (en) * | 2001-12-26 | 2003-07-17 | Eastman Kodak Company | Element with antistat layer |
US6599446B1 (en) * | 2000-11-03 | 2003-07-29 | General Electric Company | Electrically conductive polymer composite compositions, method for making, and method for electrical conductivity enhancement |
US20030143453A1 (en) * | 2001-11-30 | 2003-07-31 | Zhifeng Ren | Coated carbon nanotube array electrodes |
US20040026007A1 (en) * | 2002-02-14 | 2004-02-12 | Brian Hubert | Method and apparatus for direct fabrication of nanostructures |
US20040124504A1 (en) * | 2002-09-24 | 2004-07-01 | Che-Hsiung Hsu | Electrically conducting organic polymer/nanoparticle composites and methods for use thereof |
US20060079393A1 (en) * | 2000-10-31 | 2006-04-13 | Koichi Matsumoto | Electrode for solid polymer electrolyte fuel cell |
US20070265379A1 (en) * | 2003-05-22 | 2007-11-15 | Zyvex Corporation | Nanocomposites and methods thereto |
Family Cites Families (47)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH089662B2 (en) | 1985-02-26 | 1996-01-31 | 日東電工株式会社 | Conductive material |
US5342912A (en) | 1987-12-14 | 1994-08-30 | Fred Wudl | Self-doped zwitterionic aniline polymers |
US5863981A (en) | 1986-03-24 | 1999-01-26 | The Regents Of The University Of California | Electrically conducting water-soluble self-doping polyaniline polymers and the aqueous solutions thereof |
US5891968A (en) | 1986-03-24 | 1999-04-06 | The Regents Of University Of California | Method of making self-doped zwitterionic heterocyclic polymers |
WO1987005914A1 (en) | 1986-03-24 | 1987-10-08 | The Regents Of The University Of California | Self-doped polymers |
GB8717458D0 (en) | 1987-07-23 | 1987-08-26 | Cookson Group Plc | Electroconductive polymers |
US5137991A (en) | 1988-05-13 | 1992-08-11 | The Ohio State University Research Foundation | Polyaniline compositions, processes for their preparation and uses thereof |
US5164465A (en) | 1988-05-13 | 1992-11-17 | Ohio State University Research Foundation | Sulfonated polyaniline salt compositions, processes for their preparation and uses thereof |
JP2902727B2 (en) | 1990-05-30 | 1999-06-07 | 株式会社日立製作所 | Charged particle beam irradiation method and observation method |
JPH04268331A (en) | 1991-02-25 | 1992-09-24 | Fuji Xerox Co Ltd | Production of self-doping conductive polymer |
JP3147407B2 (en) | 1991-04-26 | 2001-03-19 | 昭和電工株式会社 | Conductive polymer composite material and method for producing the same |
JPH05226238A (en) | 1991-10-31 | 1993-09-03 | Internatl Business Mach Corp <Ibm> | Discharge top layer capable of being developed by base for e-beam resist use |
JP3182239B2 (en) | 1991-12-04 | 2001-07-03 | 昭和電工株式会社 | Novel water-soluble conductive polymer and method for producing the same |
JP3051244B2 (en) | 1991-12-27 | 2000-06-12 | 三菱レイヨン株式会社 | Sulfonated aniline copolymers and their preparation |
JP3186328B2 (en) | 1992-07-20 | 2001-07-11 | 昭和電工株式会社 | Conductive composite and manufacturing method thereof |
JP3066431B2 (en) | 1992-07-20 | 2000-07-17 | 昭和電工株式会社 | Method for producing conductive polymer composite |
JPH0656987A (en) | 1992-08-11 | 1994-03-01 | Bridgestone Corp | Produciton of conductive polymer |
JP3184642B2 (en) | 1992-11-09 | 2001-07-09 | 昭和電工株式会社 | Conductive composite material and method for producing the same |
JP2903038B2 (en) | 1993-02-15 | 1999-06-07 | 三菱レイヨン株式会社 | Aniline-based conductive polymer and method for producing the same |
JP3149290B2 (en) | 1993-03-08 | 2001-03-26 | 昭和電工株式会社 | Method for producing conductive polymer |
JP3814830B2 (en) | 1993-05-28 | 2006-08-30 | 昭和電工株式会社 | Antistatic material, antistatic method and observation or inspection method using the same, and antistatic article |
