JP2011228243A - Conductive composition, transparent conductor using the same, touch panel, and solar cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive composition which has conductivity even without being baked, and can improve durability and permeability by containing a specific dispersant; a transparent conductor which can improve writing pressure durability, flexibility and conversion efficiency by using the same; a touch panel which can improve writing pressure durability and flexibility; and an integrated solar cell which can improve conversion efficiency.SOLUTION: The conductive composition includes at least a conductive fiber and the dispersant for dispersing the conductive fiber, which contains a repeating unit represented by the following formula (1).

Description

  The present invention relates to a conductive composition that has conductivity and can improve durability and transmittance without firing, and a transparent conductor, touch panel, and solar cell using the same.

  Conductive materials such as conductive fibers and conductive pastes are widely used for forming electronic circuits, conductive adhesives, conductive paints, and the like. As a method of forming an electronic circuit using a conductive material, for example, a method of printing a conductive material on a plastic film by a screen printing method or the like is known.

  However, the conductive material does not have conductivity only by printing the conductive material on the plastic film. After printing, the conductive material has conductivity only after firing at about 800 ° C. for 3 to 30 hours. As described above, in order to make the conductive material conductive, it is necessary to bake at a high temperature for a long time. Therefore, there is a problem that the conductive material cannot be printed on a plastic film having poor heat resistance. there were.

  In order to solve such a problem, for example, a conductive composition comprising a particulate silver compound and a dispersion medium has been proposed (see Patent Document 1), and rod-shaped nano-sized metal fine particles and spherical particles are proposed. A metal fine particle-containing composition containing metal nanoparticles, a dispersant, and a dispersion medium has been proposed (see Patent Document 2), and by using the conductive composition and the metal fine particle-containing composition, It can be fired at ~ 200 ° C.

However, since the material used for the flexible substrate is inferior in heat resistance to the plastic film, there is a problem that the flexible substrate melts when fired at 180 ° C. to 200 ° C.
In recent years, conductive materials are also widely used in touch panels, which are rapidly growing in demand due to the spread of portable game machines and the like. There was also a problem. Furthermore, as part of energy measures, development of thin film solar cells, which are a clean power generation method that can obtain electricity directly from sunlight, has been studied, but there is also a problem that conversion efficiency is low.

  Thus, the improvement effects such as conductivity, writing pressure durability, flexibility and conversion efficiency are still insufficient, and further improvement is desired at present.

JP 2003-308732 A JP 2006-70300 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention includes an electroconductive composition that can be improved in durability and transmittance by containing a specific dispersant, and can be improved in durability and transmittance, and by using this. Transparent conductor capable of improving writing pressure durability, flexibility and conversion efficiency, touch panel capable of improving writing pressure durability and flexibility, and integrated solar cell capable of improving conversion efficiency The purpose is to provide.

Means for solving the problems are as follows. That is,
<1> A conductive composition comprising at least conductive fibers and a dispersant containing a repeating unit represented by the following general formula (1) for dispersing the conductive fibers.
However, in the general formula (1), ^{R 1} represents a hydrogen atom or a methyl group. J ^{is, -CO -, - COO -,} - CONR 10 -, - OCO-, a methylene group, a phenylene group, or _-C 6 _H 4 CO-. R ¹⁰ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. W represents a single bond or a divalent linking group. P represents a heterocyclic group.
<2> The conductive composition according to <1>, wherein P in the general formula (1) is a substituent represented by the following general formula (2) or a tautomer structure thereof. It is a thing.
However, in General Formula (2), R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ³ represents a hydrogen atom or a substituent represented by the following general formula (3).
However, in General Formula (3), R ²³ represents a substituted or unsubstituted aromatic ring or a heteroatom-containing heterocyclic ring.
<3> The conductivity according to any one of <1> to <2>, wherein the dispersant is a graft copolymer further containing a polymerizable oligomer having an ethylenically unsaturated double bond at a terminal as a copolymer unit. It is a composition.
<4> The conductive composition according to <3>, wherein the polymerizable oligomer is represented by the following general formula (4).
However, in General Formula (4), R ⁴ represents a hydrogen atom or a methyl group. X represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and L represents a single bond or a divalent organic linking group. R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. m represents an integer of 0 to 100, and n represents an integer of 1 to 100.
<5> The conductive composition according to any one of <1> to <4>, further including a water-insoluble binder having an SP value of 18 MPa ^{1/2 to} 30 MPa ^1/2 .
<6> The conductive composition according to any one of <1> to <5>, wherein the conductive fiber is a metal nanowire.
<7> The conductive composition according to <6>, wherein the metal nanowire includes any one of silver and an alloy of silver and a metal other than silver.
<8> The conductive composition according to <7>, wherein the metal other than silver is at least one selected from gold, palladium, iridium, platinum, and osmium.
<9> The conductive composition according to any one of <1> to <8>, wherein an average major axis diameter of the conductive fiber is 1 μm to 40 μm.
<10> Any one of <9> to <9>, wherein the content of the dispersant represented by the general formula (1) is 0.01 part by mass to 30 parts by mass with respect to 100 parts by mass of the conductive fiber. It is an electroconductive composition as described in.
<11> The conductive composition according to any one of <1> to <10>, wherein the dispersant represented by the general formula (1) has a weight average molecular weight of 5,000 to 1,000,000. is there.
<12> A transparent conductor comprising the conductive composition according to any one of <1> to <11>.
<13> The transparent conductor according to <12>, wherein the amount of the conductive fiber in the transparent conductor is 0.005 g / m ^{2 to} 0.5 g / m ² .
<14> A touch panel comprising the conductive composition according to any one of <1> to <11>.
<15> An integrated solar cell comprising the conductive composition according to any one of <1> to <11>.

  According to the present invention, the above-described problems can be solved and the object can be achieved, and by including a specific dispersant, it has conductivity without being fired, and has durability and transmittance. Composition, and a transparent conductor that can improve pen pressure durability, flexibility, and conversion efficiency by using the same, pen pressure durability, and flexibility An integrated solar cell that can improve the conversion efficiency and the touch panel that can be provided can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of a touch panel. FIG. 2 is a schematic explanatory diagram illustrating another example of the touch panel. FIG. 3 is a schematic plan view showing an example of arrangement of transparent conductors in the touch panel shown in FIG. FIG. 4 is a schematic cross-sectional view showing still another example of the touch panel.

(Conductive composition)
The conductive composition contains conductive fibers and a dispersant, and further contains other components as necessary.

<Conductive fiber>
The conductivity of the conductive fiber at 20 ° C. to 100 ° C. is 0.01 (Ω / □) to 1,000 (Ω / □). The conductivity can be measured using, for example, Loresta-GP MCP-T600 (manufactured by Mitsubishi Chemical Corporation) by preparing pellets with conductive fibers.
There is no restriction | limiting in particular as a structure of the said conductive fiber, Although it can select suitably according to the objective, It is preferable that it is either a solid structure or a hollow structure.
Here, the solid structure fiber may be referred to as a wire, and the hollow structure fiber may be referred to as a tube.
Conductive fibers having an average minor axis diameter of 5 nm to 1,000 nm and an average major axis diameter of 1 μm to 100 μm may be referred to as nanowires.
In addition, a conductive fiber having an average minor axis diameter of 1 nm to 1,000 nm and an average major axis diameter of 0.1 μm to 1,000 μm and having a hollow structure may be referred to as a nanotube.
The material of the conductive fiber is not particularly limited as long as it has conductivity, and can be appropriately selected according to the purpose, but is preferably at least one of metal and carbon. Especially, it is preferable that the said conductive fiber is at least any one of a metal nanowire, a metal nanotube, and a carbon nanotube.

<< Metal nanowires >>
-Metal-
The material of the metal nanowire is not particularly limited. For example, at least one metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the long periodic table (IUPAC 1991) is preferable. At least one metal selected from Group 2 to Group 14 is more preferable, and Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, and Group 14 are more preferable. At least one metal selected from the group is more preferable, and it is particularly preferable to include it as a main component.

Examples of the metal include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, and lead. And alloys thereof. Among these, silver and an alloy with silver are preferable in terms of excellent conductivity.
Examples of the metal used in the alloy with silver include gold, platinum, osmium, palladium and iridium. These may be used alone or in combination of two or more.

