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  • Y10S977/742—Carbon nanotubes, CNTs
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  • 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
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Definitions

• the present invention relates to a carbon nanotube-containing composition, a composite having a coating film composed of the same, and a method for producing the same.
• the present invention relates to a carbon nanotube-containing composition, a composite having a coating film composed of the same, and methods for producing the same.
• the single-walled carbon nanotube cut as proposed above is open at both ends and terminated with an oxygen-containing functional group such as a carboxylic acid group
• the carboxylic acid group is converted into an acid salt.
• a long-chain alkyl group is introduced into a single-walled carbon nanotube by a covalent bond. Problems remain, such as damage to the graph tube ensheet structure of the tube and the properties of the carbon nanotube itself.
• Another approach is to introduce a substituent containing ammonium ion into the pyrene molecule by utilizing the fact that the pyrene molecule is adsorbed on the surface of the carbon nanotube by strong interaction, and this is introduced into the water together with the single-walled carbon nanotube.
• a method for producing a water-soluble single-walled carbon nanotube by non-covalently adsorbing it on a single-walled carbon nanotube by ultrasonic treatment (Nakajima et al., Chem. Lett., 638 (2002)). According to this method, non-covalent chemical modification suppresses damage to the graphene sheet, but the non-conductive pyrene compound reduces the conductive performance of the carbon nanotube.
• An object of the present invention is to disperse or dissolve carbon nanotubes in a solvent such as water, an organic solvent, or a water-containing organic solvent without deteriorating the properties of the carbon nanotubes themselves.
• Carbon nanotubes do not separate and agglomerate, have excellent conductivity, film formability, and moldability, and can be applied and coated on substrates in a simple manner, and the coating film has excellent water resistance, weather resistance, and hardness.
• An object of the present invention is to provide a carbon nanotube-containing composition, a composite having a coating film composed of the same, and a method for producing the same.
• the present inventors have conducted intensive studies to solve these problems, and as a result, found that carbon nanotubes can be dispersed or solubilized in a solvent by coexisting a conductive polymer. Reached.
• a first aspect of the present invention is a carbon nanotube-containing composition containing a conductive polymer (a), a solvent (b), and a carbon nanotube (c).
• the carbon nanotube (c) is added to the solvent (b) together with the conductive polymer ( a ), so that the properties of the carbon nanotube (c) itself are reduced.
• Carbon nanoti Ube (c) can be dispersed or solubilized in the solvent (b), and does not separate or aggregate during long-term storage. The reason for this is unknown, but the conductive polymer (a) and the carbon nanotube (c) adsorb to each other by ⁇ - ⁇ interaction by ⁇ electrons, and the carbon nanotube (c) becomes conductive ⁇ 4 It is presumed that they are dispersed or solubilized with the polymer (a).
• the carbon nanotube-containing composition of the present invention is excellent in conductivity, film formability, and moldability because the conductive polymer (a) and the carbon nanotube (c) are used in combination.
• the carbon nanotube-containing composition further contains a polymer compound (d), a basic compound (e), a surfactant (f), a silane coupling agent (g), and / or colloidal silica (h),
• a polymer compound (d) is a water-soluble 1 "bioconductive polymer, and that the water-soluble polymer having at least one of a sulfonic acid group and a carboxyl group. Desirably, it is a conductive polymer.
• the second aspect of the present invention is a carbon nanotube-containing composition characterized by containing a heterocyclic compound trimer (i), a solvent (b), and a carbon nanotube (c).
• the polymer compound (d), the basic compound (e), the surfactant (f), the silane coupling agent (g) and Z or colloidal silica ( h) can further improve the performance.
• the first and second carbon nanotube-containing compositions of the present invention can disperse or solubilize carbon nanotubes in water, an organic solvent, and a water-containing organic solvent without impairing the properties of the carbon nanotubes themselves. It does not separate or aggregate during long-term storage.
• the composition is applied to a substrate to form a conductive polymer or a trimer itself of a heterocyclic compound having a sulfonic acid group or a carboxyl group.
• a conductive polymer (a) or a heterocyclic compound trimer (i), a solvent (b), and a carbon nanotube (c) are mixed and irradiated with ultrasonic waves. This is a method for producing a carbon nanotube-containing composition. By this ultrasonic treatment, the carbon nanotubs can be efficiently dispersed or solubilized in the solvent.
• a fourth aspect of the present invention is a composite, which has a coating film made of the carbon nanotube-containing composition of the present invention on at least one surface of a substrate.
• a fifth aspect of the present invention is to form a coating film by applying the carbon nanotube-containing composition of the present invention on at least one surface of a substrate and leaving the composition at room temperature or performing a heat treatment. This is a method for producing a characterized composite.
• the conductive polymer (a) contains phenylene vinylene, vinylene, celenylene, pyrrolylene, phenylene, iminophenylene, isothianaphthene, furylene, and phenolic zirylene as a repeating unit. Is a molecule.
• a so-called water-soluble conductive polymer is preferably used in the present invention from the viewpoint of solubility in a solvent.
• the water-soluble conductive polymer refers to an acidic group, an alkyl group substituted with an acidic group, or an alkyl group containing an ether bond on the skeleton of a ⁇ -conjugated polymer or on a nitrogen atom in the polymer.
• at least one of a sulfonic acid group and a carboxyl group is preferred in terms of solubility in a solvent, conductivity, and film forming property.
• a water-soluble conductive polymer having one is preferably used.
• Examples of the water-soluble conductive polymer having at least one of a sulfonic acid group and a carboxyl group include, for example, JP-A-61-197633 and JP-A-63-399. No. 16, JP-A-01-301714, JP-A-05-504153, JP-A-05-503953, JP-A-04-32848, JP-A-04-328181, JP-A-06-145386 JP-A-6-56987, JP-A-05-226238, JP-A-05-178989, JP-A-06-293828, JP-A-07-118524, JP-A-06-32845 JP, JP-A-06-87949, JP-A-06-256516, JP-A-07-41756, JP-A-07-48436, JP-A-04-268331, JP-A-09-59376, Water-soluble conductive polymers described in JP-A-2000-172384
• water-soluble conductive polymer having at least one of a sulfonic acid group and a carboxyl group include unsubstituted and substituted phenylenevinylene, vinylene, chelenylene, pyrrolylene, phenylene, and imine.
• a water-soluble conductive polymer having an alkyl group or an alkyl group containing an ether bond substituted with at least one of a carboxyl group or at least one of a sulfonic acid group and a carboxyl group is exemplified.
• a water-soluble conductive polymer having a skeleton including cheellene, pyrrolylene, iminophenylene, phenylenevinylene, force / resorylene, and isotianaphthene is particularly preferably used.
• Preferred water-soluble conductive polymers having at least one of a sulfonic acid group and a carboxyl group include at least one type of repeating unit selected from the following formulas (2) to (10): 20 to 100% of the total number of water-soluble conductive polymers.
• the R 1, R 2 are each independently, H, - S0 3 -, one S0 3 H, - R 35 S0 3 one, - R 35 S0 3 H, - OCH 3, - CH 3 ,
• One C 2 H 5 , — F, — C l, — B r,-I, — N (R 35 ) 2 , — NHCOR 35 , -OH, — O—, — SR 35 , -OR 35 , — OC OR 35, -N0 2, - COOH , one R 35 COOH, - COOR 35, -COR 35, - C HO ⁇ Pi is selected from the group consisting of one CN, wherein, R 35 is 1 to 24 carbon atoms alkylene Le, a Ariru or Ararukiru group or alkylene, Ariren or Araru Killen group, and R 1, at least one of one of R 2 S0 3 -, one S0 3 H, one R 35 S
• R 3 are each independently, H, one S0 3 -, one S0 3 H, one R 35 SO 3 one, - R 35 S0 3 H, one OCH 3, - CH 3, - C 2 H 5, - F , - C l, - Br, - I, one N (R 35) 2, - NHCOR 35, - OH, -0 - SR 35, -OR 35, -OC OR 35, - N0 2, -COOH, - R 35 COOH, - COOR 35, -COR 35, - C HO and selected from the group consisting of one CN, wherein, R 35 is 1 to 24 carbon atoms alkyl Le, Ariru or Ararukiru Or an alkylene, arylene or aralkylene group, and at least one of R 3 and R is one of S 0 3 —, one S 0 3 H, — R 35 SO 3 —, one R 35 S 0 3 H, one COOH and one
• R 5 ⁇ R 8 each independently, H, one S0 3 -, -SO 3 H, one R 35 S0 3 -, - R 35 SO 3 H, one OCH 3, - CH 3 , — C 2 H 5 , — F, — Cl, — B r, — I, — N (R 35 ) 2 , one NHCOR 35 , — OH, — O-, — SR 35 , -OR 35 , one OC !