JP3413956B2 (en) | 1993-05-31 | 2003-06-09 | 昭和電工株式会社 | Method for producing conductive polymer |
JP3037547B2 (en) | 1993-09-03 | 2000-04-24 | 三菱レイヨン株式会社 | Conductive composition, conductor and method of forming the same |
JP3154460B2 (en) | 1993-12-29 | 2001-04-09 | 三菱レイヨン株式会社 | Water-soluble aniline-based conductive polymer and method for producing the same |
JP2959968B2 (en) | 1994-04-04 | 1999-10-06 | 三菱レイヨン株式会社 | Method for producing soluble aniline-based conductive polymer |
JP3340893B2 (en) | 1995-08-21 | 2002-11-05 | 三菱レイヨン株式会社 | Soluble aminonaphthalene-based conductive polymer and method for producing the same |
JP3043290B2 (en) | 1996-06-10 | 2000-05-22 | 株式会社日本触媒 | Water-soluble conductive polyaniline and method for producing the same |
US6187823B1 (en) | 1998-10-02 | 2001-02-13 | University Of Kentucky Research Foundation | Solubilizing single-walled carbon nanotubes by direct reaction with amines and alkylaryl amines |
JP4416882B2 (en) | 1998-10-22 | 2010-02-17 | 株式会社日本触媒 | Method for producing water-soluble conductive polyaniline |
JP3631910B2 (en) * | 1999-02-01 | 2005-03-23 | 三菱レイヨン株式会社 | Method for producing highly conductive aniline polymer |
JP2001011344A (en) * | 1999-06-30 | 2001-01-16 | Nec Corp | Coating and film formed using the same and their production |
JP3536053B2 (en) | 2000-03-14 | 2004-06-07 | 独立行政法人理化学研究所 | Triindole derivative |
DE60136837D1 (en) | 2000-10-17 | 2009-01-15 | Mitsubishi Rayon Co | METHOD FOR PRODUCING A TRIMER OF AN INDOINDIVATE AND TRIMER OF AN INDOINDIVATE AND LAMINATED STRUCTURE THEREOF |
JP2002140930A (en) | 2000-11-01 | 2002-05-17 | Mitsubishi Rayon Co Ltd | Conductive composition and flexible conductive material |
US7265174B2 (en) * | 2001-03-22 | 2007-09-04 | Clemson University | Halogen containing-polymer nanocomposite compositions, methods, and products employing such compositions |
CA2442310A1 (en) * | 2001-03-26 | 2002-10-03 | Eikos, Inc. | Coatings containing carbon nanotubes |
US20030077515A1 (en) * | 2001-04-02 | 2003-04-24 | Chen George Zheng | Conducting polymer-carbon nanotube composite materials and their uses |
WO2003013199A2 (en) * | 2001-07-27 | 2003-02-13 | Eikos, Inc. | Conformal coatings comprising carbon nanotubes |
JP3747167B2 (en) | 2001-09-20 | 2006-02-22 | 三菱レイヨン株式会社 | Conductive composition, conductor and method for forming the same |
JP3706825B2 (en) | 2001-10-15 | 2005-10-19 | 三菱レイヨン株式会社 | Conductive composition, conductor and method for forming the same |
JP4091765B2 (en) | 2001-12-21 | 2008-05-28 | 三菱レイヨン株式会社 | Method for producing indole derivative trimer composite conductor |
JP2003292801A (en) * | 2002-02-04 | 2003-10-15 | Toray Ind Inc | Polymer composite |
CN1639246A (en) * | 2002-03-01 | 2005-07-13 | 纳幕尔杜邦公司 | Printing of organic conductive polymers containing additives |
JP4273726B2 (en) | 2002-03-26 | 2009-06-03 | 東レ株式会社 | Carbon nanotube-containing paste, carbon nanotube dispersed composite, and method for producing carbon nanotube dispersed composite |
US20040034177A1 (en) * | 2002-05-02 | 2004-02-19 | Jian Chen | Polymer and method for using the polymer for solubilizing nanotubes |
US7317047B2 (en) * | 2002-09-24 | 2008-01-08 | E.I. Du Pont De Nemours And Company | Electrically conducting organic polymer/nanoparticle composites and methods for use thereof |
US20050165155A1 (en) * | 2003-10-21 | 2005-07-28 | Blanchet-Fincher Graciela B. | Insulating polymers containing polyaniline and carbon nanotubes |
-
2003
- 2003-10-31 KR KR1020067017406A patent/KR100720628B1/en not_active IP Right Cessation
- 2003-10-31 WO PCT/JP2003/014027 patent/WO2004039893A1/en active Application Filing
- 2003-10-31 KR KR1020057007195A patent/KR100704795B1/en active IP Right Grant