-Shape-
There is no restriction | limiting in particular as a shape of the said metal nanowire, According to the objective, it can select suitably, For example, it can take arbitrary shapes, such as a column shape, a rectangular parallelepiped shape, and the column shape from which a cross section becomes a polygon. In applications where high transparency is required, a cylindrical shape or a cross-sectional shape with rounded polygonal corners is preferable.
The cross-sectional shape of the metal nanowire can be examined by applying a metal nanowire aqueous dispersion on a substrate and observing the cross-section with a transmission electron microscope (TEM).

-Average minor axis diameter and average major axis diameter-
The average minor axis diameter of the metal nanowire (the average minor axis diameter may be referred to as “average diameter”) is preferably 5 nm to 45 nm, more preferably 10 nm to 40 nm, and particularly preferably 15 nm to 35 nm.
When the average minor axis diameter is less than 5 nm, oxidation resistance deteriorates and durability may deteriorate. When the average minor axis diameter exceeds 45 nm, scattering due to metal nanowires occurs and sufficient transparency is obtained. May not be possible.
The average minor axis diameter (average diameter) of the metal nanowires was determined by observing 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average minor axis diameter of the nanowire was determined. In addition, the short axis diameter in case the short axis of the said metal nanowire is not circular made the longest diameter the short axis diameter.

The average major axis diameter of the metal nanowire (the average major axis diameter may be referred to as “average length”) is preferably 1 μm to 40 μm, more preferably 3 μm to 35 μm, and particularly preferably 5 μm to 30 μm.
If the average major axis diameter is less than 1 μm, it may be difficult to form a dense network, and sufficient conductivity may not be obtained. If it exceeds 40 μm, the metal nanowires are too long during production. Tangles may occur in the manufacturing process.
The average major axis diameter of the metal nanowires was observed using 300 transmission metal microscopes (TEM; JEM-2000FX, JEM-2000FX), and the average of the metal nanowires was determined from the average value. The major axis diameter was determined. In addition, when the said metal nanowire was bent, the circle | round | yen which makes it an arc was considered and the value calculated from the radius and curvature was made into the major axis diameter.

-Manufacturing method-
There is no restriction | limiting in particular as a manufacturing method of the said metal nanowire, Although it may manufacture by what kind of method, a metal ion is reduce | restored, heating in the solvent which melt | dissolved the halogen compound and the dispersion additive as follows. It is preferable to manufacture by.

The solvent is preferably a hydrophilic solvent, and examples thereof include water, alcohols, ethers, and ketones. These may be used alone or in combination of two or more.
Examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, and ethylene glycol.
Examples of the ethers include dioxane and tetrahydrofuran.
Examples of the ketones include acetone.

As heating temperature at the time of the said heating, 250 degrees C or less is preferable, 20 to 200 degreeC is more preferable, 30 to 180 degreeC is further more preferable, and 40 to 170 degreeC is especially preferable.
If the heating temperature is less than 20 ° C., the lower the heating temperature, the lower the nucleation probability, and the metal nanowires become too long, so the metal nanowires are likely to be entangled, and the dispersion stability may deteriorate. When it exceeds 250 ° C., the corner of the cross section of the metal nanowire becomes steep, and the transmittance in the evaluation of the coating film may be lowered.
If necessary, the temperature may be changed during the formation process of the metal nanowires, and the monodispersity can be improved by controlling the nucleation of the metal nanowires, suppressing renucleation, and promoting selective growth. The effect can be improved.

The heating is preferably performed by adding a reducing agent.
The reducing agent is not particularly limited and can be appropriately selected from those usually used. For example, borohydride metal salt, aluminum hydride salt, alkanolamine, aliphatic amine, heterocyclic amine, Aromatic amines, aralkylamines, alcohols, organic acids, reducing sugars, sugar alcohols, sodium sulfite, hydrazine compounds, dextrin, hydroquinone, hydroxylamine, ethylene glycol, glutathione and the like can be mentioned. Among these, reducing sugars, sugar alcohols as derivatives thereof, and ethylene glycol are particularly preferable.
Examples of the borohydride metal salt include sodium borohydride and potassium borohydride.
Examples of the aluminum hydride salt include lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, aluminum beryllium hydride, magnesium aluminum hydride, and calcium aluminum hydride.
Examples of the alkanolamine include diethylaminoethanol, ethanolamine, propanolamine, triethanolamine, dimethylaminopropanol, and the like.
Examples of the aliphatic amine include propylamine, butylamine, dipropyleneamine, ethylenediamine, and triethylenepentamine.
Examples of the heterocyclic amine include piperidine, pyrrolidine, N-methylpyrrolidine, and morpholine.
Examples of the aromatic amine include aniline, N-methylaniline, toluidine, anisidine, and phenetidine.
Examples of the aralkylamine include benzylamine, xylenediamine, and N-methylbenzylamine.
As said alcohol, methanol, ethanol, 2-propanol etc. are mentioned, for example.
Examples of the organic acids include citric acid, malic acid, tartaric acid, citric acid, succinic acid, ascorbic acid, and salts thereof.
Examples of the reducing saccharide include glucose, galactose, mannose, fructose, sucrose, maltose, raffinose, stachyose and the like.
Examples of the sugar alcohols include sorbitol.

  Depending on the reducing agent, it may function as a dispersion additive or a solvent as a function, and can be preferably used in the same manner.

In the production of the metal nanowire, it is preferable to add a dispersion additive and a halogen compound or metal halide fine particles.
The timing of the addition of the dispersion additive and the halogen compound may be before or after the addition of the reducing agent, and may be before or after the addition of metal ions or metal halide fine particles, but is better in monodispersity. In order to obtain metal nanowires, it is preferable to add the halogen compound in two or more stages.

The dispersion additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an amino group-containing compound, a thiol group-containing compound, a sulfide group-containing compound, an amino acid or a derivative thereof, a peptide compound, and a polysaccharide. Synthetic polymers, gels derived from these, and the like. Among these, gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, polyalkyleneamine, partial alkyl ester of polyacrylic acid, polyvinylpyrrolidone, and polyvinylpyrrolidone copolymer are preferable.
For the structure that can be used as the dispersion additive, for example, the description of “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000) can be referred to.
Moreover, the shape of the metal nanowire obtained can also be changed with the kind of dispersion additive to be used.

The halogen compound is not particularly limited as long as it is a compound containing bromine, chlorine, or iodine, and can be appropriately selected according to the purpose. For example, sodium bromide, sodium chloride, sodium iodide, potassium iodide Compounds that can be used in combination with alkali halides such as potassium bromide, potassium chloride, potassium iodide and the following dispersion additives are preferred.
Some halogen compounds may function as a dispersion additive, but can be preferably used in the same manner.

  As an alternative to the halogen compound, silver halide fine particles may be used, or both a halogen compound and silver halide fine particles may be used.

  The dispersion additive and the halogen compound or silver halide fine particles may be used in the same substance. Examples of the compound in which the dispersion additive and the halogen compound are used in combination include HTAB (hexadecyl-trimethylammonium bromide) containing an amino group and a bromide ion, HTAC (hexadecyl-trimethylammonium chloride) containing an amino group and a chloride ion, and the like. Is mentioned.

  The desalting treatment can be performed by techniques such as ultrafiltration, dialysis, gel filtration, decantation, and centrifugation after forming metal nanowires.

<< Metal Nanotubes >>
-Metal-
There is no restriction | limiting in particular as a material of the said metal nanotube, What kind of metal may be sufficient, For example, the material of the above-mentioned metal nanowire etc. can be used.

-Shape-
The shape of the metal nanotube may be a single layer or a multilayer, but a single layer is preferable in terms of excellent conductivity and thermal conductivity.

-Average minor axis diameter, average major axis diameter, thickness-
The thickness of the metal nanotube (difference between the outer diameter and the inner diameter) is preferably 30 nm or less, more preferably 20 nm or less, and particularly preferably 10 nm or less.
The thickness of the metal nanotube is preferably 3 nm to 80 nm.
When the thickness is less than 3 nm, the oxidation resistance is deteriorated and the durability may be deteriorated. When the thickness is more than 80 nm, scattering due to the metal nanotube may occur.
The average major axis diameter of the metal nanotube is preferably 1 μm to 40 μm, more preferably 3 μm to 35 μm, and particularly preferably 5 μm to 30 μm.

-Manufacturing method-
There is no restriction | limiting in particular as the manufacturing method of the said metal nanotube, You may manufacture by what kind of method, For example, well-known methods, such as US application publication 2005/0056118, etc. can be used.