• OR 35 -N0 2, one COOH, - R 35 COOH, - COOR 35, -COR 35, - selected from the group consisting of C HO ⁇ Pi one CN, wherein, R 35 is the number of carbon atoms: to 24 An alkyl, aryl or aralkyl group or an alkylene, arylene or aralkylene group, and at least one of R 5 to R 8 is one of S 3 —, —SO 3 H, — R 35 S 0 3 —, one R 35 S0 3 H, an COOH ⁇ Pi one R 35 group selected from the group consisting of COOH.)
• the R 9 to R 13 are each independently, H, one S0 3 -, -S0 3 H, one R 35 S0 3 one, - R 35 SO 3 H, - OCH 3, one CH 3 , — C 2 H 5 , one F, — C l, — B r, -I, — N (R 35 ) 2 , — NHCOR 5 , one OH, — O—, one SR 35 , -OR 35 , — OC OR 35, one N0 2, -COOH, - R 35 COOH, - COOR 35, -COR 35, selected from the group consisting of one C HO ⁇ P.
• R 35 is alkyl le 1 to 24 carbon atoms , Ariru or Ararukiru group or alkylene, Ariren or Araru Killen group, and at least one of one SO 3 of R 9 ⁇ R 13 -, -SO3 H , - R 35 S0 3 -, one R 35 SO 3 H, selected from the group consisting of one COOH ⁇ Pi one R 35 COOH Group.
• R 14 is one S0 3 one, -S0 3 H, one R 42 S0 3 - one R 42 SO 3 H, - selected from COOH and the group consisting of one R 42 COOH, wherein And R 42 is an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms.
• R 35 is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, or an alkylene, arylene or aralkylene group; at least one of 52 to R 57 is one S0 3 _, one S0 3 H, - R 35 S0 3 -, -R 35 S0 3 H, - with COOH ⁇ Pi
• R 35 selected from the group consisting of COOH group Ht is a heteroatom group selected from the group consisting of NR 82 , S, 0, Se and Te, and R 82 is hydrogen and carbon number :!
• the cyclic linking chain thus formed may contain the linkages of liponyl, ether, estenole, amide, snorefide, snorehuyenoré, snorehoninole, and imino at any position, and It represents the number of condensed rings sandwiched between a terrorist ring and a benzene ring having substituents R 53 to R 56 , and is 0 or an integer of 1 to 3.
• R 58 ⁇ R 66 are each independently, H, one S0 3 - one S0 3 H, one R 35 S0 3 primary, one R 35 S0 3 H, - OCH 3, one CH 3 one C 2 H 5, one F, one C l one B r, - I, - N (R 35) 2, - NHCOR 35, - OH, one O-, one SR 35, -OR 35, - OC oR 35, one N0 2, - COOH, one R 35 COOH, - COOR 35, -COR 35, - C HO and selected from the group consisting of one CN, wherein, R 35 is alkyl le 1 to 24 carbon atoms a Ariru or Ararukiru group or alkylene, Ariren or Araru Killen group, and at least one of one SO of R 58 ⁇ R 66 3 -, one S0 3 H, one R 35 S0 3 -, one R 35 S0 3 H is one COOH
• R 77 ⁇ R 81 each independently one SG 3 - one S0 3 H, one R 35 SO 3 -, -R 35 S0 3 H, - OCH 3, - CH 3, — C 2 H 5 , — F, — C l, — B r,-
• R 35 is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, or an alkylene, arylene or aralkylene group, and among R 77 to R 81 at least one of one S0 3 -, -S0 3 H, - R 35 S0 3 -, is an R 35 S0 3 H, one COOH ⁇ Pi one R 35 group selected from the group consisting of COOH, X a - is , Chloride, bromide, iodine, fluoride, nitrate, sulfate, hydrogensulfate, phosphat
• a anion, a is represents the ionic valence of X, an integer from. 1 to 3, p is the doping ratio, its value is 0.001 to 1.
• a preferred water-soluble conductive polymer having at least one of a sulfonic acid group and a carboxyl group polyethylene dioxythiophene polystyrene sulfate is also used.
• This water-soluble conductive polymer has a structure in which a sulfonic acid group is not introduced into the skeleton of the conductive polymer, but polystyrenesulfonic acid is provided as a dopant.
• This polymer can be produced by polymerizing 3,4-ethylenedioxythiophene (Baytron M from Peyer) with an oxidizing agent such as iron toluenesulfonate (Baytron C from Peyer). This polymer is available as Baytr on P manufactured by Peyer.
• Conductive conductive polymers are more preferably used.
• y represents an arbitrary number of 0 to 1 and R 15 to R 32 each independently represent H, one SO "-S0 3 H, —R 35 SO 3 one, — R 35 S0 3 H, — OCH 3 , — CH 3 , one C 2 H 5 , — F, — C 1, one Br, — I, — N (R 35 ) 2 , one NHCOR 35 , — OH, one O-, one SR 35, one OR 35, one OCOR 35, one NO 2, one COOH, one R 35 CO OH, one COOR 35, one COR 35, selected from the group comprising a single CHO ⁇ Pi one CN, this in this, the alkyl for R 35 having 1 to 24 carbon atoms, Ariru or Ararukiru group or alkylene, Ariren or Ararukiren groups less one is one S0 3 one also of R 15 to R 32, one S0 3 H, one R 35 S0 3 -, a -R
• a water-soluble conductive polymer having a content of a repeating unit having at least one of a sulfonic acid group and a carboxyl group of 50% or more of the total number of the repeating units in the polymer is dissolved in a solvent such as water or a water-containing organic solvent. It is preferred because of its very good properties.
• the content of the repeating unit having at least one of a sulfonic acid group and a carboxyl group is more preferably 70% or more, further preferably 90% or more, and particularly preferably 100%.
• the substituent added to the aromatic ring is preferably an alkyl group, an alkoxy group, a halogen group or the like from the viewpoint of conductivity and solubility, and most preferably a water-soluble conductive polymer having an alkoxy group.
• the most preferred water-soluble conductive polymer among these combinations is shown by the following formula (12).
• R 33 is one group selected from the group consisting of a sulfonic acid group, a carboxyl group, and their metal salts, ammonium salts, and substituted ammonium salts;
• R 34 is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a dodecyl group, a tetracosyl group, a 'methoxy group, Ethoxy, n-propoxy, iso-butoxy, sec-butoxy, tert-butoxy, heptoxy, hexoxy, otatoxy, dodecoxy, tetracosoxy, fluoro, chloro and bromo Represents one group selected from the group consisting of: X represents an arbitrary number of 0 ⁇ X ⁇ 1, and
• At least a part of R 33 is preferably at least one of a free acid type sulfonic acid group and a carboxyl group from the viewpoint of improving conductivity.
• the water-soluble conductive polymer in the present invention a polymer obtained by various synthetic methods such as chemical polymerization or electrolytic polymerization can be used.
• the synthesis methods proposed by the present inventors in Japanese Patent Application Laid-Open Nos. 7-19671 and 7-324141 are applied. That is, at least one of the acid-substituted aniline represented by the following formula (13), an alkali metal salt thereof, an ammonium salt and a substituted ammonium salt is converted into an oxidizing agent in a solution containing a basic compound. It is a water-soluble conductive polymer obtained by polymerizing the polymer.
• the R 36 to R 41 are each independently, H, - SO 3 -, - S0 3 H, one R 35 SO 3 -, - R 35 S0 3 H, - OCH 3, - CH 3 , — C 2 H 5 , one F, — C l, — B r,-
• R 35 is alkyl Le, Ariru or Ararukiru group or alkylene, Ariren or Araru Killen group having 1 to 24 carbon atoms, R 36 at least one of one S0 3 of to R 41 -, one S0 3 H, one R 35
• R 35 S0 3 H group selected from the group consisting of one COOH and one R 35 COOH.
• Particularly preferred water-soluble conductive polymers include, for example, an alkoxy group-substituted aminobenzene sulfonic acid, at least one of an alkali metal salt, an ammonium salt and a substituted ammonium salt thereof, which is polymerized with an oxidizing agent in a solution containing a basic conjugate. The resulting water-soluble conductive polymer is used.
• the acidic group contained in the water-soluble conductive polymer in the present invention is a free acid type from the viewpoint of improving conductivity.