- 2003-10-31 US US10/532,685 patent/US7645400B2/en not_active Expired - Lifetime
-
2009
- 2009-09-09 US US12/556,406 patent/US20090321688A1/en not_active Abandoned
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060079393A1 (en) * | 2000-10-31 | 2006-04-13 | Koichi Matsumoto | Electrode for solid polymer electrolyte fuel cell |
US6599446B1 (en) * | 2000-11-03 | 2003-07-29 | General Electric Company | Electrically conductive polymer composite compositions, method for making, and method for electrical conductivity enhancement |
WO2002072682A1 (en) * | 2001-03-08 | 2002-09-19 | The Board Of Governors For Higher Education, State Of Rhode Island And Providence Plantations | Conductive polymer-inorganic hybrid composites |
US20040149963A1 (en) * | 2001-03-08 | 2004-08-05 | John Sinko | Conductive polymer-inorganic hybrid composites |
US20030143453A1 (en) * | 2001-11-30 | 2003-07-31 | Zhifeng Ren | Coated carbon nanotube array electrodes |
US20030134236A1 (en) * | 2001-12-26 | 2003-07-17 | Debasis Majumdar | Composition for antistat layer |
US20030134212A1 (en) * | 2001-12-26 | 2003-07-17 | Eastman Kodak Company | Element with antistat layer |
US20040026007A1 (en) * | 2002-02-14 | 2004-02-12 | Brian Hubert | Method and apparatus for direct fabrication of nanostructures |
US20040124504A1 (en) * | 2002-09-24 | 2004-07-01 | Che-Hsiung Hsu | Electrically conducting organic polymer/nanoparticle composites and methods for use thereof |
US20070265379A1 (en) * | 2003-05-22 | 2007-11-15 | Zyvex Corporation | Nanocomposites and methods thereto |
Non-Patent Citations (1)
Title |
---|
Eptstein ("Electrical Conductivity in Conjugated Polymers." chap 2 of "Conductive Polymers & Plastics in Industrial Applications." Rupprecht, Elsevier Inc, pub 1999). * |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8455583B2 (en) | 2004-08-02 | 2013-06-04 | University Of Houston | Carbon nanotube reinforced polymer nanocomposites |
US7850874B2 (en) * | 2007-09-20 | 2010-12-14 | Xintek, Inc. | Methods and devices for electrophoretic deposition of a uniform carbon nanotube composite film |
US20090078914A1 (en) * | 2007-09-20 | 2009-03-26 | Xintek, Inc. | Methods and devices for electrophoretic deposition of a uniform carbon nanotube composite film |
US20100273263A1 (en) * | 2007-12-14 | 2010-10-28 | Meijo Nano Carbon Co., Ltd. | Cell culture vessel and method of production thereof |
US9217130B2 (en) | 2007-12-14 | 2015-12-22 | Meijo Nano Carbon Co., Ltd. | Cell culture vessel and method of production thereof |
US20100330358A1 (en) * | 2008-02-08 | 2010-12-30 | Meijo Nano Carbon Co., Ltd. | Carbon nanotube dispersion and utilization of same |
US9181090B2 (en) | 2008-02-08 | 2015-11-10 | Meijo Nano Carbon Co., Ltd. | Carbon nanotube dispersion and utilization of same |
US8709539B2 (en) | 2009-02-17 | 2014-04-29 | Meijo University | Process and apparatus for producing composite material that includes carbon nanotubes |
US20100270513A1 (en) * | 2009-04-03 | 2010-10-28 | Luke Haylock | Conductive solid film material |
WO2012068424A2 (en) | 2010-11-17 | 2012-05-24 | Battelle Memorial Institute | Carbon nanotube thin film laminate resistive heater |
US20140332728A1 (en) * | 2011-10-19 | 2014-11-13 | Environment energy nano technical research institute | Porous material including carbon nanohorns and use thereof |
WO2013074710A1 (en) * | 2011-11-14 | 2013-05-23 | Vorbeck Materials | Graphene compositions |
EP2780281A4 (en) * | 2011-11-14 | 2015-05-27 | Vorbeck Materials Corp | Graphene compositions |
EP2780282A4 (en) * | 2011-11-14 | 2015-05-27 | Vorbeck Materials Corp | Graphene containing compositions |
CN103101899A (en) * | 2011-11-15 | 2013-05-15 | 北京化工大学 | Preparation method of nano-material thin-film based on complex micelle system |