<< Carbon nanotube >>
-Shape-
The carbon nanotube (CNT) is a substance in which a graphite-like carbon atomic surface (graphene sheet) is a single-layer or multilayer coaxial tube. Single-walled carbon nanotubes are called single-walled nanotubes (SWNT), multi-walled carbon nanotubes are called multi-walled nanotubes (MWNT), and in particular, double-walled carbon nanotubes are also called double-walled nanotubes (DWNT). In the conductive fiber of the present invention, the carbon nanotube may be a single layer or a multilayer, but a single layer is preferable in terms of excellent conductivity and thermal conductivity.

-Manufacturing method-
The method for producing the carbon nanotube is not particularly limited and may be produced by any method, for example, catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, thermal CVD method, plasma CVD method, gas phase A known method such as a growth method or a HiPco method in which carbon monoxide is reacted with an iron catalyst at a high temperature and high pressure to grow in a gas phase can be used.
In addition, the carbon nanotubes obtained by these methods have been highly purified to remove residues such as by-products and catalytic metals by methods such as washing, centrifugation, filtration, oxidation, and chromatography. It is preferable at the point which can obtain a carbon nanotube.

<< Aspect ratio >>
The aspect ratio of the conductive fiber is preferably 10 or more. The aspect ratio generally means the ratio of the long side to the short side of the fibrous material (ratio of major axis diameter / minor axis diameter).
There is no restriction | limiting in particular as a measuring method of the said aspect ratio, According to the objective, it can select suitably, For example, the method etc. which measure with an electron microscope etc. are mentioned.
When measuring the aspect ratio of the conductive fiber with an electron microscope, it is only necessary to confirm whether the aspect ratio of the conductive fiber is 10 or more with one field of view of the electron microscope. In addition, the aspect ratio of the entire conductive fiber can be estimated by measuring the major axis diameter and the minor axis diameter of the conductive fiber separately.
In addition, when the said conductive fiber is a tube shape, the outer diameter of this tube is used as a diameter for calculating the said aspect ratio.

The aspect ratio of the conductive fiber is not particularly limited as long as it is 10 or more, and can be appropriately selected according to the purpose, but is preferably 50 to 1,000,000, and preferably 100 to 1,000,000. Is more preferable.
When the aspect ratio is less than 10, network formation by the conductive fibers may not be performed and sufficient conductivity may not be obtained. When the aspect ratio exceeds 1,000,000, the conductive fibers may be formed or in subsequent handling. Since the conductive fibers are entangled and aggregate before film formation, a stable liquid may not be obtained.

<< Ratio of conductive fibers having an aspect ratio of 10 or more >>
The ratio of the conductive fibers having an aspect ratio of 10 or more is preferably 50% or more, more preferably 60% or more, and particularly preferably 75% or more in volume ratio in the total conductive composition. Hereinafter, the ratio of these conductive fibers may be referred to as “the ratio of conductive fibers”.
If the ratio of the conductive fibers is less than 50%, the conductive material contributing to the conductivity may decrease and the conductivity may decrease. At the same time, a voltage concentration may occur because a dense network cannot be formed. , Durability may be reduced. In addition, particles having a shape other than the conductive fiber are not preferable because they do not greatly contribute to conductivity and have absorption. In particular, in the case of metal, transparency may be deteriorated when plasmon absorption such as a spherical shape is strong.

  Here, the ratio of the conductive fibers is, for example, when the conductive fibers are silver nanowires, the silver nanowire aqueous dispersion is filtered to separate the silver nanowires from the other particles. The ratio of the conductive fibers can be determined by measuring the amount of silver remaining on the filter paper and the amount of silver that has passed through the filter paper using an ICP emission analyzer. By observing the conductive fibers remaining on the filter paper with a TEM, observing the average minor axis diameter of 300 conductive fibers and examining their distribution, the average minor axis diameter is 200 nm or less, and the average major axis It is confirmed that the conductive fiber has a diameter of 1 μm or more. The filter paper is a TEM image having an average minor axis diameter of 200 nm or less, and measuring the longest axis of particles other than conductive fibers having an average major axis diameter of 1 μm or more. And it is preferable to use the thing of the diameter below the shortest length of the long axis of an electroconductive fiber.

  Here, the average minor axis diameter and the average major axis diameter of the conductive fiber can be determined by observing a TEM image or an optical microscope image using, for example, a transmission electron microscope (TEM) or an optical microscope, In the present invention, the average minor axis diameter and the average major axis diameter of the conductive fibers are obtained by observing 300 conductive fibers with a transmission electron microscope (TEM) and calculating the average value.

<Dispersant>
The dispersant is used for preventing and dispersing the conductive fibers. There is no restriction | limiting in particular if the said dispersing agent is a high molecular compound containing the repeating unit represented by following General formula (1), According to the objective, it can select suitably.

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group. J represents —CO—, —COO—, —CONR ¹⁰ —, —OCO—, a methylene group, a phenylene group, or —C ₆ H ₄ CO— group, and R ¹⁰ represents a hydrogen atom, an alkyl group, or an aryl group. Or an aralkyl group. Among these, J is preferably —COO—, —CONH—, or a phenylene group.
The alkyl group may be a straight chain having 1 to 8 carbon atoms, a branched chain having 1 to 8 carbon atoms, or a cyclic substituted or unsubstituted group having 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, n -Propyl group, i-propyl group, n-butyl group, n-hexyl group, n-octyl group, 2-hydroxyethyl group and the like can be mentioned.
The aryl group may be substituted or unsubstituted and represents, for example, a phenyl group.
The aralkyl group may be substituted or unsubstituted, and represents, for example, a benzyl group.

In the general formula (1), W represents a single bond or a divalent linking group, preferably a single bond, an alkylene group, or an arylene group, more preferably a single bond or an alkylene group, and particularly preferably a single bond.
Examples of the divalent linking group include a linear, branched or cyclic alkylene group, an aralkylene group, and an arylene group. These may further have a substituent. Moreover, you may have an ether bond in a molecule | numerator.
As said alkylene group, C1-C30 is preferable, for example, C1-C12 is more preferable, and C1-C4 is especially preferable. Specific examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, and decylene.
As said aralkylene group, C7-C30 is preferable, for example, and C7-C13 is more preferable. Specific examples include benzylidene and cinnamylidene.
As said arylene group, C6-C30 is preferable, for example, and C6-C15 is more preferable. Specific examples include phenylene, cumenylene, mesitylene, tolylene, and xylylene.

In the general formula (1), P represents a heterocyclic group, for example, thiophene, furan, xanthene, pyrrole, imidazole, pyrazole, pyridine, tetrazole, triazine, isoindoline, isoindolinone, benzimidazolone, indole, Examples include quinoline, carbazole, acridine, acridone, quinacridone, anthraquinone, phthalimide, quinaldine, quinophthalone, barbitur, thiobarbitur, and a substituent represented by the following general formula (2). Among these, benzimidazolone, indole, quinoline, carbazole, acridine, acridone, anthraquinone, barbitur, thiobarbitur, a residue of phthalimide, and a substituent represented by the following general formula (2) are particularly preferable.

In general formula (2), R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. Among these, a hydrogen atom, a methyl group, an ethyl group, a 2-ethylhexyl group, or a phenyl group is preferable.
R ³ represents a hydrogen atom or a substituent. The substituent represented by R ³ preferably has a structure represented by the following general formula (3).
R ²³ represents a substituted or unsubstituted aromatic ring or a hetero atom-containing (for example, oxygen atom, sulfur atom, nitrogen atom) heterocycle. Among these, as the structure of the aromatic ring and the heterocyclic ring, a 5-membered to 6-membered monocyclic or bicondensed ring is preferable. Among them, benzene ring, pyridine ring, pyrimidine ring, imidazole ring, isoxazole ring, oxazole ring, thiazole ring, pyrazole ring, triazole ring, tetrazole ring, benzimidazole ring, benzthiazole ring, benzoxazole ring, benzisoxazole ring A benzothiazole thiadiazole ring is more preferable.

  In the present invention, the “substituent” may be any group that can be substituted. For example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, Heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, Heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, Aryloxycarbonylamino group, heterocycle Xoxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group, sulfo group Examples include a famoylamino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group, and a diaryloxyphosphinyl group.

Hereinafter, preferred specific examples of the repeating unit represented by the general formula (1) will be given, but the present invention is not limited thereto. The structure listed in this specific example is an example of possible tautomeric structures, and other tautomeric structures can be taken.