• the water-soluble conductive polymer according to the present invention those having a mass average molecular weight of 2,000 to 3,000,000, in terms of GPC polyethylene glycol recall, are excellent in conductivity, film formability and film strength.
• the conductive polymer (a) can be used as it is, and is preferably used as it is.
• a method to which an external dopant is provided by performing a doping method according to the present invention can be used. For example, a conductor containing the conductive polymer (a) is immersed in an acidic solution. Doping treatment can be performed by performing such treatments as doping.
• Examples of the acidic solution used for the doping treatment include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; and organic acids such as p-toluenesulfonic acid, camphorsulfonic acid, benzoic acid, and derivatives having these skeletons. Acids; aqueous solutions containing high molecular acids such as polystyrenesulfonic acid, polyvinylsulfonic acid, poly (2-acrylamide-12-methylpropane) sulfonic acid, polybutylsulfuric acid and derivatives having these skeletons, or water-organic solvents It is a mixed solution. These inorganic acids, organic acids and polymer acids may be used alone or in combination of two or more at an arbitrary ratio.
• heterocyclic compound trimer (i) examples include an asymmetric heterocyclic compound trimer represented by the formula (16) in which the heterocyclic compound is asymmetrically bonded.
• R 1 D 1 ⁇ R 1 1 2 is hydrogen, straight-chain or branched alkyl group, a linear or branched alkoxy group having 1 to 2 carbon atoms 4 carbon atoms 1-2 4
• Ht is a heteroatom group selected from the group consisting of NR154 , S, O, Se and Te.
• R 154 is a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms.
• X a is chloride ion, bromide ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionic acid
• At least one kind of anion selected from the group of mono- to trivalent anions consisting of ions, methanesulfonate, p-toluenesulfonate, trifluoroacetate, and trifluoromethanesulfonate .
• a represents the ionic valence of X and is an integer of 1 to 3.
• m is the doping ratio, and its value is 0 to 3.0.
• it is a trimer of a heterocyclic compound represented by the formula (17).
• R 113 to R 124 represent hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched naloxy group having 1 to 24 carbon atoms, 4 linear or branched acyl group, aldehyde group, carboxyl group, 2 to 24 carbon linear or branched carboxylic acid ester group, sulfonic acid group, 1 to 24 carbon linear or branched sulfonic acid Ester group, cyano group, hydroxyl group, nitro group, amino group, amide group, dicyanovinyl group, alkyl (linear or branched alkyl group having 1 to 8 carbon atoms) oxycarbyl cyanobur group, nitrophenyl cyanobul And a substituent independently selected from the group consisting of a halogen group and a halogen group, wherein at least one of R 13 to R 24 is a cyano group, a nitro group, an amide group, a
• Ht is NR 154, S, 0, S e ⁇ Pi T e heteroatom group selected from the group consisting of.
• R 154 is a substituent selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms.
• X a is chloride ion, bromide ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionic acid
• At least one kind of anion selected from the group consisting of mono- to trivalent anions consisting of ions, methanesulfonate, p-toluenesulfonate, trifluoroacetate, and trifluoromethanesulfonate.
• a represents the ionic valence of X and is an integer of 1 to 3.
• m is the doping ratio, and its value is 0 to 3.0.
• R 125 to R 136 represent 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, and 2 to 24 carbon atoms.
• a nitro group, an amino group, an amide group, a dicyanobutyl group, an alkyl (linear or branched alkyl group having 1 to 8 carbon atoms), an oxycarbylcyanobule group, a two-way phenyl cyanobiel group and a halogen group Is a substituent independently selected from .
• X a is chloride ion, bromide ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionic acid
• At least one anion selected from the group consisting of mono- to trivalent anions consisting of cations, methanesulfonate, p-toluenesulfonate, trifluoroacetate, and trifluoromethanesulfonate. is there.
• a represents the ionic valence of X and is an integer of 1 to 3.
• m is the doping ratio, and its value is 0 to 3.0.
• heterocyclic compound trimer (i) used in the present invention is exemplified by a symmetric heterocyclic compound trimer represented by the general formula (19) in which the heterocyclic compound is symmetrically bonded. Is done.
• R 1 3 7 ⁇ R 1 4 8 represents hydrogen, straight-chain or branched alkyl group, a linear or branched alkoxy group having 1-2 4 carbon atoms of the C 1-2 4 , C2-C24 linear or branched acyl group, aldehyde group, carbonyl group, C2-C2 4 linear or branched carboxylic acid ester groups, sulfonic acid groups, 1 to 24 carbon linear or branched sulfonic acid ester groups, cyano groups, hydroxyl groups, nitro groups, amino groups, amide groups, dicyanovinyl groups, Alkyl (a linear or branched alkyl group having 1 to 8 carbon atoms) is a substituent independently selected from the group consisting of an oxycarbyl cyanobul group, a two-port phenyl cyanobul group, and a halogen group.
• H t is NR 1 5 4, S, 0 , S e ⁇ selected from Pi T e group consisting of heteroatom group.
• R 1 5 4 is a substituent selected from the group consisting of linear or branched alkyl group of hydrogen ⁇ Pi carbon atoms 1-2 4.
• X a is chloride ion, bromide ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionic acid
• At least one kind of anion selected from the group of mono- to trivalent anions consisting of ions, methanesulfonate, p-toluenesulfonate, trifluoroacetate, and trifluoromethanesulfonate .
• a represents the ionic valence of X and is an integer of 1 to 3.
• m is the doping ratio, and its value is 0 to 3.0.
• heterocyclic compound trimers (i) terpoxyl group-substituted heterocyclic compound trimers, sulfonic acid group-substituted heterocyclic compound trimers, and cyano group-substituted heterocyclic compounds Trimers, nitro-substituted heterocyclic compound trimers, amide-substituted heterocyclic compound trimers, halogen-substituted heterocyclic compound trimers and the like are practically preferable.
• trimers having an acidic group such as a terpoxyl group-substituted heterocyclic compound trimer and a sulfonic acid group-substituted heterocyclic compound trimer, can be used as a solvent because of their water solubility. It can be preferably used also from the viewpoint of environmental safety.
• indole derivative trimer is high in particular heterocyclic compounds indole derivative (i.e. the compound H t is represented by NR 1 5 4) It is more preferably used because of its conductivity and high solubility.
• heterocyclic compound trimer (i) used in the present invention a heterocyclic compound trimeric body (i) obtained by various synthetic methods such as chemical synthesis and electrochemical synthesis can be used.
• At least one heterocyclic compound represented by the following general formula (20) A heterocyclic compound trimer obtained by reacting a compound in a reaction mixture containing at least one oxidizing agent and at least one solvent is preferably used because it has high conductivity and high solubility.
• R 1 5 G ⁇ R 1 5 3 is hydrogen, straight-chain or branched alkyl group, a linear or branched alkoxy group having 1 to 2 carbon atoms 4 carbon atoms 1-2 4 A C 2 -C 24 linear or branched acyl group, an aldehyde group, a carbonyl group, a C 2 -C 24 linear or branched carboxylic ester group, a sulfonic acid group, a C 1 -C 24 Linear or branched sulfonic acid ester group, cyano group, hydroxyl group, nitro group, amino group, amide group, dicyanovinyl group, alkyl (linear or branched alkyl group having 1 to 8 carbon atoms) oxycarboryl cyanobutyl group, It is a substituent independently selected from the group consisting of a trofenilyl cyanobier group and a halogen group.
• H t is, NR 1 5 4, S, 0, S e ⁇ Pi T e heteroatom group selected from the group consisting of, R 1 5 4 is hydrogen ⁇ Pi carbon atoms 1-2 4 linear or branched It is a substituent selected from the group consisting of alkyl groups. )
• indole-14-force ruponic acid examples include indole-14-force ruponic acid, indole Carboxyl-substituted indoles such as 5-carboxylic acid, indole-6-carboxylic acid, indole-17-carboxylic acid and their salts, metal salts, ammonium salts and substituted ammonium salts, indole-4-sulfone Sulfonic acid-substituted indoles such as acid, indole-5-sulfonic acid, indole-1-6-sulfonic acid, indole-7-sulfonic acid, and their metal salts, ammonium salts and substituted ammonium salts, 4-methyl Indole, 5-methyl Indonore, 6-methinoreindore, 7-methinoreindore, 4-ethinoindole
• 6-sec butoxyindonele 7-sec-butoxyindole, 4-t-butoxyindole, 5-t-butoxyindole, 6-t-butoxyindole, 7-t-butoxyindole, etc.