US20130168012A1 (en) * | 2011-12-28 | 2013-07-04 | Hon Hai Precision Industry Co., Ltd. | Method for making lithium ion battery electrode |
US9466826B2 (en) * | 2011-12-28 | 2016-10-11 | Tsinghua University | Method for making lithium ion battery electrode |
US10813257B2 (en) * | 2016-09-05 | 2020-10-20 | Nec Corporation | Electromagnetic wave absorbing material |
Also Published As
Publication number | Publication date |
---|---|
US7645400B2 (en) | 2010-01-12 |
KR20050057680A (en) | 2005-06-16 |
KR20060103962A (en) | 2006-10-04 |
KR100720628B1 (en) | 2007-05-21 |
WO2004039893A1 (en) | 2004-05-13 |
US20060052509A1 (en) | 2006-03-09 |
KR100704795B1 (en) | 2007-04-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7645400B2 (en) | Composition containing carbon nanotubes having a coating | |
JP4266752B2 (en) | Carbon nanotube-containing composition and method for preparing the same, composite using the same, and method for producing the same | |
Waltman et al. | Substituent effects in the electropolymerization of aromatic heterocyclic compounds | |
JP3913208B2 (en) | Carbon nanotube-containing composition, composite having coating film made thereof, and method for producing them | |
JP2005281672A (en) | Carbon nanotube-containing composition, complex having coating film comprising it, and method for manufacturing them | |
US7585981B2 (en) | Method for producing trimer of indole derivative, and trimer of indole derivative and laminated structure thereof | |
WO2010058975A2 (en) | Carbon nanotube-poly(x-4-styrenesulphonate) composite, and a carbon nanotube-electrically conductive polymer composite produced using the same | |
JP4398792B2 (en) | Carbon nanotube-containing composition, composite having coating film made thereof, and method for producing them | |
Nayana et al. | Polycarbazole and its derivatives: progress, synthesis, and applications | |
US20120154980A1 (en) | Conductive polymer composites | |
Jena et al. | A novel high performance poly (2-methyl thioaniline) based composite electrode for supercapacitors application | |
Singh et al. | Recent trends on synthetic approaches and application studies of conducting polymers and copolymers: a review | |
JP4663271B2 (en) | Color conductive primer composition, method for forming color conductive primer, and electrostatic coating method | |
Contal et al. | Investigation of polycarbazoles thin films prepared by electrochemical oxidation of 3-and 9-substituted carbazoles | |
JP3747167B2 (en) | Conductive composition, conductor and method for forming the same | |
JP4091765B2 (en) | Method for producing indole derivative trimer composite conductor | |
JP2003281934A (en) | Conductive packaging material and container for electronic part molded therefrom | |
JP3706825B2 (en) | Conductive composition, conductor and method for forming the same | |
JP3860003B2 (en) | Anticorrosion composition containing indole derivative trimer and anticorrosion method | |
JP2003300980A (en) | Electron attractive group-substituted n-alkylindole derivative trimer and method for producing the same | |
JP4163890B2 (en) | Method for obtaining indole derivative trimer with suppressed aggregation | |
JP2004002286A (en) | Method for producing oxidized compound of indole derivative trimer, oxidized compound of indole derivative trimer and its laminated structure | |
JP2003300981A (en) | Method for producing acidic group-containing heterocyclic compound trimer | |
JP2005241600A (en) | Method for evaluating physical property of carbon nanotube | |
JP2004210747A (en) | High-crystallinity indole derivative trimer and method for obtaining the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |