JP2010212096A - Conductive film and method of manufacturing the same, and organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive film having high conductivity and high transparency at a conductive evaluation at time progress, and an organic electroluminescent element (hereafter, called organic EL element) which is excellent on stability after an environmental test under a high temperature and high humidity environment. <P>SOLUTION: In the conductive film including conductive nanowires and a binder, the conductive nanowire is a mixed valence compound made of a compound expressed by formula (I) and salt of an oxidant of the compound expressed by formula (I). Here, X<SB>1</SB>-X<SB>4</SB>show chalcogen atoms in formula (I), and it is acceptable that they may be the same or different. R<SB>1</SB>-R<SB>4</SB>independently show hydrogen atoms or substituents, respectively. Preferably, R<SB>1</SB>and R<SB>2</SB>, or R<SB>3</SB>and R<SB>4</SB>may form a cyclic structure by combining each other. Also, a conductive film manufacturing method and the organic EL element are provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a conductive film, a method for producing the same, and an organic electroluminescent element having the conductive film, and in various fields such as a liquid crystal display element, an organic light emitting element, an inorganic electroluminescent element, a solar cell, an electromagnetic wave shield, electronic paper, and a touch panel. The present invention relates to a conductive film, a method for producing the same, and an organic electroluminescence device having the conductive film, which can be suitably used.

  In recent years, various types of display technologies such as liquid crystal, plasma, organic electroluminescence, and field emission have been developed in response to the increasing demand for thin TVs. In any of these displays having different display methods, the conductive film is an essential constituent technology. In addition to televisions, conductive films are an indispensable technical element in touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescent light control elements.

  Conventionally, an ITO transparent electrode in which an indium-tin composite oxide (ITO) film is formed on a transparent base material such as glass or a transparent plastic film by a vacuum deposition method or a sputtering method has been mainly used. It was. However, indium used in ITO is a rare metal and removal of indium is desired due to the rising price. Also, roll-to-roll production technology using a flexible substrate has been desired along with an increase in display screen and productivity.

  In recent years, a conductive film using a conductor made of an organic substance has been disclosed, and a conductive film made of a cation radical of tetrafulvalene dicarboxylate and polyvinyl alcohol has been proposed (for example, see Non-Patent Document 1). However, in this conductive film, the conductor is not a mixed valence compound, and in the highly conductive region, the tetrafulvalenedicarboxylate cation radical forms a star-shaped crystal, which has a problem of low film transmittance. It was.

  A conductor using metal nanowires is also disclosed, and a transparent electrode in which a conductive polymer material is laminated on silver nanowires has been proposed (for example, see Patent Document 1). However, these have a structure in which conductive polymers such as PEDOT / PSS, polyaniline, and polypyrrole having low transmittance are laminated on the silver nanowire layer, and have a problem of achieving both high transmittance and conductivity. .

  In addition, a conductor in which silver nanowires are coated on PET and then spin-coated with a polyurethane methylethylketone solution has been proposed (see, for example, Patent Document 2). Since the electrode locally becomes a high temperature and is one of the factors that degrade the device life, it has a problem of improving the stability with high conductivity and transmittance over time.

  An organic electroluminescence device including a modified electrode using a tetrathiafulvalene / tetracyanoquinodimethane complex has been proposed (see, for example, Patent Document 3). However, a tetrathiafulvalene / tetracyanoquinodimethane complex solution is dropped onto the water surface during electrode preparation, and the formed film is transferred onto the Ag electrode with a PET film mask, which causes a reduction in the lifetime of the organic electroluminescence device. There is concern about water remaining. When water is present in the organic electroluminescence device, it causes dark spots, which has a problem of improving stability after an environmental test in a high temperature and high humidity environment.

US Patent No. 2008-259262 US Patent No. 2007-74316 JP 2002-353165 A

Synthetic Materials, (1995), vol. 68,281

  An object of the present invention is to provide a conductive film having high conductivity and transparency in the evaluation of conductivity over time, and an organic electroluminescence element (hereinafter referred to as an organic EL element) having excellent stability even after an environmental test under a high temperature and high humidity environment. (Also called).

  The above object of the present invention can be achieved by the following configuration.

  1. A conductive film containing a conductive nanowire and a binder, wherein the conductive nanowire is composed of a compound represented by the following general formula (I) and a salt of an oxidant of the compound represented by the general formula (I) A conductive film characterized by being a mixed valence compound.

[Wherein, X _{1 to} X ₄ each represent a chalcogen atom and may be the same or different. R _{1 to} R ₄ each independently represents a hydrogen atom or a substituent, but R ₁ and R ₂ , or R ₃ and R ₄ may be bonded to each other to form a cyclic structure. ]
2. _2. The conductive film according to 1 above, wherein X ₁ , X ₂ , X ₃ and X _{4 of the} compound represented by the general formula (I) are sulfur atoms.

  3. 3. The conductive film as described in 1 or 2 above, wherein the counter anion of the oxidized salt of the compound represented by the general formula (I) is an anion represented by the following general formula (II).

Formula (II) R ₅ COO ⁻
[Wherein R ₅ represents a substituent. ]
4). The organic electroluminescent element characterized by using the electrode comprised from the electrically conductive film of any one of said 1-3.

  5. The conductive film according to any one of the above 1 to 3, a solution containing a compound represented by the general formula (I) and a salt containing an oxidant of the compound represented by the general formula (I) And a solution containing a binder, followed by coating and drying on a support, and a method for producing a conductive film.

  As a result of diligent studies to overcome the problems of the present invention, a conductive film having high conductivity and transparency in the evaluation of conductivity over time, and excellent stability even after an environmental test under a high temperature and high humidity environment An organic EL device could be provided.

It is a structure schematic diagram of the electrically conductive film of this invention. It is a figure which shows the time change of the electrical conductivity of the electrically conductive film which concerns on this invention. It is a scanning microscope picture of the electrically conductive film surface concerning this invention. It is an ultraviolet-visible near-infrared absorption spectrum of the electrically conductive film of this invention. It is a powder X-ray diffraction spectrum of the electrically conductive film which concerns on this invention.

  The present invention will be described in more detail.

  The present invention is characterized by containing a nanowire composed of a mixed valence compound composed of a binder and a salt of an oxidant of the compound represented by the general formula (I) and the general formula (I).

  In the present invention, in particular, by including nanowires in the binder, it has high stability in the evaluation of conductivity over time, and further has excellent stability even after environmental tests under high temperature and high humidity environments. Electroluminescence is obtained.

[Conductive nanowires]
The conductive nanowire according to the present invention is conductive and has a length that is sufficiently longer than its diameter (thickness). The conductive nanowire according to the present invention is considered to function as an auxiliary electrode by forming a three-dimensional conductive network when the conductive nanowires contact each other in the transparent conductive layer. Accordingly, a longer conductive nanowire is preferable because it is advantageous for forming a conductive network. On the other hand, when the conductive nanowires become long, the conductive nanowires are entangled to form aggregates, which may deteriorate the optical characteristics. Conductive network formation and aggregate formation are also affected by the rigidity and diameter of the conductive nanowires, so use the optimal average aspect ratio (aspect = length / diameter) according to the conductive nanowire used. It is preferable to do. As a rough guide, the average aspect ratio is preferably 10 to 10,000, more preferably 15 to 1,000.

  In the present invention, the average values of the length, diameter and aspect ratio of the conductive nanowires are obtained from the arithmetic average of the measured values of the individual conductive wire images by taking electron micrographs of a sufficient number of conductive nanowires. be able to. The length of the conductive wire should be measured in a linearly stretched state, but in reality, it is often bent, so the projected diameter of the nanowire using an image analyzer from an electron micrograph The projected area can also be calculated and calculated assuming a cylindrical body (length = projected area / projected diameter). The relative standard deviation of length and diameter is expressed by a value obtained by multiplying 100 by the value obtained by dividing the standard deviation of the measured value by the average value. The number of conductive nanowire samples to be measured is preferably at least 100 or more, more preferably 300 or more.

Relative standard deviation [%] = standard deviation of measured value / average value × 100
Examples of the shape of the nanowire of the present invention include a hollow tube shape, a wire shape, a fiber shape, and a rod shape. The conductive nanowire of the present invention is composed only of organic components, but is used in combination with the organic conductive nanowire and inorganic nanowire, conductive metal oxide nanowire, metal nanowire, carbon fiber, carbon nanotube, etc. May be used. Further, the conductive nanowire of the present invention may be coated with a metal, a metal oxide or the like. From the viewpoint of cost (raw material cost, manufacturing cost) and performance (conductivity, transparency, flexibility), oxidation of the compound represented by the general formula (I) and the general formula (I), which are organic conductive nanowires Conductive nanowires composed of mixed valence compounds consisting of body salts are most preferred.

The conductive nanowire of the present invention includes a compound represented by the general formula (I), an oxidant of the compound represented by the general formula (I), an anion of a carboxylic acid represented by the general formula (II), or a sulfonic acid Of these, an anion and a halogen anion are preferred. The conductive nanowire of the present invention is composed of a compound represented by the general formula (I) and an oxidized salt of the compound represented by the general formula (I). In the absorption spectrum, wide absorption was observed in the vicinity of 2000 cm ⁻¹ , suggesting a mixed atomized state. A mixed-valence compound is a chemical substance in which the same kind of atoms constituting the substance have different oxidation numbers (electronic states).

In the general formula (I) of the present invention, X _{1 to} X ₄ each represent a chalcogen and may be the same or different. A chalcogen atom is an element generic name belonging to Group 16 in the periodic table, and oxygen, sulfur, selenium, tellurium and polonium are classified into this. The chalcogen in the present invention is preferably sulfur, selenium or tellurium, more preferably sulfur.

In the general formula (I) of the present invention, R _{1 to} R ₄ each independently represent a hydrogen atom or a substituent, and R ₁ and R ₂ , or R ₃ and R ₄ are bonded to each other to form a cyclic structure. Also good.

Examples of said substituent represented by R ₁ to R ₄ of the general formula (I) of the present invention, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, an arylthio group, cycloalkoxy Group, aryl group, aryloxy group, heterocycloalkyl group, heteroaryl group, acyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, ureido group, aralkyl group, nitro group, Alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, acyloxy group, alkenyl group, alkynyl group, alkylsulfonyl group, aryl Ruhoniru group, alkyloxy sulfonyl group, aryloxy sulfonyl group, alkylsulfonyloxy group, and an aryl sulfonyloxy group. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 8. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, octyl group and 2-ethylhexyl group.

  The number of carbon atoms of the cycloalkyl group is preferably 3-20, more preferably 3-12, and still more preferably 3-8. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The alkoxy group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6, and further preferably 1 to 4. Most preferably. Examples of the alkoxy group include methoxy group, ethoxy group, 2-methoxyethoxy group, 2-methoxy-2-ethoxyethoxy group, butyloxy group, hexyloxy group and octyloxy group. The number of carbon atoms of the alkylthio group may be branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6, Most preferably, it is 1-4. Examples of the alkylthio group include a methylthio group and an ethylthio group. The arylthio group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylthio group include a phenylthio group and a naphthylthio group. The number of carbon atoms of the cycloalkoxy group is preferably 3-12, more preferably 3-8. Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group. The aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group. The aryloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxy group include a phenoxy group and a naphthoxy group. The heterocycloalkyl group preferably has 2 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Examples of the heterocycloalkyl group include a piperidino group, a dioxanyl group, and a 2-morpholinyl group. The number of carbon atoms in the heteroaryl group is preferably 3-20, and more preferably 3-10. Examples of the heteroaryl group include a thienyl group and a pyridyl group. The acyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group. The alkylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylcarbonamide group include an acetamide group. The arylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylcarbonamide group include a benzamide group and the like. The alkylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the sulfonamido group include a methanesulfonamido group and the like, and the arylsulfonamido group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylsulfonamide group include a benzenesulfonamide group and p-toluenesulfonamide group. The number of carbon atoms in the aralkyl group is preferably 7-20, and more preferably 7-12. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group. The alkoxycarbonyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the alkoxycarbonyl group include a methoxycarbonyl group. The aryloxycarbonyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group. The aralkyloxycarbonyl group preferably has 8 to 20 carbon atoms, and more preferably 8 to 12 carbon atoms. Examples of the aralkyloxycarbonyl group include a benzyloxycarbonyl group. The acyloxy group preferably has 1 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group. The alkenyl group has preferably 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group and isopropenyl group. The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkynyl group include an ethynyl group. The alkylsulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyl group include a methylsulfonyl group and an ethylsulfonyl group. The arylsulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group. The alkyloxysulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkyloxysulfonyl group include a methoxysulfonyl group and an ethoxysulfonyl group. The aryloxysulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxysulfonyl group include a phenoxysulfonyl group and a naphthoxysulfonyl group. The alkylsulfonyloxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group and an ethylsulfonyloxy group.

  The number of carbon atoms of the arylsulfonyloxy group is preferably 6-20, and more preferably 6-12. Examples of the arylsulfonyloxy group include a phenylsulfonyloxy group and a naphthylsulfonyloxy group. The substituents may be the same or different, and these substituents may be further substituted.

R ₁ and R ₂ , or R ₃ and R ₄ represented by the general formula (I) of the present invention may be bonded to each other to form a cyclic structure. In that case, an unsaturated hydrocarbon ring, aromatic A structure in which an aromatic ring, an aliphatic heterocyclic ring, an aromatic heterocyclic ring or the like is condensed is preferable. The condensed rings formed by combining R ₁ and R ₂ , and R ₃ and R ₄ may be the same or different, and preferably form an unsaturated hydrocarbon ring or an aromatic ring. These rings may be further substituted with the above-described substituents.

In the general formula (I) of the present invention, R ₁ , R ₂ , R ₃ and R ₄ are each preferably a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, and more preferably R ₁ , R ₂ , R _3. And R ₄ is all hydrogen.

  Although the typical example of a compound represented with general formula (I) of this invention below is shown, this invention is not limited to these.

  The compound represented by the general formula (I) of the present invention can be synthesized by a known method such as Journalofthe Chemical Society, Chemical Communications, 1980, 38-39 or JP-A No. 2002-265466.

  The salt of the oxidized form of the compound represented by the general formula (I) of the present invention includes an oxidized form (cation radical) of the compound represented by the general formula (I) and an anion of the carboxylic acid represented by the general formula (II). Alternatively, it is composed of a sulfonic acid anion and a halogen anion.

  The anion of the carboxylic acid represented by the general formula (II) of the present invention or the anion of the sulfonic acid is not particularly limited as long as it contains a carboxylic acid anion and a sulfonic acid anion moiety in the molecule. It may be a polymer. In addition, a carboxylate anion or a plurality of anions such as a sulfonate anion and a halogen anion may be contained, or these anion species may be contained simultaneously.

  Examples of the carboxylate anion represented by the general formula (II) of the present invention include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodencanic acid, tetra Dodecanoic acid, hexadecanoic acid, heptadecanoic acid, heptadecanoic acid, octadecanoic acid, isobutyric acid, isovaleric acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, henicosafluorododecanoic acid, oleic acid, linoleic acid, linolenic acid, Arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, oxalic acid, malonic acid, succinic acid, adipic acid, benzoic acid, phthalic acid, salicylic acid, gallic acid, melicic acid, cinnamic acid, lactic acid, malic acid, citric acid, fumaric acid , Maleic acid, aconitic acid, amino acid, nitrocarboxylic acid, polyacrylic acid Acid, copolymers of polyacrylic acid, polymethacrylic acid, anions of a copolymer of polymethacrylic acid. Examples of sulfonic acid anions include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, undecanesulfonic acid, 10-camphorsulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutane. Sulfonic acid, 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, 1,5-naphthalenedisulfonic acid, polystyrene Examples include anions such as sulfonic acid and polystyrene sulfonic acid copolymers. The halogen anion represents an anion of fluorine, chlorine, bromine, iodine, or astatine belonging to Group 17, and anion of chlorine, bromine, or iodine is preferable. More preferably, it is a chlorine anion. The counter anion of the oxidant of the compound represented by the general formula (I) of the present invention includes trifluoroacetic acid, heptafluorobutyric acid, henicosafluorododecanoic acid, methanesulfonic acid, propanesulfonic acid, undecanesulfonic acid, and benzenesulfonic acid. And an anion of chlorine, more preferably an anion of heptafluorobutyric acid.

  In the conductive nanowire of the present invention, a metal nanowire and a carbon nanotube can be used in combination.

  As a metal nanowire, in order to form a long conductive path with one metal nanowire, the average length is preferably 3 μm or more, more preferably 3 to 500 μm, and particularly preferably 3 to 300 μm. preferable. In addition, the relative standard deviation of the length is preferably 40% or less. Moreover, it is preferable that an average diameter is small from a transparency viewpoint, On the other hand, the larger one is preferable from an electroconductive viewpoint. In this invention, 10-300 nm is preferable as an average diameter of metal nanowire, and it is more preferable that it is 30-200 nm. In addition, the relative standard deviation of the diameter is preferably 20% or less.

  There is no restriction | limiting in particular as a metal composition of metal nanowire, Although it can comprise from the 1 type or several metal of a noble metal element and a base metal element, it is a noble metal (For example, gold | metal | money, platinum, silver, palladium, rhodium, iridium, ruthenium) And at least one metal belonging to the group consisting of iron, cobalt, copper, and tin. When the metal nanowire includes two or more kinds of metal elements, for example, the metal composition may be different between the inside and the surface of the metal nanowire, and the entire metal nanowire has the same metal composition. Also good.

  A carbon nanotube is a carbon-based fiber material having a shape in which a graphite-like carbon atomic plane (graphene sheet) having a thickness of several atomic layers is wound into a cylindrical shape, and single-walled nanotubes (SWNT) and multilayers are formed from the number of peripheral walls. It is roughly divided into nanotubes (MWNT), and it is divided into a chiral type, a zigzag type, and an armchair type depending on the structure of the graphene sheet, and various types are known. The shape of the carbon nanotube is preferably a single-walled carbon nanotube having a large aspect ratio (= length / diameter), that is, a thin and long carbon nanotube, in order to form a long conductive path with one carbon nanotube. For example, carbon nanotubes having an aspect ratio of 102 or more, preferably 103 or more can be mentioned. The average length of the carbon nanotubes is preferably 3 μm or more, more preferably 3 to 500 μm, and particularly preferably 3 to 300 μm. In addition, the relative standard deviation of the length is preferably 40% or less. Moreover, it is preferable that an average diameter is smaller than 100 nm, 1-50 nm is preferable and it is more preferable that it is 1-30 nm. In addition, the relative standard deviation of the diameter is preferably 20% or less.

〔binder〕
Any transparent binder may be used as long as it is transparent. What is necessary is just to select arbitrarily from compositions, such as water-soluble polymer, organic-solvent soluble polymer, polymer latex, aqueous | water-based ionomer, thermosetting resin, photocuring resin, energy-beam curable resin. Moreover, after apply | coating a polymerizable monomer, an oligomer, or those mixtures, you may superpose | polymerize with light, a heat | fever, an electron beam, etc., and may form a transparent binder layer. Among these, when a polymer binder is used as the transparent binder layer, those listed in Polymer Handbook VI / 453-VI / 461 can be preferably used as examples of the polymer binder.

  The binder of the present invention is not particularly limited as long as it is a natural polymer, synthetic resin, polymer and copolymer, or other medium for forming a film, but may be hydrophilic or hydrophobic.

  Examples of hydrophilic binders include: gelatin, casein, starch, gum arabic, poly (vinyl alcohol), poly (vinyl pyrrolidone), carboxymethyl ether cellulose, hydroxyethyl cellulose, cellulose such as methyl hydroxyethyl ether cellulose, chitosan, dextran , Guar gum, poly (acrylamide), poly (acrylamide-acrylic acid), poly (acrylic acid), poly (methacrylic acid), poly (allylamine), poly (butadiene-maleic anhydride), poly (n-butyl acrylate-2) -Methacryloyltrimethylammonium bromide), poly (3-chloro-2-hydroxypropyl-2-methacryloxytrimethylammonium bromide), poly (2-dimethylaminoethyl methacrylate) ), Poly (ethylene glycol), poly (ethylene glycol) -bisphenol A-diglycidyl ether adduct, poly (ethylene glycol) bis 2-aminoethyl, poly (ethylene glycol) dimethyl ether, poly (ethylene glycol) monocarboxymethyl ether Monomethyl ether, poly (ethylene glycol) monomethyl ether, poly (ethylene oxide), poly (ethylene oxide-b-propylene oxide), polyethyleneimine, poly (2-ethyl-2-oxazoline), poly (1-glycerol methacrylate), poly ( 2-hydroxyethyl acrylate), poly (2-ethyl methacrylate), poly (2-hydroxyethyl methacrylate-methacrylic acid), poly (maleic acid), poly (methacrylamido) ), Poly (2-methacryloxyethyltrimethylammonium bromide), poly (N-iso-propylacrylamide), poly (styrenesulfonic acid), poly (N-vinylacetamide), poly (N-methyl-N-vinylacetamide) , Poly (vinylamine), poly (2-vinyl-1-methylpyridinium bromide), poly (phosphoric acid), poly (2-vinylpyridine), poly (4-vinylpyridine), poly (2-vinylpyridine-N- Oxide), poly (vinyl sulfonic acid) and the like. In the above binder, the polymer having carboxylic acid, sulfonic acid, phosphoric acid or the like may have a salt such as lithium, sodium or potassium, and the polymer having a nitrogen atom has a structure such as hydrochloride. Also good. Moreover, the melamine resin, urea resin, glyoxal resin, etc. which are thermosetting resins can also be mentioned. One or more of the binders can be used.

  Examples of the hydrophobic binder include homopolymers and copolymers (for example, polymethyl methacrylate) such as acrylic acid ester and methacrylic acid ester, polyethylene, polypropylene, polystyrene, vinyl chloride copolymer, vinyl chloride-vinyl acetate. Copolymers, vinyl polymers such as polyvinyl vinyl ether, polyvinyl acetate, polystyrene, copolymers of vinyl compounds, condensation polymers such as polyester, polyurethane, polyamide, rubber heat such as butadiene-styrene copolymers Examples thereof include a plastic polymer. Moreover, curable resin, such as the composition of an acid generator and an epoxy compound which generate | occur | produce an acid with a heat | fever or light, the composition of an optical radical generator and an acrylate and a methacrylate compound which generate | occur | produce a radical by light irradiation, can also be mentioned.

  “Polymer latex” is a water-insoluble hydrophobic polymer dispersed as fine particles in a water-soluble dispersion medium. As the dispersion state, the polymer is emulsified in the dispersion medium, the emulsion polymerized, the micelle-dispersed, or the polymer molecule has a partially hydrophilic structure and the molecular chain itself is molecularly dispersed. Any of them may be used. For polymer latex, see "Synthetic Resin Emulsion (Hiraku Okuda, Hiroshi Inagaki, published by Polymer Press (1978))", "Applications of Synthetic Latex (Takaaki Sugimura, Tatsuo Kataoka, Junichi Suzuki, Keiji Kasahara, edited by Koshihara Kogyo) Publication (1993)), “Synthetic Latex Chemistry (Muroichi Soichi, published by Kobunshi Shuppankai (1970))” and the like. The average particle size of the dispersed particles is preferably from 1 to 50000 nm, more preferably from about 5 to 1000 nm. The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution. The polymer latex may be a so-called core / shell type latex other than a normal polymer latex having a uniform structure. In this case, it may be preferable to change the glass transition temperature between the core and the shell.

  Examples of the polymer species used for the polymer latex include acrylic resins, vinyl acetate resins, polyester resins, polyurethane resins, rubber resins, vinyl chloride resins, vinylidene chloride resins, polyolefin resins, and copolymers thereof. The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized or a copolymer in which two or more monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer. A preferred polymer is a linear random copolymer. The molecular weight of the polymer is 5,000 to 1,000,000, preferably 10,000 to 100,000 in terms of number average molecular weight. When the molecular weight is too small, the mechanical strength is insufficient, and when the molecular weight is too large, the film formability is poor, which is not preferable. Specific examples of the polymer latex include: methyl methacrylate / ethyl acrylate / methacrylic acid copolymer latex, methyl methacrylate / butadiene / itaconic acid copolymer latex, ethyl acrylate / methacrylic acid copolymer latex, methyl methacrylate / 2-ethylhexyl acrylate / styrene. / Latex of acrylic acid copolymer, latex of styrene / butadiene / acrylic acid copolymer, latex of styrene / butadiene / divinylbenzene / methacrylic acid copolymer, latex of methyl methacrylate / vinyl chloride / acrylic acid copolymer, vinylidene chloride / ethyl acrylate / acrylonitrile / Examples thereof include latex of methacrylic acid copolymer.

  The binder used in the present invention is preferably gelatin, poly (vinyl alcohol), cellulose acetate propionate, poly (vinyl pyrrolidone), poly (vinyl butyral), polymethyl methacrylate, or polystyrene, and more preferably poly (vinyl). Pyrrolidone), polymethyl methacrylate, and polystyrene.

[Conductive film]
The conductive film of the present invention may be a self-supporting film composed of the conductive nanowires of the present invention and a binder, or may be laminated on a support.

  An example of a structural schematic diagram of the conductive film of the present invention is shown in FIG. FIG. 1 is a structural schematic diagram of a representative conductive film of the present invention, which has a conductive film 31 on a transparent substrate 51, and the conductive film includes a conductive nanowire 11 and a binder 21. . In the present invention, other configurations are not particularly limited.

  The transparent substrate can be subjected to a surface treatment as described above, and various functional layers can be provided depending on the purpose.

In the conductive film of the present invention, the total light transmittance is preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like. In addition, the electrical resistance value of the conductive film of the present invention is preferably 1000Ω / □ or less, more preferably 100Ω / □ or less as the surface resistivity. Furthermore, in order to apply to a current drive type optoelectronic device, it is preferably 50Ω / □ or less, particularly preferably 10Ω / □ or less. It is preferable that it is 10 ³ Ω / □ or less because it can function as a conductive film in various optoelectronic devices. The surface resistivity can be measured in accordance with, for example, JIS K7194: 1994 (resistivity test method using conductive plastic 4-probe method), and can be easily measured using a commercially available surface resistivity meter. can do.

  There is no restriction | limiting in particular in the thickness of the electrically conductive film of this invention, Although it can select suitably according to the objective, Generally it is preferable that it is 10 micrometers or less, and transparency and a softness | flexibility improve, so that thickness becomes thin. More preferred. Although it differs depending on the shape of the conductive nanowire used and the binder content, as a rough guide, the average diameter of the conductive nanowire is preferably 500 nm or less. It is preferable to reduce the thickness of the conductive film according to the present invention by a pressurizing method or the like because the network formation of conductive nanowires in the thickness direction can be made dense.

[Support]
As the support of the present invention, there is no particular limitation as long as the conductive nanowire of the present invention and a conductive film composed of a binder can be laminated, but glass and resin films are preferable, and when used for optical purposes, it is a colorless and transparent transparent substrate. Preferably there is.

  In the present invention, “transparent” means total light transmission in the visible light wavelength region measured by a method in accordance with “Testing method of total light transmittance of plastic-transparent material” of JIS K7361-1 (corresponding to ISO13468-1). The rate is 60% or more.

  The transparent substrate used for the conductive film of the present invention is not particularly limited as long as it has high light transmittance. For example, base materials such as a glass substrate, a resin substrate, and a resin film are preferable in terms of excellent hardness as a base material and ease of forming a conductive layer on the surface.

  There is no restriction | limiting in particular in the transparent resin film which can be used as a transparent base material of this invention, About the material, a shape, a structure, thickness, etc., it can select suitably from well-known things. For example, polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate, modified polyester, polyethylene (PE) resin films, polypropylene (PP) resin films, polystyrene resin films, polyolefin resin films such as cyclic olefin resins, Vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate (PC) resin film, polyamide resin A film, a polyimide resin film, an acrylic resin film, a triacetyl cellulose (TAC) resin film, and the like can be given. If the resin film transmittance of 80% or more in nm), can be preferably applied to a transparent resin film of a transparent substrate according to the present invention. Among these, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, it is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. More preferred are polyethylene terephthalate films and biaxially stretched polyethylene naphthalate films.

  The transparent substrate used in the present invention can be subjected to a surface treatment or an easy-adhesion layer in order to ensure the wettability and adhesion of the coating solution. A conventionally well-known technique can be used about a surface treatment or an easily bonding layer. For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment. Examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer. When the transparent resin film is a biaxially stretched polyethylene terephthalate film, by making the refractive index of the easy adhesion layer adjacent to the film 1.57-1.63, the interface reflection between the film substrate and the easy adhesion layer can be achieved. Since it can reduce and can improve the transmittance | permeability, it is more preferable. The method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion. Moreover, the barrier coat layer may be formed in advance on the transparent substrate, or the hard coat layer may be formed in advance on the opposite side to which the transparent conductive layer is transferred.

〔Production method〕
In the method for producing a conductive film of the present invention, a solution (A) containing a compound represented by the general formula (I), a solution (B) containing a salt of an oxidant of the compound represented by the general formula (I) And after mixing the solution (C) containing a binder, it apply | coats on a support body, it dries after that and is manufactured. The solvent of the solution (A) containing the compound represented by the general formula (I) is not particularly limited as long as the compound represented by the general formula (I) is dissolved, but acetonitrile is preferable. The concentration of the solution (A) is preferably a concentration at which the compound represented by the general formula (I) does not precipitate, preferably 1 to 20 mM, particularly preferably 3 to 10 mM. The salt of the oxidized form of the compound represented by the general formula (I) is produced in a solution in which the compound represented by the general formula (I) and the oxidizing agent are dissolved. The oxidizing agent is not particularly limited, but potassium ferricyanide (K ₃ Fe (CN) ₆ ) and iodobenzene diacetate are preferable, and iodobenzene diacetate is particularly preferable. Although there is no restriction | limiting in particular in the solvent used when manufacturing the salt of the oxidant of the compound represented by general formula (I), Acetonitrile is preferable. The solvent of the solution (B) containing the oxidized salt of the compound represented by the general formula (I) is not particularly limited as long as the oxidized salt of the compound represented by the general formula (I) is dissolved. Acetonitrile is preferred. The concentration of the solution (B) is preferably a concentration at which the salt of the oxidant represented by the general formula (I) does not precipitate, preferably 1 to 50 mM, particularly preferably 5 to 30 mM. The solvent of the solution (C) containing the binder is not particularly limited as long as the binder to be used is dissolved. For example, in the case of polymethyl methacrylate, polyvinyl pyrrolidone and polystyrene, methylene chloride, acetonitrile and benzene are preferable, respectively. The preparation of the coating solution includes a solution (A) containing the compound represented by the general formula (I), a solution (B) containing a salt of an oxidant of the compound represented by the general formula (I), and a binder. The solution (C) to be obtained is mixed and then stirred at room temperature. The stirring time is preferably 1 to 180 minutes, more preferably 3 to 120 minutes, and further preferably 5 to 60 minutes.

  Although there is no restriction | limiting in particular in the method of forming the electrically conductive nanowire and the electrically conductive film containing a binder on a transparent base material in the manufacturing method of the electrically conductive film of this invention, The electrically conductive film of productivity improvement, smoothness, uniformity, etc. From the viewpoint of improving the quality and reducing the environmental burden, it is preferable to use a liquid phase film forming method such as a coating method or a printing method for forming the conductive film. Application methods include roll coating, bar coating, dip coating, spin coating, casting, die coating, blade coating, bar coating, gravure coating, curtain coating, spray coating, and doctor coating. Etc. can be used. As the printing method, a letterpress (letter) printing method, a stencil (screen) printing method, a lithographic (offset) printing method, an intaglio (gravure) printing method, a spray printing method, an ink jet printing method, and the like can be used. In addition, as necessary, physical surface treatment such as corona discharge treatment or plasma discharge treatment can be applied to the surface of the releasable substrate as a preliminary treatment for improving the adhesion and coating properties.

  In the manufacturing method of the electrically conductive film of this invention, after forming the electrically conductive film containing electroconductive nanowire and a binder on the mold release surface of a smooth moldable base material, this electrically conductive film is formed on an adhesive transparent base material. A method of forming a conductive film by transferring may be used. By using this method, the surface of the conductive film can be easily and stably highly smoothed.

  Suitable examples of the releasable substrate used in the method for producing a conductive film of the present invention include a resin substrate and a resin film. There is no restriction | limiting in particular in this resin, It can select suitably from well-known things, For example, synthesis | combination, such as a polyethylene terephthalate resin, a vinyl chloride resin, an acrylic resin, a polycarbonate resin, a polyimide resin, a polyethylene resin, a polypropylene resin A substrate or film composed of a single layer or multiple layers of resin is preferably used. Furthermore, a glass substrate or a metal substrate can also be used. Further, the surface (release surface) of the releasable substrate may be subjected to a surface treatment by applying a release agent such as silicone resin, fluororesin, or wax as necessary.

  Since the surface of the releasable substrate affects the smoothness of the surface after the conductive film is transferred, it is desirable that the surface of the releasable substrate be highly smooth. Specifically, Ry ≦ 50 nm is preferable, and Ry ≦ 40 nm. It is more preferable that Ry ≦ 30 nm. Further, Ra ≦ 5 nm is preferable, Ra ≦ 3 nm is more preferable, and Ra ≦ 1 nm is still more preferable. Ry and Ra representing the smoothness of the surface mean Ry = maximum height (difference between the top and bottom of the surface) and Ra = arithmetic mean roughness, and are defined in JIS B601 (1994). It is a value according to the roughness, and a commercially available atomic force microscope (AFM) can be used for the measurement of Ry and Ra.

  As a specific method for forming a conductive film excellent in smoothness including conductive nanowires and a binder on a transparent substrate, for example, the following process can be exemplified.

  On the release surface of the release substrate, a conductive nanowire and binder dispersion liquid is applied (or printed) and dried to form a conductive network structure composed of conductive nanowires. An adhesive layer is coated on a transparent base material, and both are bonded together. After the adhesive layer is cured, the conductive film is transferred to the transparent substrate by peeling the release substrate. Further, a conductive nanowire dispersion liquid is applied (or printed) and dried on the release surface of the release substrate to form a conductive network structure made of conductive nanowires. Next, a dispersion liquid of a conductive material is applied (or printed) on the network structure of the conductive nanowires, and the conductive material is impregnated in the gaps of the network structure of the conductive nanowires on the substrate surface. A conductive film layer including a wire and a conductive material is formed. Next, an adhesive layer is applied on the conductive film layer or another transparent substrate, and both are bonded together. After the adhesive layer is cured, the conductive film layer is transferred to the transparent substrate by peeling the release substrate.

  In the above process, after applying and drying conductive nanowires, calendar treatment and heat treatment are applied to increase the adhesion between conductive nanowires, or plasma treatment is applied to reduce contact resistance between conductive nanowires. This is effective as a method for improving the conductivity of the network structure of conductive nanowires. In the above process, the release surface of the release substrate may be previously hydrophilized by corona discharge (plasma) or the like.

  In the above process, the adhesive layer may be provided on the releasable substrate side or on the transparent base material side. The adhesive used for the adhesive layer is not particularly limited as long as it is a material that is transparent in the visible region and has transfer ability. As long as it is transparent, a curable resin or a thermoplastic resin may be used.

  Examples of curable resins include thermosetting resins, ultraviolet curable resins, and electron beam curable resins. Among these curable resins, the equipment for resin curing is simple and excellent in workability. It is preferable to use an ultraviolet curable resin. The ultraviolet curable resin is a resin that is cured through a crosslinking reaction or the like by ultraviolet irradiation, and a component containing a monomer having an ethylenically unsaturated double bond is preferably used. For example, acrylic urethane type resin, polyester acrylate type resin, epoxy acrylate type resin, polyol acrylate type resin and the like can be mentioned. In the present invention, it is preferable that an acrylic or acrylic urethane-based ultraviolet curable resin is a main component as a binder.

  Acrylic urethane-based resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates including methacrylates) to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used. For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.

  Examples of UV curable polyester acrylate resins include those which are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added to the oligomer, and a reaction. Those described in US Pat. No. 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.

  Examples of the resin monomer may include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  Among these, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolethane (meth) acrylate as the main component of the binder , An acrylic selected from dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate A system active ray curable resin is preferred.

  Specific examples of the photoinitiator of these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer. The photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photoinitiator, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.

  The transparent conductive film is made transparent by bonding (bonding) the release substrate on which the transparent conductive film is formed and the transparent base material, curing the adhesive by irradiating ultraviolet rays and the like, and then peeling the release substrate. It can be transferred to the substrate side. Here, the bonding method is not particularly limited and can be performed by a sheet press, a roll press or the like, but is preferably performed using a roll press machine. The roll press is a method in which a film to be bonded is sandwiched between the rolls, and the rolls are rotated. The roll press is uniformly applied with pressure, and has a higher productivity than the sheet press and can be used preferably.

  The conductive film of the present invention can contain a conductive material. Examples of the conductive polymer applied to the conductive material include polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, Examples include compounds selected from the group consisting of polydiacetylene and polynaphthalene derivatives.

  The conductive material may contain one kind of conductive polymer alone or may contain two or more kinds of conductive polymers in combination, but from the viewpoint of conductivity and transparency, Polyaniline having a repeating unit represented by the general formula (1) or general formula (2) or a derivative thereof, a polypyrrole derivative having a repeating unit represented by the following general formula (3), or represented by the following general formula (4) More preferably, it contains at least one compound selected from the group consisting of polythiophene derivatives having repeating units.

In the general formula (1), M represents H ⁺ , an alkali metal ion, or an ammonium ion. In the general formula (2), A represents an optionally substituted alkylene group having 1 to 4 carbon atoms, and Q represents an oxygen atom or a sulfur atom. In general formula (5) and general formula (6), R is mainly a linear organic substituent, preferably an alkyl group, an alkoxy group, an allyl group, or a combination of these groups. It is sufficient that the above properties are not lost, and a sulfonate group, an ester group, an amide group or the like may be bonded to or combined with these. Note that n is an integer.

The conductive polymer can be subjected to a doping treatment in order to further increase the conductivity. As a dopant for the conductive polymer, for example, a sulfonic acid having a hydrocarbon group having 6 to 30 carbon atoms (hereinafter also referred to as a long-chain sulfonic acid) or a polymer thereof (for example, polystyrene sulfonic acid), a halogen atom , Lewis acid, proton acid, transition metal halide, transition metal compound, alkali metal, alkaline earth metal, MClO ₄ (M = Li ⁺ , Na ⁺ ), R ₄ N ⁺ (R═CH ₃ , C ₄ H ₉ , C ₆ H ₅ ), or R ₄ P ⁺ (R═CH ₃ , C ₄ H ₉ , C ₆ H ₅ ). Of these, the long-chain sulfonic acid is preferable.

  The dopant for the conductive polymer may be introduced into fullerenes such as hydrogenated fullerene, hydroxylated fullerene, and sulfonated fullerene. In the transparent conductive film, the dopant is preferably contained in an amount of 0.001 part by mass or more with respect to 100 parts by mass of the conductive polymer. Furthermore, it is more preferable that 0.5 mass part or more is contained.

The conductive material of the present invention includes a long-chain sulfonic acid, a polymer of long-chain sulfonic acid (for example, polystyrene sulfonic acid), halogen, Lewis acid, proton acid, transition metal halide, transition metal compound, alkali metal, Both at least one dopant selected from the group consisting of alkaline earth metals, MClO ₄ , R ₄ N ⁺ , and R ₄ P ⁺ and fullerenes may be included.

  As the conductive polymer, a conductive polymer modified with a metal disclosed in JP-T-2001-511581, JP-A-2004-99640, JP-A-2007-165199, or the like can also be used.

  The conductive material containing a conductive polymer may contain a water-soluble organic compound. Among water-soluble organic compounds, compounds having an effect of improving conductivity by adding to a conductive polymer material are known, and 2nd. Sometimes called a dopant (or sensitizer).

  2nd. Which can be used for conductive materials. There is no restriction | limiting in particular in a dopant, It can select suitably from well-known things, For example, a dimethyl sulfoxide (DMSO), diethylene glycol, and another oxygen containing compound are mentioned suitably.

  In the conductive material containing a conductive polymer, the 2nd. 0.001 mass part or more is preferable, as for content of a dopant, 0.01-50 mass parts is more preferable, and 0.01-10 mass parts is especially preferable.

  The conductive material containing a conductive polymer may contain a transparent resin component or additive in addition to the conductive polymer in order to ensure film formability and film strength. The transparent resin component is not particularly limited as long as it is compatible or mixed and dispersed with the conductive polymer, and may be a thermosetting resin or a thermoplastic resin. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyimide resins such as polyimide and polyamideimide, polyamide resins such as polyamide 6, polyamide 6,6, polyamide 12 and polyamide 11, polyvinylidene fluoride, Fluorine resin such as polyvinyl fluoride, polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene, etc., vinyl resin such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride, epoxy resin, xylene Resin, aramid resin, polyurethane resin, polyurea resin, melamine resin, phenol resin, polyether, acrylic resin and their co-polymer Body, and the like.

  A polyanion may be used for the conductive material in order to improve conductivity. Examples of the polyanion used in the present invention include compounds selected from the group consisting of polymer carboxylic acids, polymer sulfonic acids, and derivatives of these salts, preferably polymer sulfonic acids and salts thereof. . The polyanions may be contained alone or in combination of two or more. The polyanion may form a copolymer with a structural unit having carboxylic acid or sulfonic acid and a monomer having no acid residue, such as acrylate, methacrylate, styrene, or the like.

  Specific examples of the polymer carboxylic acid, polymer sulfonic acid and salts thereof include, for example, polyacrylic acid, polymethacrylic acid or polymaleic acid, polymer sulfonic acid, polystyrene sulfonic acid and polyvinyl sulfonic acid and salts thereof. Polystyrene sulfonic acid and its salt are preferable.

[Patterning method]
The conductive film of the present invention can be patterned. There is no particular limitation on the patterning method or process, and a known method can be applied as appropriate. For example, a method of forming a patterned conductive film by forming a patterned conductive film on a release surface and then transferring it onto a transparent substrate can be used. The method can be preferably used.

i) A method of directly forming the conductive film of the present invention in a pattern-like manner on a releasable substrate using a printing method.
ii) A method of uniformly forming the conductive film of the present invention on a releasable substrate and then patterning using a general photolithography process
iii) A method of patterning like a photolithography process after uniformly forming the conductive film of the present invention using, for example, a conductive material containing an ultraviolet curable resin
iv) A method of uniformly forming the conductive film of the present invention on a negative pattern previously formed of a photoresist on a releasable substrate and patterning it using the lift-off method In any of the above methods, the releasable substrate By transferring the conductive film layer patterned above onto the transparent substrate, the patterned conductive film of the present invention can be formed.

[Preferred use]
The conductive film of the present invention has both high conductivity and transparency, and various optoelectronic devices such as liquid crystal display elements, organic light emitting elements, inorganic electroluminescent elements, electronic paper, organic solar cells, inorganic solar cells, electromagnetic wave shields, touch panels. It can be suitably used in such fields. Among these, it can use especially preferably as an electrically conductive film of the organic electroluminescent element by which the smoothness of the surface of a transparent electrode is calculated | required severely.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

Synthesis example 1
(Salt synthesis of oxidized form of compound represented by general formula (I))
In a 100 ml eggplant flask, tetrathiafulvalene (hereinafter abbreviated as TTF) (286 mg, 1.40 mmol, purchased from Tokyo Kasei) and heptafluorobutyric acid (363 μL, 2.80 mmol, purchased from Wako Pure Chemical Industries, Ltd.) In the presence of diacetate (225 mg, 0.70 mmol, purchased from Tokyo Kasei Co., Ltd.), it was dissolved in 15 ml of acetonitrile (purchased from Wako Pure Chemical Industries, Ltd.) solution. After the solution turned brown by stirring for 30 minutes at room temperature, 200 ml of diethyl ether (purchased from Wako Pure Chemical Industries, Ltd.) was added to form a precipitate of TTF radical cation salt having heptabutyl butyrate anion as a counter anion. The precipitate was filtered and then washed with acetonitrile to obtain 434 mg (yield 74%) as a brown precipitate. The physical property data of the compound was subjected to elemental analysis, UV-visible absorption spectrum measurement and mass measurement.

Elemental _{analysis: C 10 H 4 F 7 O} 2 S 4
Calculated Value (%): C, 28.78; H, 0.97; F, 31.86; O, 7.67; S, 30.73
Experimental value (%): C, 29.07; H, 1.18; F, 31.66.
UV / vis / NIR (CH ₃ CN)
λmax (ε) = 265 (1200), 339 (4900), 436 (14600), 578 (4000).
HRMS (EI ⁺ )
Calculated value: 203.9196 as C ₆ H ₄ S ₄ (TTF ⁺ )
Measurement value: 203.9192.
(FAB)
Calculated value: C ₄ F ₇ O ₂ (C ₃ F ₇ COO ⁻ ), 212.9792
Measurement value: 212.9786.
Comparative Example 1
(Production of comparative conductive film 1 (PEDOT / PSS film))
A PEDOT / PSS aqueous solution purchased from Aldrich was dropped on a glass substrate and allowed to stand at room temperature for 16 hours to prepare a comparative conductive film 1 having a dry film thickness of 2 μm.

(Preparation of comparative conductive film 2 (TTF film))
A solution prepared by dissolving TTF (10 mg, 0.049 mmol) and an oxidized salt of TTF obtained in Synthesis Example 1 (28.8 mg, 0.069 mmol) in 10 ml of acetonitrile was dropped onto a glass substrate, and the solution was stirred at room temperature for 16 hours. By allowing to stand, a comparative conductive film 2 having a dry film thickness of 4 μm was produced. As a result of measuring the transparency and conductivity of the comparative conductive film 2 by the method of the comparative conductive film 1, the transmittance was 69% and the conductivity was 1.6 × 10 ⁻² S / cm.

Example 1
(Preparation of conductive films 1-1 to 1-6)
Scheme 1 shows an outline of a method for manufacturing a conductive film including conductive nanowires.

  Using a 100 ml eggplant flask, a solution of 5.3 mM neutral TTF in acetonitrile and an acetonitrile solution containing 14.7 mM of the TTF radical cation salt obtained above according to the quantities in Table 1, polymethyl methacrylate (PMMA, Mw = 700,000-750,000, purchased from Nacalai Tesque) was added to 10 ml of a polymer solution having a monomer concentration of 20 mM. Thereafter, acetonitrile was added to prepare a total volume of 20 ml, and the mixture was stirred at room temperature for 1 hour. The solution was dropped on a glass substrate and allowed to stand at room temperature for 16 hours to prepare the conductive films 1-1 to 1-6 of the present invention having a dry film thickness of 2 μm.

Evaluation The following evaluation was performed about the obtained electrically conductive film 1 and the comparative electrically conductive films 1 and 2. FIG.

<Conductivity measurement>
The conductivity at five different points on the conductive film was calculated by the four-terminal method, and the average value was calculated. Table 2 shows the average conductivity of each of the TTF species in the conductive film with respect to the concentration. The standard deviation of the value is shown in parentheses. The obtained results are shown in Table 2.

<Calculation of transmittance>
The ultraviolet-visible absorption spectrum was measured between 400 nm and 800 nm, and the transmittance was measured. The transmittance obtained by converting the average transmittance between wavelengths per 1 μm was defined as the transmittance. The obtained results are shown in Table 2.

  The conductive film of the present invention was also found to have conductivity, and the value was comparable to that of a conductive film composed only of conductive nanowires composed of a TTF and an oxide salt of TTF. This proved that it is possible to impart conductivity to the material by adding a small amount of the conductive nanowire of the present invention to a general-purpose polymer.

  All of the conductive films of the present invention had a transparency of 90% or more. On the other hand, PEDOT is less than 10%, and it was revealed that the conductive film of the present invention has high transparency.

Example 2
Preparation of conductive films 2-1 to 2-6 The conductive film 2- of the present invention was the same as in Example 1 except that polymethyl methacrylate was replaced with polyvinylpyrrolidone (PVP, Mw = 10,000, purchased from Aldrich). 1-2-6 were produced.

Example 3
Preparation of conductive films 3-1 to 3-6 The conductive film of the present invention was the same as in Example 1 except that polymethyl methacrylate was replaced with polystyrene (Mw = 100,000 to 140,000, purchased from Nacalai Tesque). 3-1 to 3-6 were produced.

  The obtained conductive films 2-1 to 2-6 and the conductive films 3-1 to 3-6 were measured for conductivity and transmittance in the same manner as in Example 1, and the obtained results are shown in Table 3.

  As is apparent from Table 3, the conductive film of the present invention is a conductive film having excellent conductivity and transmittance.

<Change in conductivity of conductive film over time>
The conductive film is allowed to stand at room temperature in the air, and the change in conductivity over time is examined. The result is shown in FIG.

  The conductivity was measured by the four probe method at five different points on the film, and the average points were plotted. In FIG. 2, circles represent data points of samples containing 35 mol% and squares containing 15 mol% TTF. Error represents standard deviation.

In FIG.
a. Change with time of conductivity of the conductive film (PS binder) of Example 3,
b. Change over time of conductivity of the conductive film (PMMA binder) of Example 1,
c. Change over time of conductivity of the conductive film (PVP binder) of Example 2,
d. It is a figure which shows the time change of the electrical conductivity of the electrically conductive film (only electroconductive nanowire) of the comparative example 2.

  In the conductive film composed only of conductive nanowires made of TTF and an oxide salt of TTF, the conductivity was greatly impaired in 24 hours. However, the conductive film of the present invention was greatly prevented from deteriorating. In particular, it was revealed that the 35 mol% TTF-containing conductive film with PMMA binder showed almost no decrease in conductivity for more than one week, and the stability over time was dramatically improved. Moreover, in visual evaluation, the change was not seen at all in the color tone and transmittance | permeability of each electrically conductive film of this invention.

<Surface observation of the film with a scanning electron microscope>
The surface of the conductive film was observed using a scanning electron microscope (JEOL JSM-5600). Measurement was performed at a voltage of 1.5 kV, and the results are shown in FIG.

In FIG.
a. Scanning photomicrograph of conductive film 3-6 (PS conductive film containing 35 mol% TTF),
b. Scanning photomicrograph of conductive film 1-3 (PMMA conductive film containing 35 mol% TTF),
c. Scanning photomicrograph of conductive film 2-3 (PTF conductive film containing 35 mol% TTF),
d. It is a scanning microscope picture of the comparison electrically conductive film 2 (conductive film which consists only of TTF).

  Although the conductive film of the present invention had a high concentration of conductive nanowires of 35 mol%, the result was that nanofibers were uniformly dispersed in any polymer binder. It has been clarified that the homogeneity of the conductive film suppresses dispersion of light and imparts high transparency to the conductive film.

<Observation of film by UV-Vis near-infrared absorption spectrum>
A 35 mol% conductive nanowire-containing conductive film was observed by ultraviolet-visible-near infrared absorption spectrum, and the results are shown in FIG.

In FIG.
a. An ultraviolet-visible near-infrared absorption spectrum of conductive film 3-6 (PS conductive film containing 35 mol% of conductive nanowires) b. An ultraviolet-visible near-infrared absorption spectrum of the conductive film 1-3 (PMMA conductive film containing 35 mol% of conductive nanowires) is shown. C. It is a figure which shows the ultraviolet visible near-infrared absorption spectrum of the electrically conductive film 2-3 (Conductive nanowire 35 mol% containing PVP electrically conductive film).

  In general, it is known that when a mixed valence is formed, a broad absorption appears in the vicinity of 2000 nm, and the absorption was also observed in the conductive film of the present invention. From this, it was clarified that TTF forms a mixed valence state among polymers and becomes a medium for electron transfer.

<Observation of film by powder X-ray diffraction>
After the conductive films 1 to 3 of the present invention were peeled off from the glass substrate, a powdery sample was prepared by crushing. A powder X-ray diffraction spectrum (SHIMADZUX-ray diffractometer-6000) was measured using 10 mg of the obtained sample. Measurement was performed from 2 degrees to 90 degrees at 0.02 degrees / S with CuKα rays. FIG. 5 shows the result.

In FIG.
a. Powder X-ray diffraction spectrum of conductive film 3,
b. Powder X-ray diffraction spectrum of conductive film 1,
c. The powder X-ray diffraction spectrum of the electrically conductive film 2 is shown.

  In any conductive film, a sharp peak was observed at a site where the diffraction angle 2θ derived from the conductive nanowire structure was 6, 14, and 20 degrees. This indicates that the stacking structure between TTF and oxidized salt of TTF is maintained even in the polymer. It became clear that mixed valence conductive nanowires can be grown in a polymer without impairing conductivity by using the method of the present invention together with the results of the above-mentioned ultraviolet-visible-near infrared absorption spectrum.

Example 4
[Production of organic electroluminescence element (organic EL element)]
Using the conductive films 1-3, 2-3, 3-3 and 1-6, 2-6, 3-6 of the present invention prepared in Examples 1 to 3 as the first electrode (anode electrode), the following Organic EL elements OEL-101 to 106 were produced by the procedure.

<Formation of hole transport layer>
A solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water on each conductive film of the present invention. A film was formed by spin coating at 3000 rpm for 30 seconds, and then dried at 200 ° C. for 1 hour to provide a hole transport layer having a thickness of 30 nm.

<Formation of light emitting layer>
On each film on which the hole transport layer was formed, a solution of 20 mg of H-1 as a host material and 2 mg of D-1 as a luminescent dopant in 2 ml of toluene was spinned at 1500 rpm for 30 seconds. A film was formed by a coating method, and heat-dried at 120 ° C. for 1 hour to provide a light-emitting layer having a thickness of 40 nm.

<Formation of electron transport layer and second electrode [cathode electrode]>
Each sample was formed to the light emitting layer attached to the vacuum vapor deposition apparatus, pressure in the vacuum tank was reduced to 4 × 10 -4 ^Pa. Next, as an electron transport layer, E-1 (bis (2-methyl-8-quinolate) -p-phenylphenolate aluminum complex; BAlq) was deposited to 30 nm, lithium fluoride 1 nm as a cathode buffer layer, and aluminum 110 nm as a cathode. Thus, the second electrode (anode electrode) was formed, and organic EL elements OEL-101 to 106 were produced.

<Formation of sealing film>
The formed on the second electrode, a polyethylene terephthalate as a substrate, using a flexible sealing member which is deposited to a thickness 300nm to for Al ₂ O ₃ sealing film. Apply the adhesive around the second electrode except for the end so that the external lead terminals of the first electrode and the second electrode can be formed, paste the flexible sealing member, and then cure the adhesive by heat treatment It was.

(Preparation of comparative conductive film TC-107)
A comparative conductive film was prepared as follows with reference to Synthetic Metals, 1995, 68, 281. Distilled water was added to 0.5 g of polyvinyl alcohol (manufactured by Aldrich, MW = 15,000) to make 10 ml, and the mixture was dissolved by heating at 90 ° C. The solution was purged with argon, tetrafulvalenedicarboxylic acid T-1 25 mg (6.8 × 10 ⁻⁵ mol, Fw 368.6), potassium ferricyanide 7 synthesized using the method of The Journal of Organic Chemistry, 1974, 2456 ^{.3mg (2.2 × 10 -5 mol,} Fw 329.2) was added while maintaining the temperature at 50 ° C., and stirred for 10 minutes. This solution was cast on a glass substrate to prepare a comparative conductive film TC-107 having a thickness of 10 μm.

(Preparation of comparative conductive films TC-108 and TC-109)
Comparative conductive films TC-108 and TC-109 having a thickness of 10 μm were prepared by the same method as TC-107 except that the addition temperatures of tetrafulvalenedicarboxylic acid and potassium ferricyanide were changed to 80 ° C. and 90 ° C.

(Production of comparative organic EL elements OEL-107 to 109)
Using the produced TC-107 to 109, comparative organic EL elements OEL-107 to 109 were produced by the same method as the organic EL elements OEL-101 to 106 of the present invention.

[Organic EL device emission test]
A direct measure voltage was applied to the organic EL element using a source measure unit 2400 type manufactured by KEITHLEY for the organic EL elements OEL-101 to 106 and comparative organic EL elements OEL-107 to 109 of the present invention, and 23 ± 3 ° C., 55 Light was emitted in an environment of ± 3% RH. Further, after placing the organic EL elements OEL-101 to 106 of the present invention and the comparative organic EL elements OEL-107 to 109 in an environment of 80 ° C. and 60% RH for 30 minutes, the above 23 ± 3 ° C. and 55 ± 3% RH are again obtained. After adjusting the humidity for 1 hour or more in the above environment, the device was similarly made to emit light.

Evaluation criteria for emission uniformity ◎: Light emission of EL element is recognized ○: Light emission of EL element is recognized Δ: Non-uniform light emission of EL element is recognized ×: Light emission of EL element is not recognized Is shown in Table 4.

  From Table 4, the comparative organic EL elements OEL-107 to OEL-109 are significantly deteriorated in light emission after heating (forced deterioration) at 80 ° C. and 60% RH for 30 minutes, whereas the organic EL elements OEL-101 to OEL- It became clear that the light emission of 106 was stable even after forced deterioration.

DESCRIPTION OF SYMBOLS 11 Conductive fiber 21 Conductive material 31 Transparent conductive layer 51 Transparent base material

Claims (5)

A conductive film containing a conductive nanowire and a binder, wherein the conductive nanowire is composed of a compound represented by the following general formula (I) and a salt of an oxidant of the compound represented by the general formula (I) A conductive film characterized by being a mixed valence compound.
[Wherein, X _{1 to} X ₄ each represent a chalcogen atom and may be the same or different. R _{1 to} R ₄ each independently represents a hydrogen atom or a substituent, but R ₁ and R ₂ , or R ₃ and R ₄ may be bonded to each other to form a cyclic structure. ] The conductive film according to claim ₁ , wherein X ₁ , X ₂ , X ₃ and X _{4 of the} compound represented by the general formula (I) are sulfur atoms. The conductive film according to claim 1 or 2, wherein the counter anion of the salt of the oxidant of the compound represented by the general formula (I) is an anion represented by the following general formula (II).
Formula (II) R ₅ COO ⁻
[Wherein R ₅ represents a substituent. ]   The organic electroluminescent element characterized by using the electrode comprised from the electrically conductive film of any one of Claims 1-3.   The electrically conductive film of any one of Claims 1-3 contains the solution containing the compound represented by general formula (I), and the salt of the oxidant of the compound represented by general formula (I). A method for producing a conductive film, which is produced by mixing a solution and a solution containing a binder, and then applying and drying the solution on a support.