• benzo [b] furans represented by the general formula (20) include benzo [b] furan-14-carboxylic acid, benzo [b] furan-15-carboxylic acid, and benzo [b [B] Furan-6-carboxylic acid, benzo [b] Carboxyl group-substituted benzo such as furan-17-carboxylic acid [b] Furans and their alkali metal salts, ammonium salts and substituted ammonium salts, benzo [b] Furan-4-sulfonic acid, benzo [b] Furan-5-sulfonic acid, benzo [b] furan-6-sulfonic acid Benzo [b] furan-17-sulfonic acid and other sulfonic acid group-substituted benzo [b] furans and their alkali metal salts, ammonium salts and substituted ammonium salts, 4-methylbenzo [b] furan, 5-methylbenzo [b] furan, 6-methylbenzo [
• benzo [b] thiophenes represented by the general formula (20) include benzo [b] thiophen-14-carboxylic acid and benzo [b] thiophen-15-force / reponic acid.
• Carboxyl-substituted benzo [b] thiophenes such as benzo [b] thiophene-6-carboxylic acid, benzo [b] thiophen-17-carboxylic acid, and their alkali metal salts, ammonium salts Ammonium salt, benzo [b] thiophene-14-snoroleic acid, benzo [b] thiophene-15-snorolenic acid, benzo [b] thiophene-16-sulfonic acid, benzo [b] thiophene-17-sulfonate, etc.
• Benzo [b] thiophenes 4-hydroxybenzo [b] thiophene, 5-hydroxybenzene Hydroxy-substituted benzo [b] thiophenes such as benzo [b] thiophene, 6-hydroxybenzo [b] thiophene, 7-hydroxybenzo [b] thiophene, 4-nitrobenzo [b] thiophene , 5-nitrobenzo [b] thiophene, 6-nitrobenzene [b] thiophene, 7-nitrobenzo [b] thiophene, and other substituted benzo [b] thiophenes; 4-aminoaminozo [b] thiophene, 5-aminoaminozo [b] thiophene, 6-aminoaminozo [b] thiophene, 7-aminoaminozo [b] amino-substituted thiophene Benzo [b] thiophenes, 4-potassium benzone [b]
• benzo [b] selenophene represented by the general formula (20) include benzo [b] selenophene 4-carboxylic acid, benzo [b] selenophene 5-carboxylic acid, and benzo [b Selenophen 6-carboxylic acid, benzo [b] -Selenophene 7-carboxylic acid and other carboxyl-substituted benzo [b] selenophenes and their alkali metal salts, ammonium salts and substituted ammonium salts, benzo [B] Selenophen 4-Snolephonic acid, Benzo [b] Selenophen 5-Snolephonic acid, Benzo [b] Selenophen 6-sulfonic acid, Benzo [b] Selenophen 7-Sulfonate-substituted benzo [b] Selenophenes and their alkali metal salts, ammonium salts and substituted ammonium salts, 4-
• Benzo [b] selenophenes 4-aminoamino [b] selenophene, 5-amino aminobenzo [b] selenophene, 6-aminobenzo [b] selenophene, 7-Aminobenzo [b]
• Amino group-substituted benzo such as selenophene [b] selenophenes, 4 lipamoyl benzo [b] selenophene, 5-carpamoyl benzo [b] selenophen, 6-levamoinolebenzo [B] Selenophene, 7-Levamoinolebenzo [b]
• Amide group-substituted benzo such as selenophene [b] Selenophenes, 4-benzophenol benzo [b] Nofen, 5-Fuzoreo opening downy down zone [b] selenophene,
• Halogen-substituted benzo [b] selenophenes, 4-dicyano bulbenzo [b] selenophene, 5-dicyanobi dinolebenzo [b] selenophene, 6-di cyanoviel Down zone [b] selenophene, 7-di Xia
• Roh vinyl benzo [b] Serre Disianovinyl-substituted benzo [b] selenophenes such as nophen, N-methylbenzo [b] selenophene, N-ethylbenzo [b] selenophene, Nn-n-pyruvenzo [b] selenophene, N-iso N-alkyl, such as propinolebenzo [b] selenophene, Nn-butynolebenzo [b] selenophene, N-sec-butynolebenzo [b] selenophene, Nt-butylbuty
• benzo [b] te antivirusphenes represented by the general formula (20) include benzo [b] te antivirusphen-4-carboxylic acid, benzo [b] tellurophene-5-ironolevon Acid, benzo [b] phenolic 6-canoleponic acid, benzo [b] mono-te antivirus 7-carboxyl-substituted benzo [b] teruo antivirus and its alkali metal salts Ammonium salt substituted ammonium salt, benzo [b] te antivirus phen-4-sulfonic acid, benzo [b] te antivirus phen-5-sulfonic acid, benzo [b] te antivirus phen-6-sulfonic acid, benzo [ b) Te antivirus-phen-1 sulfonic acid-substituted benzo such as 7-sulfonic acid [b] Te les and their alkali metal salts, ammonium salts, substituted ammonium salts, 4-methyl benzene
• carboxyl-substituted heterocyclic compounds carboxyl-substituted heterocyclic compounds, sulfonic acid-substituted heterocyclic compounds, cyano-substituted heterocyclic compounds, nitro-substituted heterocyclic compounds, amide-substituted heterocyclic compounds, and halogen-substituted compounds
• carboxyl-substituted heterocyclic compounds and sulfonic acid group-substituted heterocyclic compounds are particularly preferred.
• heterocyclic compound indole derivatives are preferably used.
• the oxidizing agent used in the method for synthesizing the heterocyclic compound trimer (i) is not particularly limited, and examples thereof include ferric chloride hexahydrate, anhydrous ferric chloride, and ferric nitrate nonahydrate.
• nitrosonium tetrafluoroborate hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, potassium periodate and the like.
• ferric chloride hexahydrate anhydrous ferric chloride, cupric chloride, cupric tetrafluoroborate, and ammonium persulfate are practically preferable, and among them, ferric chloride hexahydrate Japanese products and anhydrous ferric irons are most practically preferable.
• ferric chloride hexahydrate Japanese products and anhydrous ferric irons are most practically preferable.
• These oxidizing agents may be used alone or in combination of two or more at an arbitrary ratio.
• the solvent used in the method for synthesizing the heterocyclic compound trimer (i) water and an organic solvent can be used.
• the organic solvent is not particularly limited.
• Nitromethane N, N-dimethylformamide, N-methylacetamide, dimethylsulfoxide, dimethylsulfone, N-methylpyrrolidone, benzene, toluene, xylene, methylene chloride, chloroform, dichloroethane, and the like are used. These solvents may be used alone or in combination of two or more at an arbitrary ratio. Among these solvents, acetone, acetonitrile, 1,4-dioxane, ⁇ -butyrolactone, ⁇ , ⁇ -dimethylformamide and the like are preferable, and especially acetonitrile is most practically preferable.
• the method for synthesizing the heterocyclic compound trimer (i) it is particularly preferable to carry out the reaction in the presence of water and an organic solvent.
• the oxidizing agent has water of crystallization, the amount of water of crystallization is also converted to water.
• the reaction ratio of the water is low to structural deterioration by peracid I inhibit the trimer and runaway may X a one as the dopant relative to trimers can not be efficient well dope
• the conductivity may decrease. Conversely, if the ratio is too high, the progress of the oxidation reaction may be hindered and the reaction yield may be reduced.
• the concentration of the heterocyclic compound at the time of the reaction is 0.01% by mass or more, preferably 0.1 to 50% by mass, based on the solvent. It is more preferably in the range of 1 to 30% by mass.
• X a — in the heterocyclic compound trimer (i) represented by the general formulas (16) to (19) used in the present invention is a dopant, and a protonic acid derived from an oxidizing agent or the like during polymerization. Is an anion.
• chloride bromide, iodine, fluoride, nitrate, sulfate, hydrogen sulfate, phosphate, borofluoride, perchlorate, thiocyanate, acetate, propionate Ion, p-toluenesulfonic acid ion, trifluoroacetic acid ion, trifluoroacetic acid It is a monovalent to trivalent anion such as methanesulfonic acid ion, and preferably a monovalent to divalent anion such as chlorine ion, sulfate ion, and borofluoride ion. Most preferred are monovalent anions such as chloride.
• the dopant X a in the indole derivative trimer becomes a chlorine ion
• the polymerization is performed using cupric trifluoroacetate
• de one dopant X a one becomes Torifuruoro acetate ion.
• heterocyclic compound trimer (i) those which have been undoped for the purpose of further improving the solubility in the solvent (b) can be used.
• the method of undoping is not particularly limited.
• the heterocyclic compound trimer (i) may have a higher conductive property due to having a laminated structure.
• the layer spacing preferably has a laminated structure of 0.1 to 5.0 nm, more preferably 0.1 to 2.0 nm, and particularly preferably 0.1 to 1.0 nm.
• Compounds having such an ultrafine laminated structure have good physical properties such as rigidity, strength, and heat resistance.
• the layer spacing is 0.1 nm or more, the laminated structure tends to be more stable, and when it is 2.0 nm or less, electron hopping conduction between trimers becomes easier, and the conductivity tends to be improved. is there.
• the heterocyclic compound trimer (i) can be used as it is, but it is possible to use a compound to which an external dopant is added by performing a doping treatment with an acid by a known method.
• a heterocyclic compound trimer is immersed in an acidic solution. Doping treatment can be performed.
• the acidic solution used for the doping treatment include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, p-toluenesulfonic acid, camphorsulfonic acid, benzoic acid, and derivatives having these skeletons.
• Aqueous solutions containing high-molecular acids such as organic acids, polystyrene sulfonic acid, polyvinyl sulfonic acid, poly (2-acrylamide-12-methylpropane) sulfonic acid, polyvinyl sulphate and derivatives having these skeletons, or A mixed solution of water and an organic solvent.
• organic acids polystyrene sulfonic acid, polyvinyl sulfonic acid, poly (2-acrylamide-12-methylpropane) sulfonic acid, polyvinyl sulphate and derivatives having these skeletons, or A mixed solution of water and an organic solvent.
• organic acids, organic acids and polymer acids may be used alone or in combination of two or more at an arbitrary ratio.
• an asymmetric indole derivative trimer is used as a method for producing an oxidized trimer of the indole derivative represented by the general formula (18), which is an asymmetric heterocyclic compound trimer (i).
• an asymmetric indole derivative trimer is used.
• a Indoru derivative trimer external dopant X a one doped by simply deacidification or reduction treatment from doped
• the oxidation reaction can proceed more efficiently without using an oxidizing agent, and an oxidized trimer of indole derivative may be obtained, which is an industrially very suitable production method.
• a method for producing an oxidized heterocyclic compound represented by the general formula (19), which is a symmetrical heterocyclic compound trimer (i) a known method can be used.
• a symmetric indole derivative trimer can be produced by the method described in JP-A-2001-261680.
• heterocyclic compound trimers (i) may be used after purification to improve their performance if they are used after being highly purified using a purification method such as recrystallization, reprecipitation purification, or sublimation purification. There is.
• a purification method such as recrystallization, reprecipitation purification, or sublimation purification.
• conductivity, film formability and moldability are improved.
• the solvent (b), which is an essential component of the present invention, comprises a conductive polymer (a) or a heterocyclic compound trimer (i), a carbon nanotube (c), a polymer compound (d), a basic compound (e ),
• the surfactant (f), the silane coupling agent (g), and the colloidal silica (h) are not particularly limited.
• solvent (b) water, methanol, ethanol, isopropyl alcohol, Alcohols such as mouth pill alcohol and butanol; ketones such as acetone, methylethylketone, ethylisobutylinoketone, and methylisobutylinoletone; ethylene glycolone, ethylene glycolone methylenoate ether, ethylene glycolone n — Ethylene glycols such as propyl ether; propylene glycol, propylene glycol / remethinoleate //, propylene glycolone retinoleatene, propylene glycol / lebutinoleatene, propylene glycol Propylene glycols; amides such as dimethylformamide and dimethylacetamide; pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; dimethyl sulfoxide, y-butyrolactone, and methyl lact
• a water-soluble conductive polymer When a water-soluble conductive polymer is used as the conductive polymer (a), water or a water-containing organic solvent is used as the solvent (b) in view of the solubility of the water-soluble conductive polymer and the dispersibility of the carbon nanotube (c). Solvents are preferably used.
• the carbon nanotube (c), which is an essential component of the carbon nanotube-containing composition of the present invention, is not particularly limited.
• a cylinder with a few atomic layers of graphitic carbon atoms rounded into a nested structure with an extremely small outer diameter on the order of nm Substances are exemplified.
• a carbon nanohorn having a closed shape on one side of a carbon nanotube or a cup-shaped nanocarbon material having a hole at the head thereof can also be used.
• the method for producing the carbon nanotube (c) in the present invention is not particularly limited. Specifically, catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, CVD method, vapor phase growth method, H2 that reacts carbon monoxide with iron catalyst at high temperature and pressure to grow in gas phase i Pco method and the like.
• carbon nanotube (c) obtained by the above manufacturing method It is a single-walled carbon nanotube.
• Carbon nanotubes that have been further purified by various purification methods such as washing, centrifugation, filtration, oxidation, and chromatography have more functions. Is preferably used because it sufficiently expresses.
• Examples of carbon nanotubes (c) include those that have been pulverized using a pole-type kneading device such as a bono reminore, vibrating mill, sand mill, or roll mill, and those that have been cut short by chemical or physical treatment. Can be used.
• a pole-type kneading device such as a bono reminore, vibrating mill, sand mill, or roll mill, and those that have been cut short by chemical or physical treatment. Can be used.
• the use of the polymer compound further improves the substrate adhesion and strength of the coating film.
• the polymer compound (d) in the present invention is not particularly limited as long as it can be dissolved or dispersed (emulsion-formed) in the solvent (b) used in the present invention.
• Specific examples include polyvinyl alcohol and polyvinyl alcohol.
• Polyvinyl alcohols such as formal and polybutyral; polyacrylamides such as polyacrylamide, poly (N-t-butylacrylamide) and polyacrylamide methylpropanesulfonic acid; polybutylpyrrolidones , Polystyrene sulfonic acid and its soda salts, cellulose, alkyd resin, melamine resin, urea resin, phenol resin, epoxy resin, polybutadiene resin, acrylic resin, urethane resin, butyl ester resin, urea resin, polyimide resin, maleic resin
• a water-soluble polymer compound or a polymer compound that forms an emulsion in an aqueous system is preferably used in view of solubility in a solvent, stability of a composition, and conductivity.
• a polymer compound having an anion group is used.
• one or two or more of an aqueous acrylic resin, an aqueous polyester resin, an aqueous urethane resin and an aqueous chlorinated polyolefin resin are preferably used in combination.
• the basic aldehyde compound (e) constituting the carbon nanotube-containing composition of the present invention dedopes a water-soluble conductive polymer or a heterocyclic compound trimer by being added to the carbon nanotube-containing composition. This has the effect of further improving the solubility in the solvent (b). Further, by forming a salt with a sulfonic acid group and a carboxyl group, the solubility in water is particularly improved, and the solubilization or dispersion of the carbon nanotube ( c ) in the solvent (b) is promoted.
• Examples of the basic compound (e) include, but are not particularly limited to, ammonia, aliphatic amines, cyclic saturated amines, cyclic unsaturated amines, ammonium salts, and inorganic bases.
• ammonia aliphatic amines
• cyclic saturated amines cyclic unsaturated amines
• ammonium salts and inorganic bases.
• R 45 to R 47 each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms (C, to C 4 ), CH 2 OH, CH 2 CH 2 OH, CONH 2 or Represents NH 2.
• R 48 to R 51 each independently represent hydrogen, carbon number 1 to 4 (C, to C 4 Alkyl group), CH 2 represents OH, CH 2 CH 2 OH, a CONH 2 or NH 2, X- is OH-, 1/2 ⁇ SO / -, N0 3 -, 1 Bruno 2_Rei_0 3 2 -, HC0 3 ⁇ 1/2. (C OO) 2 2 — or R, COO-, where R, is an alkyl group having 1 to 3 carbon atoms (C! To C 3 ). )
• cyclic saturated amines piperidine, pyrrolidine, morpholine, piperazin, derivatives having these skeletons, and ammonium hydroxide compounds thereof are preferably used.
• cyclic unsaturated amines pyridine, ⁇ -picoline,] 3-picoline, ⁇ -picoline, quinoline, isoquinoline, pyrroline, derivatives having these skeletons, and ammonium hydroxide compounds thereof are preferable. Used.
• hydroxide salts such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferably used.
• the basic compound (e) may be used as a mixture of two or more kinds.
• conductivity can be further improved by using a mixture of amines and ammonium salts.
• NH 3 / (NH 4) 2 C0 3, NH 3 / (NH 4) HCO 3, NH 3 ZCH 3 COONH 4, NH 3 / (NH 4) 2 S0 4, N (CH 3) 3 / CH 3 COONH 4, N ( CH 3)% / (NH 4) such as 2 S0 4 and the like.
• the carbon nanotube-containing composition of the present invention includes the conductive polymer (a) or the heterocyclic compound trimer (i), the solvent (b), the carbon nanotube (c), the high molecular compound (d), and a base.
• the carbon nanotube (c) can be solubilized or dispersed even with only the neutral compound (e), it is possible to form a high-performance film without separation or aggregation even during long-term storage.
• Addition of (f) further promotes solubility or dispersibility, and improves flatness, coatability, conductivity, and the like.
• the surfactant (f) include alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl force / reponic acid, alkyl naphthalene sulfonic acid, ⁇ -olefin sulfonic acid, dialkyl sulfosuccinic acid, ⁇ -sulfonated fatty acid, and ⁇ — Met Le-N-oleyl taurine, petroleum sulfonic acid, alkyl sulfuric acid, sulfated fats, polyoxyethylene alkyl ether ether sulfate, polyoxyethylene styrenated phenyl ether ether sulfate, alkyl phosphoric acid, polyoxyethylene alkyl ether phosphoric acid Polyoxyethylene alkyl phenyl ether phosphoric acid, naphthalene sulfonic acid formaldehyde condensate, or a salt thereof, or other aunion-based surfactants; primary
• a silane coupling agent (g) can be further used in combination with the carbon nanotube-containing composition containing the component of the activator (f).
• the water resistance of the coating film obtained from the carbon nanotube-containing composition using the silane coupling agent (g) in combination is remarkably improved.
• a silane coupling agent (g) represented by the following formula (1) is used as the silane coupling agent (g) represented by the following formula (1) is used.
• R 242 , R 243 , and R 244 each independently represent hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, X is a group selected from the group consisting of an amino group, an acetyl group, a phenyl group, and a halogen group;
• Y is a group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, an epoxy group and an epoxycyclyl hexyl group.
• examples of those having an epoxy group include glycidyloxypropyl methoxysilane, ⁇ -glycidyloxypropylmethyldimethoxysilane, ⁇ -glycidyloxypropyltriethoxysilane and the like.
• Examples of those having an amino group include 0 / -aminopropyltriethoxysilane, ⁇ - Aminoethyltrimethoxysilane, ⁇ -aminopropoxyprovirtrimethoxysilane, etc. can be used.
• Examples of those having a thiol group include ⁇ -mercaptopropyl trimethoxysilane and J3-mercaptoethylmethyldimethoxysilane.
• Examples of those having a hydroxyl group include 3-hydroxyethoxyethyltriethoxysilane and hydroxypropyltrimethoxysilane.
• Examples of those having an epoxycyclohexyl group include ⁇ - (3,4-epoxycyclylhexyl) ethyltrimethoxysilane.
• the conductive polymer (a) or the heterocyclic compound trimer (i), the solvent (b), the carbon nanotube (c :), the polymer compound (d), the basic compound (e), Colloidal silica (h) can be used in combination with the crosslinkable carbon nanotube-containing composition containing the components of the surfactant (f) and the silane coupling agent (g).
• a coating film obtained from a carbon nanotube-containing composition using colloidal silica (h) in combination has significantly improved surface hardness and weather resistance.
• the colloidal silica (h) in the present invention is not particularly limited, but preferably used is one that is dispersed in water, an organic solvent or a mixed solvent of water and an organic solvent.
• the organic solvent include, but are not limited to, alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol, and pentanol; and acetone, methyl ethyl ketone, ethyl isobutyl ketone, and methyl isobutyl ketone.
• Ketones such as polyethylene glycol, ethylene glycol methinolate ether, and ethylene glycolone mono-n-propynoleether; propylene glycol, propylene glycol alcohol, propylene glycol ethyl ether, propylene glycol butyl ether, and propylene glycol Propylene glycols such as propylendalcol propyl ether are preferably used.
• colloidal silica (h) those having a particle size of 1 nm to 300 nm are used, preferably those having a particle size of 1 nm to 150 nm, more preferably those having a particle size of 1 nm to 50 nm. Used. If the particle size is too large, the hardness will be insufficient, and The solution stability of the oral silica itself is also reduced.
• the ratio of the conductive polymer (a) or the heterocyclic compound trimer (i) and the solvent (b) used is 100 parts by mass of the solvent (b) and the conductive polymer (a) or the solvent (b) is used.
• the amount of the heterocyclic compound trimer (i) is preferably from 0.001 to 50 parts by mass, and more preferably from 0.01 to 30 parts by mass.
• the amount of the conductive polymer (a) or the heterocyclic compound trimer (i) is less than 0.001 parts by mass, the conductivity is poor, and the solubilization or dispersion efficiency of the carbon nanotube (c) is reduced. Decreases. On the other hand, if it exceeds 50 parts by mass, the conductivity reaches a peak and does not greatly increase, and the viscosity increases, and the efficiency of dissolving or dispersing the carbon nanotube (c) decreases.
• the usage ratio of the carbon nanotube (c) and the solvent (b) is preferably such that the carbon nanotube (c) is 0.0001 to 2.0 parts by mass, more preferably 100 parts by mass of the solvent (b). 0.0 0.01 to 10 parts by mass. If the carbon nanotube (c) is less than 0.0001 parts by mass, the performance of the carbon nanotube (c) such as conductivity is reduced. On the other hand, if it exceeds 20 parts by mass, the efficiency of solubilizing or dispersing the carbon nanotubes (c) decreases.
• the ratio of the polymer compound (d) to the solvent (b) is preferably 0.1 to 400 parts by mass, more preferably 100 parts by mass of the solvent (b). Is from 0.5 to 300 parts by mass.
• amount of the polymer compound (d) is 0.1 part by mass or more, film formability, moldability, and strength are further improved.
• the amount is 400 parts by mass or less, the water-soluble conductive polymer (a) or the heterocyclic ring is used. Dissolution of the formula compound trimer (i) and the carbon nanotube (c) 14 is small, and high conductivity is maintained.
• the ratio of the basic compound (e) and the solvent (b) used is preferably such that the basic compound (e) is 0.1 to 10 parts by mass, more preferably 100 parts by mass of the solvent (b). 0.1 to 5 parts by mass.
• the basic compound (e) is in this range, the solubility of the water-soluble conductive polymer is improved, and the carbon nanotube (c) is soluble or dispersible in the solvent (b). The conductivity is improved.
• the ratio of the surfactant (f) and the solvent (b) used is 100 parts by mass of the solvent (b).
• the content of the surfactant (f) is preferably from 0.0001 to 10 parts by mass, and more preferably from 0.01 to 5 parts by mass. If the amount of the surfactant (f) exceeds 10 parts by mass, the coatability is improved, but phenomena such as poor conductivity occur, and the efficiency of dissolving or dispersing the carbon nanotube (c) is reduced. Decrease.
• the ratio of the silane coupling agent (g) and the solvent (b) used is preferably such that the silane coupling agent (g) is 0.001 to 20 parts by mass with respect to 100 parts by mass of the solvent (b). More preferably, it is 0.01 to 15 parts by mass.
• the silane coupling agent (g) is less than 0.001 part by mass, the improvement in water resistance and / or solvent resistance is relatively small, while when it exceeds 20 parts by mass, the solubility, flatness, transparency, and ⁇ Conductivity may be poor.
• the use ratio of the colloidal silica (h) and the solvent (b) is preferably 0.001 to 100 parts by mass of the colloidal silica (h) per 100 parts by mass of the solvent (b), more preferably 100 parts by mass. Is 0.01 to 50 parts by mass.
• the amount of the colloidal silica (h) is 0.001 parts by mass or more, the improvement in water resistance, weather resistance and hardness becomes large. On the other hand, if it exceeds 100 parts by mass, solubility, flatness, transparency, and conductivity may be deteriorated.
• the carbon nanotube-containing composition of the present invention may further contain, if necessary, a plasticizer, a dispersant, a coating surface adjuster, a fluidity adjuster, an ultraviolet absorber, an antioxidant, a storage stabilizer, an adhesion aid, Various known substances such as a thickener can be added and used.
• the carbon nanotube-containing composition of the present invention may contain a conductive substance in order to further improve the conductivity.
• a conductive substance include carbon-based substances such as carbon fiber, conductive carbon black, and graphite; metal oxides such as tin oxide and zinc oxide; and metals such as silver, nickel, and copper.
• a stirring or kneading device such as an ultrasonic wave, a homogenizer, a spiral mixer, a planetary mixer, a disperser, and a hybrid mixer is used.