Here, tautomerism will be described. Tautomerism is reversible interconversion between isomers, and is a phenomenon in which hydrogen atoms are rearranged mainly by proton rearrangement. In addition, tautomers refer to those in which interconvertible structural isomers can reach an equilibrium state in which both isomers can coexist at a high rate of isomerization. As a common example, it occurs by a rearrangement reaction of a hydrogen atom, that is, a proton accompanied by conversion of a single bond and a double bond. In the case of temperature, pH, liquid phase, solid phase, or solution, the isomerization rate and equilibrium ratio also vary depending on the type of solvent. Even when equilibrium is reached for several hours to several days, it is often referred to as tautomerism.
In the present invention, the chemical structure (part) showing the tautomerism in the polymer compound is referred to as tautomer structure (part), and tautomerization in the repeating unit represented by the general formula (1) is performed. The chemical structure (tautomer structure) obtained by the reaction is as shown in the following formulas (a) to (h).

  The dispersant may be a graft copolymer including a repeating unit represented by the general formula (1) and a polymerizable oligomer having an ethylenically unsaturated double bond at a terminal as a copolymer unit.

The polymerizable oligomer having an ethylenically unsaturated double bond at the terminal is also referred to as a macromonomer because it is a compound having a predetermined molecular weight. This specific polymerizable oligomer is preferably composed of a polymer chain part and a part of a polymerizable functional group having an ethylenically unsaturated double bond at its terminal. The group having such an ethylenically unsaturated double bond is preferably contained only at one end of the polymer chain from the viewpoint of obtaining a desired graft polymer. As the group having an ethylenically unsaturated double bond, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable.
As the number average molecular weight of the macromonomer, the polystyrene equivalent number average molecular weight (Mn) is preferably 1,000 to 10,000, and more preferably 2,000 to 9,000.
The polymer chain part is a homopolymer or copolymer formed from at least one monomer selected from the group consisting of alkyl (meth) acrylate, styrene and derivatives thereof, acrylonitrile, vinyl acetate and butadiene, polyethylene oxide, Polypropylene oxide and polycaprolactone are common.
The polymerizable oligomer is preferably an oligomer represented by the following general formula (5).
However, R < ⁹ > and R < ¹¹ > represents a hydrogen atom or a methyl group each independently, R < ¹⁰ > is a C1-C12 alkylene group (preferably C2-C4 alkylene group, a substituent ( For example, it may have a hydroxyl group) and may be further linked via an ester bond, an ether bond, an amide bond, etc., and Z represents a phenyl group or an alkyl group having 1 to 4 carbon atoms. And -COOR ¹² (wherein R ¹² represents an alkyl group having 1 to 6 carbon atoms, a phenyl group or an arylalkyl group having 7 to 10 carbon atoms), and q is 20 to 200 is there. Z is preferably a phenyl group or —COOR ¹² (wherein R ¹² is an alkyl group having 1 to 12 carbon atoms).
Examples of the polymerizable oligomer (macromonomer) include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and poly-i-butyl (meth) acrylate, and (meth) acryloyl at one molecular end of polystyrene. Examples thereof include a polymer having a group bonded thereto.
Examples of the polymerizable oligomer available on the market include one-end methacryloylated polystyrene oligomer (Mn = 6,000, trade name: AS-6, manufactured by Toagosei Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer ( Mn = 6,000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-terminal methacryloylated poly-n-butyl methacrylate oligomer (Mn = 6,000, trade name: AB-6, Toa Gosei) Chemical Industry Co., Ltd.).

The polymerizable oligomer is preferably not only a polymerizable oligomer represented by the general formula (5) but also a polymerizable oligomer represented by the following general formula (6).

In the general formula (6), R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents an alkylene group having 1 to 8 carbon atoms. Q represents ^{-OR 15} or -OCOR ^16. Here, R ¹⁵ and R ¹⁶ represent a hydrogen atom, an alkyl group, or an aryl group. n represents 2 to 200.
In the general formula (6), R ¹³ represents a hydrogen atom or a methyl group. R ¹⁴ represents an alkylene group having 1 to 8 carbon atoms. Among them, an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is more preferable. Q represents ^{-OR 15} or -OCOR ^16. Here, R ¹⁵ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms. R ¹⁶ represents an alkyl group having 1 to 18 carbon atoms. Moreover, n represents 2-200, 5-100 are preferable and 10-100 are especially preferable.

  Examples of the polymerizable oligomer represented by the general formula (6) include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, and polytetramethylene glycol monomethacrylate. Etc.

As a commercial item of the polymerizable monomer represented by the general formula (6), for example, methoxypolyethylene glycol methacrylate (trade names: NK ester M-40G, M-90G, M-230G (above, Shin-Nakamura Chemical Co., Ltd.) Product name: Blemmer PME-100, PME-200, PME-400, PME-1000, PME-2000, PME-4000 (above, manufactured by NOF Corporation)), polyethylene glycol monomethacrylate (product) Name: Blemmer PE-90, PE-200, PE-350, manufactured by NOF Corporation, polypropylene glycol monomethacrylate (trade name: BREMMER PP-500, PP-800, PP-1000, manufactured by NOF Corporation) ), Polyethylene glycol polypropylene glycol monomethacrylate (trade name: blemma) 70PEP-350B (manufactured by NOF Corporation), polyethylene glycol polytetramethylene glycol monomethacrylate (trade name: BLEMMER 55PET-800, manufactured by NOF Corporation), polypropylene glycol polytetramethylene glycol monomethacrylate (trade name: BLEMMER) NHK-5050, manufactured by NOF Corporation).
In addition to the polymerizable oligomers represented by the general formulas (5) and (6), polycaprolactone monomers are also preferable. Examples of commercially available products include polycaprolactone monomethacrylate (trade names: Plexel FM2D, FM3, FM5, FA1DDM, FA2D, Daicel). Chemical Industry Co., Ltd.).

There is no restriction | limiting in particular as said polymerizable oligomer, Although it can change suitably according to the intended purpose, For example, the compound represented by following General formula (4) is preferable.

In General Formula (4), R ⁴ represents a hydrogen atom or a methyl group, and a methyl group is preferable.
X represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and —C (═O) O— or —CONH— is preferable.
m represents an integer of 0 to 100, and n represents an integer of 1 to 100.

In the general formula (4), L represents a single bond or a divalent organic linking group. The divalent organic linking group is preferably a substituted or unsubstituted alkylene group or a divalent organic linking group comprising the alkylene group and a hetero atom or a partial structure containing a hetero atom.
As said alkylene group, a C1-C12 alkylene group is preferable, for example, a C1-C8 alkylene group is more preferable, and a C1-C4 alkylene group is especially preferable. Specific examples include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group. When the alkylene group has a substituent, examples of the substituent include a hydroxy group.
As said hetero atom, an oxygen atom, a nitrogen atom, a sulfur atom etc. are mentioned, for example, Among these, an oxygen atom and a nitrogen atom are preferable.
Examples of the divalent organic linking group include an ethylene group.

In General Formula (4), R ⁵ represents a hydrogen atom or a methyl group, and a methyl group is preferable.
In General Formula (4), R ⁶ represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. Examples of the linear alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group.
Examples of the branched alkyl group having 1 to 20 carbon atoms include isopropyl group, isobutyl group, t-butyl group, neopentyl group and the like.

Hereinafter, preferred specific examples of the polymerizable oligomer represented by the general formula (4) will be given, but the present invention is not limited thereto.

The dispersant made of the graft copolymer is not particularly limited, but for example, the following compounds are preferable. Here, l, m, and n represent the mass composition ratio of the polymer, and can be arbitrarily selected within a range where l + m + n = 1.
The l is preferably 0.4 to 0.95, more preferably 0.5 to 0.9, and particularly preferably 0.6 to 0.85.
As said m, 0.01-0.3 are preferable, 0.03-0.25 are more preferable, 0.06-0.2 are especially preferable.
As said n, 0.01-0.3 are preferable, 0.03-0.25 are more preferable, 0.06-0.2 are especially preferable.
(P-11) Monomer giving the above exemplary compound M-4 / AA-6 (manufactured by Toagosei Chemical Industry Co., Ltd., terminal methacryloylated polymethyl methacrylate oligomer) / methacrylic acid copolymer
(P-12) Monomer / AB-6 (Terminal methacryloylated poly-n-butyl methacrylate oligomer) / Methacrylic acid copolymer to give the above exemplified compound M-4
(P-13) Monomer giving the above exemplary compound M-4 / AS-6 (manufactured by Toagosei Chemical Co., Ltd., terminal methacryloylated polystyrene oligomer) / methacrylic acid copolymer
(P-14) Monomer / Blemmer PME-1000 (manufactured by NOF Corporation, methoxypolyethylene glycol monomethacrylate) / methacrylic acid copolymer giving the above exemplified compound M-4
(P-15) Monomer / Blemmer PP-1000 (manufactured by NOF Corporation, polypropylene glycol monomethacrylate) / methacrylic acid copolymer giving the above exemplified compound M-4
(P-16) Monomer / Blemmer 70PEP-350B (manufactured by NOF Corporation, polyethylene glycol polypropylene glycol monomethacrylate) / methacrylic acid copolymer which gives the exemplified compound M-4
(P-17) Monomer / Placcel FM5 (produced by Daicel Chemical Industries, Ltd., polycaprolactone monomethacrylate) / methacrylic acid copolymer to give the exemplified compound M-4

The weight average molecular weight of the dispersant is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 10,000 to 300,000.
When the weight average molecular weight is less than 5,000, the conductive fibers may be aggregated in the dispersion. Sexuality may worsen. The weight average molecular weight can be measured using, for example, gel permeation chromatography (GPC).

As content of the said dispersing agent, 0.01 mass part-50 mass parts are preferable with respect to 100 mass parts of conductive fibers, 0.1 mass part-50 mass parts are more preferable, 0.5 mass part-40 mass parts Part by mass is more preferable, and 1 part by mass to 30 parts by mass is particularly preferable.
When the content is less than 0.01 parts by mass, the conductive fibers may aggregate in the dispersion, and when it exceeds 50 parts by mass, a stable liquid film cannot be formed in the coating process. Application unevenness may occur.

<Other ingredients>
Examples of the other components include various additives such as water-insoluble polymers, surfactants, antioxidants, sulfidation inhibitors, metal corrosion inhibitors, viscosity modifiers, and preservatives. These components may be appropriately contained as necessary.

-Water-insoluble polymer-
The water-insoluble polymer has a function as a binder, and is a polymer that does not substantially dissolve in water near neutrality. The water-insoluble polymer specifically means a polymer having an SP value (calculated by the Okitsu method) of 18 MPa ^{1/2 to} 30 MPa ^1/2 .

As the SP value ^is preferably 18MPa ^1/2 ~30MPa ^1/2, more preferably ^{19MPa 1/2 ~28MPa 1/2, 19.5MPa 1/2 ~27MPa} 1/2 is particularly preferred.
The SP value is less than ^{18 MPa 1/2,} there are cases where to wash the adhered organic stains difficult, exceeds ^{30 MPa 1/2,} the higher the affinity for water, the coating film The conversion efficiency may decrease when a solar cell is manufactured because the absorption in the infrared region is increased due to the increase in water content.

Here, the SP value is calculated by the Okitsu method (Toshinao Okitsu, “Journal of the Adhesion Society of Japan” 29 (3) (1993)). Specifically, the SP value is calculated by the following formula. Note that ΔF is a value described in the literature.

SP value (δ) = ΣΔF (Molar Attraction Constants) / V (molar volume)

When using a plurality of water-insoluble polymers, the SP value (σ) and the hydrogen bond term (σh) of the SP value are calculated by the following equations.

(However, σn is the SP bond value of the water-insoluble polymer and water or the hydrogen bond term of the SP value, Mn is the molar fraction of the water-insoluble polymer and water in the mixed solution, Vn is the molar volume of the solvent, n represents an integer of 2 or more representing the type of solvent.)

The water-insoluble polymer is not particularly limited as long as the SP value is 18 MPa ^{1/2 to} 30 MPa ^1/2 , but is not ethylenic in terms of adhesion of the coating film to the substrate and durability against sliding. Polymers having saturated groups are preferred. Among these, it is preferable that the side chain connected to the main chain contains at least one ethylenically unsaturated bond. A plurality of the ethylenically unsaturated bonds may be contained in the side chain. The ethylenically unsaturated bond may be included in the side chain of the water-insoluble polymer together with the branched and / or alicyclic structure and / or the acidic group.

The ethylenically unsaturated bond is bonded to the main chain of the water-insoluble polymer via at least one ester group (—COO—), and the water-insoluble polymer is composed of only the ethylenically unsaturated bond and the ester group. The side chain may be constituted. Further, it may have either a divalent organic linking group between the main chain of the water-insoluble polymer and the ester group, or between the ester group and the ethylenically unsaturated bond. The bond may constitute a side chain of the water-insoluble polymer as “group having an ethylenically unsaturated bond”.
Examples of the divalent organic linking group include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, and (meth) acrylamides. Among these, (meth) acrylates, vinyl esters, and (meth) acrylamides are preferable, and (meth) acrylates are more preferable.

The ethylenically unsaturated bond is preferably arranged by introducing a (meth) acryloyl group.
The method for introducing a (meth) acryloyl group into the side chain of the water-insoluble polymer can be appropriately selected from known methods. For example, a repeating unit having an acidic group has an epoxy group (meth). Examples thereof include a method of adding an acrylate, a method of adding a (meth) acrylate having an isocyanate group to a repeating unit having a hydroxyl group, and a method of adding a (meth) acrylate having a hydroxy group to a repeating unit having an isocyanate group.
Among these, the method of adding (meth) acrylate having an epoxy group to a repeating unit having an acidic group is most preferable because it is the easiest to produce and is low in cost.

  The (meth) acrylate having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these. For example, in the compound represented by the following structural formula (1) and the following structural formula (2) The compounds represented are preferred.

However, in the structural formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group. As a hydrocarbon group, a C1-C10 hydrocarbon group is preferable, a C1-C5 hydrocarbon group is more preferable, and a C1-C3 hydrocarbon group is further more preferable. As the hydrocarbon group, an alkyl group is preferable, and a methyl group is more preferable. L ¹ represents a divalent organic group. As the divalent organic group, a divalent hydrocarbon group is preferable, and a divalent hydrocarbon group having 1 to 4 carbon atoms is more preferable. As a specific example of the divalent hydrocarbon group, an alkylene group is preferable, and a methylene group is more preferable.

In the Structural formula (2), R ² represents a hydrogen atom or a hydrocarbon group. As said hydrocarbon group, a C1-C10 hydrocarbon group is preferable, a C1-C5 hydrocarbon group is more preferable, and a C1-C3 hydrocarbon group is more preferable. As a specific example of the hydrocarbon group, an alkyl group is preferable, and a methyl group is more preferable. L ² represents a divalent organic group. As the divalent organic group, a divalent hydrocarbon group is preferable, and a divalent hydrocarbon group having 1 to 4 carbon atoms is more preferable. As a specific example of the divalent hydrocarbon group, an alkylene group is preferable, and a methylene group is more preferable. W represents a 4- to 7-membered aliphatic hydrocarbon group.

Among the compounds represented by the structural formulas (1) and (2), when combined with a photo-curing resin and used as a negative type or positive type resist, the structure is good in terms of good developability and film strength. The compound represented by Formula (1) is preferable. In the structural formulas (1) and (2), L ¹ and L ² are each independently more preferably an alkylene group having 1 to 4 carbon atoms.

  Although there is no restriction | limiting in particular as a compound represented by the said Structural formula (1) and Structural formula (2), For example, the following compounds (1)-(10) are preferable.

As the content ratio of the water-insoluble polymer, the mass ratio (A / B) of the conductive fiber content (A) and the water-insoluble polymer content (B) is preferably 0.1 to 5. 0.25 to 3.5 is more preferable, and 0.5 to 2.5 is particularly preferable.
If the ratio is less than 0.1, the in-plane distribution of the resistance value may be non-uniform, and if it exceeds 0.5, the temporal stability of the conductive fiber dispersion may decrease.

(Transparent conductor)
The transparent conductor of the present invention comprises the conductive composition. The conductive composition is preferably formed as a transparent conductive layer on a support. Here, the conductor refers to, for example, a film (interlayer conductive film) provided to conduct between elements arranged in layers, a conductive film that ensures in-plane conduction, or the like.

<Support>
The support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a transparent glass substrate, a synthetic resin sheet, a film, a metal substrate, other ceramic plates, and a semiconductor substrate having a photoelectric conversion element. Can be mentioned. If necessary, these supports can be subjected to pretreatment such as chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction, and vacuum deposition.
Examples of the transparent glass substrate include white plate glass, blue plate glass, and silica-coated blue plate glass.
Examples of the synthetic resin sheet and film include PET, polycarbonate, polyethersulfone, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, and polyimide.
Examples of the metal substrate include an aluminum plate, a copper plate, a nickel plate, and a stainless plate.

The total visible light transmittance of the support is preferably 70% or more, more preferably 85% or more, and particularly preferably 90% or more.
If the total visible light transmittance is less than 70%, the transmittance may be low and may cause a problem in practical use.
In the present invention, a support that is colored to the extent that the object of the present invention is not hindered can also be used.

The average thickness of the support is preferably 1 μm to 5,000 μm, more preferably 3 μm to 4,000 μm, and particularly preferably 5 μm to 3,000 μm.
If the average thickness is less than 1 μm, the yield may decrease due to the difficulty in handling in the coating process, and if it exceeds 5,000 μm, the thickness and mass of the support in portable applications may be reduced. May be a problem.
The average thickness can be calculated by observing a cross section with an optical microscope or performing multipoint measurement with a micrometer and obtaining an average value.

<Formation method>
-Formation of transparent conductor-
As a method for forming the transparent conductor, a method of applying the conductive composition of the present invention on a support by a known method such as spin coating, roll coating, slit coating, etc. For example, a method of transferring to the top.

As a form of the transparent conductor, a transparent conductive layer may be formed on one side of the support by applying the conductive composition to one side of the support.
Further, for example, a structure in which two or more transparent conductive layers are laminated on the support via a dielectric layer may be used.
Furthermore, you may form the said transparent conductive layer on both surfaces of the said support body by apply | coating the said electroconductive composition on both surfaces of the said support body.

The amount of conductive fibers in the transparent ^{conductor, 0.005g / m 2 ~0.5g / m} 2 are ^{preferred, 0.01g / m 2 ~0.45g / m} 2 , more preferably 0.015 g / m ^{2 to} 0.4 g / m ² is particularly preferable.
When the amount is less than 0.005 g / m ² , there may be a portion where the resistance is locally increased, and the in-plane resistance distribution may be deteriorated. When the amount exceeds 0.5 g / m ² , Haze may deteriorate due to aggregation of conductive fibers during drying after application.

The average thickness of the transparent conductive layer is preferably 20 nm to 5,000 nm, more preferably 25 nm to 4,000 nm, and particularly preferably 30 nm to 3,500 nm.
When the average thickness is less than 20 nm, it becomes a region that is not different from the short axis diameter of the conductive fiber, and the film strength may be lowered. May get worse.

The transparent conductive layer can be patterned as necessary.
Examples of the patterning method include a patterning method using a photocurable resin, a thermosetting resin, a negative type or a positive type resist, an inkjet method, a screen printing, a printing method by gravure printing or offset printing, a laser scribing method, In addition, after forming a hydrophilic / hydrophobic pattern or a silver-silver pattern using microcontact printing or the like, a method of fixing by applying a silver nanowire dispersion liquid or immersing the support in a silver nanowire dispersion liquid may be used.

Moreover, as said transparent conductor, according to the intended purpose, you may laminate | stack a functional layer other than a transparent conductive layer.
Examples of the functional layer include an undercoat layer, an adhesion layer, a cushion layer, an overcoat protective layer, a protective film layer, an antifouling layer, a water repellent layer, an oil repellent layer, a hard coat layer, an adhesive layer, and a barrier layer. . These may be a single layer or a plurality of layers.
Further, as the transparent conductor, for example, an optical function can be imparted by laminating an antiglare layer, an antireflection layer, a low reflection layer, a λ / 4 layer, a polarizing layer, a retardation layer, and the like. . These may be a single layer or a plurality of layers.

(Touch panel)
The touch panel of the present invention has a transparent conductor comprising the conductive composition of the present invention.
The touch panel is not particularly limited as long as it has the transparent conductor, and can be appropriately selected according to the purpose. For example, a surface capacitive touch panel, a projected capacitive touch panel, a resistive film type Examples include touch panels.

An example of the surface capacitive touch panel will be described with reference to FIG. In FIG. 1, the touch panel 10 is provided with a transparent conductor 12 so as to uniformly cover the surface of the transparent substrate 11, and an external detection circuit (not shown) is formed on the transparent conductor 12 at the end of the transparent substrate 11. The electrode terminal 18 for electrical connection is formed.
In the figure, reference numeral 13 denotes a transparent conductor serving as a shield electrode, reference numerals 14 and 17 denote protective films, reference numeral 15 denotes an intermediate protective film, and reference numeral 16 denotes an antiglare film.
When an arbitrary point on the transparent conductor 12 is touched with a finger, the transparent conductor 12 is grounded through the human body at the touched point, and changes to a resistance value between each electrode terminal 18 and the ground line. Occurs. The change of the resistance value is detected by the external detection circuit, and the coordinates of the touched point are specified.

Another example of the surface capacitive touch panel will be described with reference to FIG. In FIG. 2, the touch panel 20 includes a transparent conductor 22 and a transparent conductor 23 disposed so as to cover the surface of the transparent substrate 21, and an insulating layer 24 that insulates the transparent conductor 22 and the transparent conductor 23. The insulating cover layer 25 that generates capacitance between the contact object such as a finger and the transparent conductor 22 or the transparent conductor 23 detects the position of the contact object such as the finger. Depending on the configuration, the transparent conductors 22 and 23 may be configured integrally, and the insulating layer 24 or the insulating cover layer 25 may be configured as an air layer.
When the insulating cover layer 25 is touched with a finger or the like, the capacitance value between the finger and the transparent conductor 22 or the transparent conductor 23 changes. This change in capacitance value is detected by the external detection circuit, and the coordinates of the touched point are specified.
3 schematically illustrates the touch panel 20 as a projection capacitive touch panel through an arrangement in which the transparent conductor 22 and the transparent conductor 23 are viewed from the plane.
The touch panel 20 is provided with a plurality of transparent conductors 22 capable of detecting positions in the X-axis direction and a plurality of transparent conductors 23 in the Y-axis direction so as to be connectable to external terminals. The transparent conductor 22 and the transparent conductor 23 are in contact with a plurality of contact objects such as fingertips, and contact information can be input at multiple points.
When an arbitrary point on the touch panel 20 is touched with a finger, the coordinates in the X-axis direction and the Y-axis direction are specified with high positional accuracy.
In addition, as other structures, such as a transparent substrate and a protective layer, the structure of the said surface type capacitive touch panel can be selected suitably, and can be applied. Moreover, although the example of the pattern of the transparent conductor by the some transparent conductor 22 and the some transparent conductor 23 was shown in the touch panel 20, the shape, arrangement | positioning, etc. are not restricted to these.

An example of the resistive touch panel will be described with reference to FIG. In FIG. 4, the touch panel 30 can come into contact with the transparent conductor 32 via the substrate 31 on which the transparent conductor 32 is disposed, the spacers 36 disposed on the transparent conductor 32, and the air layer 34. A transparent conductor 33 and a transparent film 35 disposed on the transparent conductor 33 are supported.
When the touch panel 30 is touched from the transparent film 35 side, the transparent film 35 is pressed, the pressed transparent conductor 32 and the transparent conductor 33 come into contact with each other, and a potential change at this position is not illustrated. By detecting with a circuit, the coordinates of the touched point are specified.

(Integrated solar cell)
The integrated solar cell of the present invention has the conductive composition. There is no restriction | limiting in particular as said integrated solar cell (henceforth a solar cell device), What is generally used as a solar cell device can be used. For example, a single crystal silicon solar cell device, a polycrystalline silicon solar cell device, an amorphous silicon solar cell device composed of a single junction type or a tandem structure type, gallium arsenide (GaAs), indium phosphorus (InP), etc. III-V compound semiconductor solar cell devices, II-VI compound semiconductor solar cell devices such as cadmium tellurium (CdTe), copper / indium / selenium system (so-called CIS system), copper / indium / gallium / selenium system ( So-called CIGS-based), copper / indium / gallium / selenium / sulfur-based (so-called CIGS-based) I-III-VI group compound semiconductor solar cell devices, dye-sensitized solar cell devices, organic solar cell devices, etc. Can be mentioned. Among these, in the present invention, the solar cell device is an amorphous silicon solar cell device constituted by a tandem structure type or the like, a copper / indium / selenium system (so-called CIS system), copper / indium / gallium / A selenium-based (so-called CIGS-based), copper / indium / gallium / selenium / sulfur-based (so-called CIGS-based) I-III-VI group compound semiconductor solar cell device is preferable.

  In the case of an amorphous silicon solar cell device composed of a tandem structure type or the like, amorphous silicon, a microcrystalline silicon thin film layer, a thin film containing germanium in these, and further, a tandem structure of two or more layers is a photoelectric conversion layer. Used as For film formation, plasma CVD or the like is used.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Dispersant Preparation Example 1)
—Synthesis of Monomer to give Compound M-4—
45.28 parts by mass of 2-thiobarbituric acid and 13.82 parts by mass of sodium hydroxide were dissolved in 200 parts by mass of dimethyl sulfoxide and heated to 25 ° C. To this was added dropwise 57.53 parts by mass of chloromethylstyrene, and the mixture was further stirred with heating at 55 ° C. for 5 hours. After heating and stirring, 150 parts by mass of methanol and 150 parts by mass of distilled water were added to the reaction solution, and the mixture was stirred for 1 hour. Subsequently, this solution was poured into 2,000 parts by mass of distilled water while stirring, By filtering and washing, 80.1 parts by mass of a monomer giving exemplary compound M-4 was obtained.

-Synthesis of polymerizable oligomer N-1-
500 parts by mass of JEFFAMINE M-2005 (manufactured by Huntsman) and 0.061 parts by mass of hydroquinone monomethyl ether were dissolved in 500 parts by mass of 1-methyl-2-pyrrolidone and cooled to 10 ° C. To this, 38.01 parts by mass of Karenz MOI (manufactured by Showa Denko KK) and 38.01 parts by mass of 1-methyl-2-pyrrolidone were added dropwise. After completion of the dropwise addition, the mixture was stirred at 25 ° C. for 1 hour to obtain 1,076 parts by mass of a 50% by mass polymerizable oligomer N-1 1-methyl-2-pyrrolidone solution.

-Synthesis of Dispersant (1)-
The following monomer solution was introduced into a nitrogen-substituted three-necked flask and stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor). did. Then, the following initiator solution was added to said liquid, and it heat-stirred at 80 degreeC for 2 hours. The following initiator solution was further added after heating and stirring, and the operation of heating and stirring at 80 ° C. for 2 hours was repeated twice in total. After stirring for the last 2 hours, 7.33 parts by mass of 1-methyl-2-pyrrolidone was added to give a graft polymer represented by the following structural formula (dispersant (1): copolymer P-1) A 25 mass% 1-methyl-2-pyrrolidone solution was obtained.
--- Monomer solution--
-2.0 parts by mass of monomer that gives the compound M-4-Polymerizable oligomer N-1 (50% by mass 1-methyl-2-pyrrolidone solution)
32.0 parts by mass-2.0 parts by mass of methacrylic acid-0.210 parts by mass of n-dodecyl mercaptan-30.67 parts by mass of 1-methyl-2-pyrrolidone

--Initiator solution--
2.2'-azobis (isobutyric acid) dimethyl (V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
0.159 parts by mass / 3.0 parts by mass of 1-methyl-2-pyrrolidone

(Dispersant Preparation Example 2)
—Synthesis of Monomer to give Compound M-11—
16.73 parts by mass of 2-mercaptobenzothiazole, 4.40 parts by mass of sodium hydroxide, and 0.018 parts by mass of 4-methoxyphenol were dissolved in 100 parts by mass of dimethyl sulfoxide and stirred at room temperature. To this, 15.26 parts by mass of chloromethylstyrene was dropped over 20 minutes, and the mixture was further heated and stirred at 55 ° C. for 3.5 hours. After completion of the reaction, 200 parts by mass of distilled water, 1 part by mass of concentrated hydrochloric acid and 200 parts by mass of ethyl acetate were added and extracted into an ethyl acetate layer, and the solvent was distilled off to obtain 22.67% of a monomer that gave compound M-11. A mass part was obtained.
-Synthesis of Dispersant (2)-
The following monomer solution was introduced into a nitrogen-substituted three-necked flask and stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor). did. Then, the following initiator solution was added to said liquid, and it heat-stirred at 80 degreeC for 2 hours. The following initiator solution was further added after heating and stirring, and the operation of heating and stirring at 80 ° C. for 2 hours was repeated twice in total. After stirring for the last 2 hours, 7.33 parts by mass of 1-methyl-2-pyrrolidone was added to give a graft polymer represented by the following structural formula (dispersant (2): the copolymer P-6). A 25 mass% 1-methyl-2-pyrrolidone solution was obtained.
--- Monomer solution--
-2.0 parts by weight of monomer that gives the compound M-11-Polymerizable oligomer N-1 (50% by weight 1-methyl-2-pyrrolidone solution)
32.0 parts by mass, 2.0 parts by mass of methacrylic acid, 0.114 parts by mass of n-dodecyl mercaptan, 30.67 parts by mass of 1-methyl-2-pyrrolidone

--Initiator solution--
2.2'-azobis (isobutyric acid) dimethyl (V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
0.087 parts by mass-1-methyl-2-pyrrolidone 3.0 parts by mass

(Dispersant Preparation Example 3)
—Synthesis of Monomer to give Compound M-2—
20.00 parts by mass of 2-aminobenzimidazole and 0.0065 parts by mass of 4-nitrophenol were dissolved in 225 parts by mass of 1-methyl-2-pyrrolidone and stirred at room temperature. 34.96 mass parts of 2-methacryloyloxyethyl isocyanate was dripped at this over 20 minutes. The mixture was stirred at room temperature for 30 minutes, and further heated and stirred at 70 ° C. for 1 hour. After heating and stirring, the solution was allowed to cool to 40 ° C., poured into 1,000 parts by mass of methanol with stirring, and stirred for 1 hour. The obtained precipitate was separated by filtration and washed to obtain 55.21 parts by mass of a monomer that gave the compound M-2.
-Synthesis of Dispersant (3)-
The following monomer solution was introduced into a nitrogen-substituted three-necked flask and stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor). did. Then, the following initiator solution was added to said liquid, and it heat-stirred at 80 degreeC for 2 hours. The following initiator solution was further added after heating and stirring, and the operation of heating and stirring at 80 ° C. for 2 hours was repeated twice in total. After stirring for the last 2 hours, 7.33 parts by mass of 1-methyl-2-pyrrolidone was added to give a graft polymer represented by the following structural formula (dispersant (3): copolymer P-9) A 25 mass% 1-methyl-2-pyrrolidone solution was obtained.
--- Monomer solution--
-2.0 parts by weight of monomer that gives the compound M-2-Polymerizable oligomer N-1 (50% by weight 1-methyl-2-pyrrolidone solution)
32.0 parts by mass-2.0 parts by mass of methacrylic acid-0.205 parts by mass of n-dodecyl mercaptan-30.67 parts by mass of 1-methyl-2-pyrrolidone

--Initiator solution--
2.2'-azobis (isobutyric acid) dimethyl (V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
0.155 parts by mass 1-methyl-2-pyrrolidone 2 parts by mass

(Dispersant Preparation Example 4)
-Synthesis of Dispersant (4)-
The following monomer solution was introduced into a nitrogen-substituted three-necked flask and stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor). did. Then, the following initiator solution was added to said liquid, and it heat-stirred at 80 degreeC for 2 hours. The following initiator solution was further added after heating and stirring, and the operation of heating and stirring at 80 ° C. for 2 hours was repeated twice in total. After stirring for the last 2 hours, 7.33 parts by mass of 1-methyl-2-pyrrolidone was added to obtain 25% by mass of 1-methyl-grafted polymer (dispersant (4): copolymer P-11). A 2-pyrrolidone solution was obtained.
--- Monomer solution--
-Monomer giving said exemplary compound M-4 2.0 mass parts-Polymerizable oligomer, AA-6 (manufactured by Toagosei Co., Ltd.) 16.0 mass parts-Methacrylic acid 2.0 mass parts-n- Dodecyl mercaptan 0.082 mass parts 1-methyl-2-pyrrolidone 46.67 mass parts

--Initiator solution--
2.2'-azobis (isobutyric acid) dimethyl (V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
0.062 parts by mass-1-methyl-2-pyrrolidone 3.0 parts by mass