• a stirring or kneading device such as an ultrasonic wave, a homogenizer, a spiral mixer, a planetary mixer, a disperser, and a hybrid mixer.
• mixing the conductive polymer (a) or the above-mentioned heterocyclic compound trimer (i), the solvent (b), the carbon nanotube (c), and other components and irradiating the mixture with ultrasonic waves.
• ultrasonic irradiation and homo It is preferable to perform the treatment using a homogenizer in combination (ultrasonic homogenizer).
• the conditions of the ultrasonic irradiation treatment are not particularly limited, but the ultrasonic intensity and the processing time are sufficient to uniformly disperse or dissolve the carbon nanotube (c) in the solvent (b).
• the rated output of the ultrasonic oscillator is preferably 0.1 to 2.0 watts / cm 2 per unit area of the ultrasonic oscillator, more preferably 0.3 to 1.5 watts cm 2 .
• the oscillation frequency is preferably from 10 to 200 KHz, more preferably from 20 to 100 KHz.
• the time of the ultrasonic irradiation treatment is preferably 1 minute to 48 hours, more preferably 5 minutes to 48 hours. After this, it is desirable to thoroughly disperse or dissolve using a pole-type kneading apparatus such as a ball mill, a vibration mill, a sand mill, and a roll mill.
• the base material for forming a coating film by applying the carbon nanotube-containing composition includes a polymer compound, plastic, wood, paper material, ceramics, fiber, non-woven fabric, carbon fiber, carbon fiber paper, And their films, foams, porous membranes, elastomers, and glass plates.
• polymer compounds, plastics and films include polyethylene, polyvinyl chloride, polypropylene, polystyrene, ABS resin, AS resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, polyvinylidene fluoride, polyester, polyamide, Polyimides, polyaramids, polyphenylene selenolides, polyetherenolates, ketones, polyphenylene ethers, polyether nitriles, polyamides, polyamides, polyethersulfones, polysulfones, polyetherimides, polybutylene terephthalates, polyurethanes Films, foams, elastomers, etc. can be fisted in.
• a spraying method such as spray coating such as air spray and airless spray, and a dipping method such as dip are used.
• the composition can be left at room temperature, but the coating film can be subjected to heat treatment.
• the heat treatment further promotes a crosslinking reaction between the carbon nanotube (c;), the polymer compound (d), the basic compound (e) and the conductive polymer (a) or the heterocyclic compound trimer (i). It is preferable because the water resistance can be imparted in a shorter time by promoting it, the amount of the remaining solvent (b) can be further reduced, and the conductivity is further improved.
• the heat treatment temperature is preferably from 20 ° C. to 250 ° C., and more preferably from 40 ° C. to 200 ° C. If the temperature is higher than 250 ° C., the conductive polymer (a) itself or the heterocyclic compound trimer (i) itself may be decomposed, and the conductivity may be significantly reduced.
• the thickness of the coating film is preferably in the range of 0.01 to 100 ⁇ , more preferably in the range of 0.1 to 50 m.
• the composite of the present invention has excellent conductivity as it is, it is coated with a carbon nanotube-containing composition on at least one surface of a base material to form a coating film, and then treated with an acid. Conductivity can be further improved by performing a doping process and then performing a standing process or a heating process at room temperature.
• the method of doping treatment with an acid is not particularly limited, and a known method can be used.
• a doping process can be performed by performing a process such as immersing a conductor in an acidic solution.
• the acidic solution include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as p-toluenesulfonic acid, camphorsulfonic acid, benzoic acid, and derivatives having these skeletons; and polystyrene sulfonate.
• An aqueous solution containing a polymer acid such as acid, polyvinyl sulfonic acid, poly (2-acrylamido-2-methylpropane) sulfonic acid, polybutyl sulfate and derivatives having these skeletons, or a mixed solution of water and an organic solvent .
• a polymer acid such as acid, polyvinyl sulfonic acid, poly (2-acrylamido-2-methylpropane) sulfonic acid, polybutyl sulfate and derivatives having these skeletons, or a mixed solution of water and an organic solvent .
• These inorganic acids, organic acids, and polymer acids may be used alone or as a mixture of two or more at an arbitrary ratio.
• Aniline I O Ommo 1 was stirred and dissolved in an lmo 1 / L aqueous sulfuric acid solution at 25 ° C., and an aqueous solution of ammonium peroxodisulfate 10 Ommo 1 was added dropwise thereto. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was separated by filtration, washed and dried to obtain 8 g of a polymer powder. The obtained polymer in the dope state was molded under pressure with a tablet molding machine, cut into a shape having a diameter of 1 Omm and a thickness of lmm, and the conductivity was measured by a four-terminal method. there were.
• Example 2 5 parts by mass of the conductive polymer (A-1) of Production Example 1 and 0.4 parts by mass of carbon nanotubes (manufactured by ILJIN, multi-walled carbon nanotubes produced by a CVD method) were mixed with 100 parts by mass of water at room temperature. Thus, a carbon nanotube-containing composition 1 was prepared.
• Example 2 5 parts by mass of the conductive polymer (A-1) of Production Example 1 and 0.4 parts by mass of carbon nanotubes (manufactured by ILJIN, multi-walled carbon nanotubes produced by a CVD method) were mixed with 100 parts by mass of water at room temperature. Thus, a carbon nanotube-containing composition 1 was prepared.
• Example 2 5 parts by mass of the conductive polymer (A-1) of Production Example 1 and 0.4 parts by mass of carbon nanotubes (manufactured by ILJIN, multi-walled carbon nanotubes produced by a CVD method) were mixed with 100 parts by mass of water at room temperature. Thus, a carbon nano
• the conductive polymer (A- 1) 5 parts by weight of the preparation Example 1, the carbon nanotube 0.1 part by mass, the acrylic resin "DIANAL an aqueous Emarujiyon MX- 184 5 J (Mitsubishi Reiyon Co., resin content 40 mass 0 / 0 ) 20 parts by mass were mixed with 100 parts by mass of water at room temperature to prepare a composition 2 containing carbon nanotubes.
• Carbon nanotubes-containing composition 8 was prepared by mixing 0.1 parts by mass of carbon nanotubes with 100 parts by mass of water at room temperature. Comparative Example 2
• a carbon nanotube-containing composition 9 was prepared by mixing 0.1 part by mass of carbon nanotubes and 1 part by mass of ammonia with 100 parts by mass of water at room temperature. Comparative Example 3
• a carbon nanotube-containing composition 10 was prepared by mixing 0.1 part by mass of carbon nanotubes and 20 parts by mass of an acrylic resin "Dyanal MX-1845 J (manufactured by Mitsubishi Rayon Co., Ltd.)" as an aqueous emulsion in 100 parts by mass of water at room temperature. Comparative Example 4
• a conductive composition 1 was prepared by mixing 5 parts by mass of the conductive polymer (A-1) of Production Example 1 with 100 parts by mass of water at room temperature.
• elemental analysis was measured using Thermoquestone EA1110.
• the conductivity was measured with a Mitsubishi Chemical Lorester meter MCP-T350 (four-terminal method: lmm between electrodes).
• X-rays diffraction analysis is Rigaku Co.
• RI NT- 1100 measured in (tube Cu K a X-ray).
• Acetonitrile (1 Oml) was placed in a 200-ml flask and 1.42 g of indole-15-carboxylic acid was dissolved therein.
• anhydrous ferric chloride (16.2 g) and water (5.4 g) were dissolved in acetonitrile (4 Oml) and stirred for 10 minutes.
• the prepared oxidizing agent solution was added dropwise to the indole-15-carboxylic acid aqueous solution over 30 minutes, followed by stirring at 60 ° C. for 10 hours.
• the reaction solution generates some heat At the same time, the color changed from pale yellow to pale green, and its pH was 1 or less.
• the obtained trimer was subjected to pressure molding with a tablet molding machine, cut into a shape having a diameter of 1 Omm and a thickness of 1 mm, and the conductivity was measured by a four-terminal method. As a result, it was 0.41 Scm. Elemental analysis was (C 9. 00 H 4. 90 N X. 09 O 98 C 1 o. 1 X) 3. Further, as a result of X-ray diffraction crystal analysis, the layer interval was 0.48 nm.
• trimer was molded under pressure by a tablet molding machine, cut into a shape having a diameter of 1 Omm and a thickness of 1 mm, and the conductivity was measured by a four-terminal method. As a result, it was 0.56 SZ cm. Elemental analysis was filed by (C 8. 00 H 4. 06 O 3. OI S X. 06 C 1 o. 1X) 3. Production example 7 Synthesis of indole-5-caprolitolitr trimer
• Example 10 5 parts by mass of the indole-5-carboxylic acid trimer of Production Example 5 and 0.4 parts by mass of carbon nanotubes (multi-walled carbon nanotubes produced by a CVD method manufactured by ILJIN) are mixed with 100 parts by mass of water at room temperature. Thus, a carbon nanotube-containing composition was prepared.
• Example 10 5 parts by mass of the indole-5-carboxylic acid trimer of Production Example 5 and 0.4 parts by mass of carbon nanotubes (multi-walled carbon nanotubes produced by a CVD method manufactured by ILJIN) are mixed with 100 parts by mass of water at room temperature. Thus, a carbon nanotube-containing composition was prepared.
• Example 10 5 parts by mass of the indole-5-carboxylic acid trimer of Production Example 5 and 0.4 parts by mass of carbon nanotubes (multi-walled carbon nanotubes produced by a CVD method manufactured by ILJIN) are mixed with 100 parts by mass of water at room temperature. Thus, a carbon nanotube-
• Example 11 A carbon nanotube-containing composition was prepared by
• Example 1 2 3 parts by mass of the indole-5-sulfonic acid trimer, 0.1 part by mass of carbon nanotubes, and 1 part by mass of ammonia in Production Example 6 were mixed with 100 parts by mass of water at room temperature to produce a mixture of carbon nanotubes. A containing composition was prepared.
• Example 1 2 3 parts by mass of the indole-5-sulfonic acid trimer, 0.1 part by mass of carbon nanotubes, and 1 part by mass of ammonia in Production Example 6 were mixed with 100 parts by mass of water at room temperature to produce a mixture of carbon nanotubes. A containing composition was prepared.
• Example 1 2 3 parts by mass of the indole-5-sulfonic acid trimer, 0.1 part by mass of carbon nanotubes, and 1 part by mass of ammonia in Production Example 6 were mixed with 100 parts by mass of water at room temperature to produce a mixture of carbon nanotubes. A containing composition was prepared.
• Example 1 2 3 parts by mass of the indole-5-sul
• Example 13 3 parts by mass of indole-5-sulfonic acid trimer, 0.2 parts by mass of carbon nanotubes, 1 part by mass of triethylamine, and an aqueous resin emulsion etalyl resin “DIANAL MX-1845” (Mitsubishi) 20 parts by mass (manufactured by Rayon Co., Ltd.) were mixed with 100 parts by mass of water at room temperature to prepare a carbon nanotube-containing composition.
• Example 13 3 parts by mass of indole-5-sulfonic acid trimer, 0.2 parts by mass of carbon nanotubes, 1 part by mass of triethylamine, and an aqueous resin emulsion etalyl resin “DIANAL MX-1845” (Mitsubishi) 20 parts by mass (manufactured by Rayon Co., Ltd.) were mixed with 100 parts by mass of water at room temperature to prepare a carbon nanotube-containing composition.
• Example 14 1 part by mass of the indole-5-carbonitrile trimer of Production Example 7 above, 0.4 part by mass of carbon nanotubes, 0.5 part by mass of dodecylbenzenesulfonic acid were added to 100 parts by mass of dimethyl sulfoxide at room temperature. By mixing, a carbon nanotube-containing composition was prepared.
• Example 14 1 part by mass of the indole-5-carbonitrile trimer of Production Example 7 above, 0.4 part by mass of carbon nanotubes, 0.5 part by mass of dodecylbenzenesulfonic acid were added to 100 parts by mass of dimethyl sulfoxide at room temperature. By mixing, a carbon nanotube-containing composition was prepared.
• Example 14 1 part by mass of the indole-5-carbonitrile trimer of Production Example 7 above, 0.4 part by mass of carbon nanotubes, 0.5 part by mass of dodecylbenzenesulfonic acid were added to 100 parts by mass of dimethyl sulfoxide at room temperature.
• Example 15 3 parts by mass of the indole-5-carboxylic acid trimer oxidized product of Production Example 8 above, 0.4 parts by mass of carbon nanotubes, and 0.5 parts by mass of glycidoxypropyltrimethoxysilane in 100 parts by mass of water at room temperature To prepare a carbon nanotube-containing composition.
• Example 15 3 parts by mass of the indole-5-carboxylic acid trimer oxidized product of Production Example 8 above, 0.4 parts by mass of carbon nanotubes, and 0.5 parts by mass of glycidoxypropyltrimethoxysilane in 100 parts by mass of water at room temperature To prepare a carbon nanotube-containing composition.
• a conductive composition was prepared by mixing 1 part by mass of the indole-5-carbonitrile trimer of Production Example 7 and 0.5 part by mass of dodecylbenzene sulfonic acid with 100 parts by mass of dimethyl sulfoxide at room temperature. . Evaluation method>
• the composition was applied to a glass substrate by a per coater method (using a Percoat No. 5), and then at 80 ° C. for 5 minutes. After drying, a coating film was formed. After observing the external appearance, the surface resistance was measured. Table 1 shows the results.
• composition 8 containing carbon nanotubes obtained in Example 8 was applied to a glass substrate by a bar coater method (using a percoat No. 5), dried at 150 ° C. for 5 minutes, and coated. Was formed, immersed in an lmo 1 / L sulfuric acid aqueous solution for 5 minutes, dried at 80 ° C for 5 minutes, observed for appearance, and measured for surface resistance.
• compositions obtained in the above Examples and Comparative Examples were subjected to ultrasonic treatment (Shinmeidai Co., Ltd., ⁇ ⁇ , UA100, 36 KHz) for 1 hour, and after visually observing the state, the compositions were applied to a glass substrate.
• the coating was applied by a per coater method (using Bar Coat No. 5.), and dried at 80 ° C. for 5 minutes to form a coating film. Table 1 shows the results.
• composition 8 containing carbon nanotubes obtained in Example 8 was applied to a glass substrate by a bar coater method (percoat No. 5 was used), dried at 150 ° C. for 5 minutes, and coated. Was formed, immersed in an lmo 1 / L sulfuric acid aqueous solution for 5 minutes, dried at 80 ° C for 5 minutes, observed for appearance, and measured for surface resistance.
• Example 5 ⁇ 2.9 X ⁇ Yes ⁇ 5.3 X 10 2 ⁇
• Example 6 ⁇ 9.2 X 10 3 ⁇ Yes ⁇ 7.9 X 10 2 ⁇
• Example 1 4 ⁇ 9.1 X ⁇ Yes ⁇ 1.5 X 10 5 ⁇ Example 1 5 ⁇ 5.2 X 10 5 ⁇ Yes ⁇ 8.4 X 10 4 4
• Comparative Example 5 ⁇ ⁇ Yes ⁇ 4.2 X 1 0 7 ⁇
• the solution containing the carbon nanotubes of the present example was uniformly dispersed or dissolved, and a uniform coating film was formed. Also, the surface resistance is small. In particular, the surface resistance can be further reduced by performing ultrasonic treatment.
• Comparative Examples 1 to 3 are inferior in any of the solution state, the surface resistance value, and the appearance of the coating film surface. Comparative Examples 4 and 5 using the conductive composition 1 did not have sufficient conductivity.
• the carbon nanotube-containing composition of the present invention can be prepared by various simple antistatic agents, capacitors, batteries, fuel cells and polymer electrolyte membranes, electrode layers, and the like by using simple coating techniques such as coating, spraying, casting, and dipping.
• Materials such as catalyst layer, gas diffusion layer, gas diffusion electrode layer, separator, EMI shield, chemical sensor, display element, non-linear material, anticorrosive, adhesive, fiber, spinning material, antistatic paint, anticorrosive paint, It can be applied to applications such as electrodeposition paints, paint primers, conductive primers for electrostatic coating, cathodic protection, and improvement of battery storage capacity.
• the composite of the present invention can be used for industrial packaging materials such as semiconductors and electric / electronic parts, antistatic films such as electrophotographic recording materials such as films for overhead projectors and slide films, audio tapes and video tapes.
• Antistatic of magnetic recording tapes such as computer tapes and floppy disks, LSI wiring of electronic devices, electron guns (sources) and electrodes for field 'emission' displays (FED), hydrogen storage agents, and transparent touch panels , Electro-port luminescence display, Anti-static of input and display device surface such as liquid crystal display, and transparent electrode, Light-emitting material, buffer material, electron transport material, hole transport material and fluorescent material for organic electro-luminescence device, thermal transfer Sheet, transfer sheet, thermal transfer Door, is used as the image-receiving sheet.

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