(Dispersant Preparation Example 5)
-Synthesis of Dispersant (5)-
The following monomer solution was introduced into a nitrogen-substituted three-necked flask and stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor). did. Then, the following initiator solution was added to said liquid, and it heat-stirred at 80 degreeC for 2 hours. The following initiator solution was further added after heating and stirring, and the operation of heating and stirring at 80 ° C. for 2 hours was repeated twice in total. After stirring for the last 2 hours, 7.33 parts by mass of 1-methyl-2-pyrrolidone was added to give a graft polymer represented by the following structural formula (dispersant (5): copolymer P-13). A 25 mass% 1-methyl-2-pyrrolidone solution was obtained.
--- Monomer solution--
-Monomer giving the above exemplified compound M-4 2.0 parts by weight-Polymerizable oligomer, AS-6 (16.0 parts by weight, manufactured by Toagosei Chemical Co., Ltd.-2.0 parts by weight methacrylic acid-n-dodecyl Mercaptan 0.082 parts by mass 1-methyl-2-pyrrolidone 46.67 parts by mass

--Initiator solution--
2.2'-azobis (isobutyric acid) dimethyl (V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
0.062 parts by mass 1-methyl-2-pyrrolidone 2 parts by mass

(Preparation example 1 of water-insoluble polymer)
-Preparation of water-insoluble polymer (1)-
8.57 parts by mass of 1-methoxy-2-propanol (MMPGAC, manufactured by Daicel Chemical Industries, Ltd.) was added in advance to the reaction vessel, the temperature was raised to 90 ° C., and cyclohexyl methacrylate, methyl methacrylate, methacrylic acid (additional mass) as monomers. Cyclohexyl methacrylate, methyl methacrylate, methacrylic acid, and glycidyl methacrylate described later were prepared so that the ratio was 45.5 mol%: 2 mol%: 19 mol%: 33.5 mol% in this order.), An azo polymerization initiator (sum) A mixed solution consisting of 1 part by mass of V-601) and 8.57 parts by mass of 1-methoxy-2-propanol was added dropwise to a 90 ° C. reaction vessel over 2 hours in a nitrogen gas atmosphere. Reaction was performed for 4 hours after the dropwise addition to obtain an acrylic resin solution.
Subsequently, after adding 0.025 mass part of hydroquinone monomethyl ether and 0.084 mass part of tetraethylammonium bromide to the said acrylic resin solution, glycidyl methacrylate was dripped over 2 hours. After dropping, after reacting at 90 ° C. for 4 hours while blowing air, a solution of the water-insoluble polymer (1) having an unsaturated group is prepared by adding a solvent so that the solid content concentration is 45%. (Weight average molecular weight (Mw); 30,000, 1-methoxy-2-propanol 45% solution).
In addition, as a measuring method of the said weight average molecular weight, it measured using gel permeation chromatography (GPC).
The SP value of the water-insoluble polymer 1 was calculated by the Okitsu method and was 22 MPa ^1/2 .

(Preparation example 2 of water-insoluble polymer)
-Preparation of water-insoluble polymer (2)-
8.57 parts by mass of 1-methoxy-2-propanol (MMPGAC, manufactured by Daicel Chemical Industries, Ltd.) was added in advance to the reaction vessel and the temperature was raised to 90 ° C., and 6.27 parts by mass of isopropyl methacrylate and methacrylic acid as monomers. A mixed solution consisting of 5.15 parts by mass, 1 part by mass of an azo polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) and 8.57 parts by mass of 1-methoxy-2-propanol was added under a nitrogen gas atmosphere. The solution was dropped into a reaction vessel at 0 ° C. over 2 hours. Reaction was performed for 4 hours after the dropwise addition to obtain an acrylic resin solution.
Subsequently, after adding 0.025 mass part of hydroquinone monomethyl ether and 0.084 mass part of tetraethylammonium bromide to the said acrylic resin solution, 5.41 mass parts of glycidyl methacrylate was dripped over 2 hours. After dropping, after reacting at 90 ° C. for 4 hours while blowing air, it is prepared by adding a solvent (1-methoxy-2-propanol) so that the solid content concentration is 45%, and has an unsaturated group A solution of the water-insoluble polymer (2) (solid content acid value; 73 mg KOH / g, Mw; 10,000, 1-methoxy-2-propanol 45% solution) was obtained. The SP value of the water-insoluble polymer (2) was calculated by the Okitsu method and was 20 MPa ^1/2 .

(Preparation example 1 of silver nanowire dispersion)
A silver nitrate solution in which 0.51 g of silver nitrate powder was dissolved in 50 mL of pure water was prepared. Thereafter, 1N ammonia water was added to the silver nitrate solution until it became transparent, and pure water was added so that the total amount became 100 mL, whereby an additive solution A was prepared.

  An additive solution G was prepared by dissolving 0.5 g of glucose powder in 140 mL of pure water.

27.5 g of HTAB (hexadecyl-trimethylammonium bromide) powder
The additive solution H was prepared by dissolving in mL of pure water.

20.6 mL of additive liquid A was placed in a three-necked flask and stirred at room temperature. Silver nanowire aqueous dispersion was prepared by adding 41 mL of pure water, 20.6 mL of additive solution H and 16.5 mL of solution B to this solution with a funnel and heating at 90 ° C. for 5 hours with stirring at 200 rpm. (1) was obtained.
After cooling the obtained aqueous dispersion, the dispersant (1) is added with stirring so as to be 0.05 with respect to the weight of silver, and then centrifuged to obtain a conductivity of 50 μS / cm or less. Then, the mixture was further centrifuged with propylene glycol monomethyl ether to remove water, and finally propylene glycol monomethyl ether acetate was added to prepare a silver nanowire solvent dispersion (1).
The average minor axis diameter, average major axis diameter, coefficient of variation of minor axis diameter, and ratio of conductive fibers (silver nanowires) having an aspect ratio of 10 or more of the obtained silver nanowire dispersion (1) are shown below. The results are shown in Table 1.

<Average minor axis diameter (diameter) and average major axis diameter of silver nanowire>
Using a transmission electron microscope (TEM; JEM-2000FX, JEM-2000FX), 300 silver nanowires were observed, and the average minor axis diameter and average major axis diameter of the silver nanowires were determined from the average values. .

<Coefficient of variation of short axis diameter of silver nanowire>
Using a transmission electron microscope (TEM; JEM-2000FX, manufactured by JEOL Ltd.), 300 short axis diameters of the silver nanowires were observed, and the short axis diameter of the silver nanowires was measured from the average value. The coefficient of variation was determined by calculating the deviation and the average value.

<Ratio of conductive fibers having an aspect ratio of 10 or more>
Each silver nanowire aqueous dispersion is filtered to separate silver nanowires and other particles, and the amount of silver remaining on the filter paper using an ICP emission analyzer (ICPS-8000, manufactured by Shimadzu Corporation) The amount of silver that has passed through the filter paper is measured, and the ratio of the conductive nanofibers having an aspect ratio of 10 or more to silver nanowires having an average minor axis diameter of 50 nm or less and an average major axis diameter of 5 μm or more (% ).
In addition, isolation | separation of the silver nanowire at the time of calculating | requiring the ratio of an electroconductive fiber was performed using the membrane filter (The product made by Millipore, FALP 02500, the hole diameter of 1.0 micrometer).

(Preparation example 2 of silver nanowire dispersion)
In Preparation Example 1 of the silver nanowire dispersion, HTAB (hexadecyl-trimethylammonium bromide) was replaced with octadecyl-trimethylammonium bromide, and the reaction time was changed to 2 hours. Thus, a silver nanowire dispersion (2) was obtained. At this time, the obtained silver nanowire particles were in the form of a wire having an average minor axis length of 18 nm and an average major axis length of 0.7 μm. The average minor axis diameter, average major axis diameter, coefficient of variation of minor axis diameter, and ratio of conductive fibers (silver nanowires) having an aspect ratio of 10 or more of the obtained silver nanowire dispersion (2) are silver nanowires. Measurements were made in the same manner as (1), and the results are shown in Table 1.

(Preparation example 3 of silver nanowire dispersion)
In Preparation Example 1 of the silver nanowire dispersion, HTAB (hexadecyl-trimethylammonium bromide) was replaced with octadecyl-trimethylammonium bromide, and the reaction time was changed to 3 hours. Thus, a silver nanowire dispersion (3) was obtained. At this time, the obtained silver nanowire particles were in the form of a wire having an average minor axis length of 22 nm and an average major axis length of 1.2 μm. The average minor axis diameter, average major axis diameter, coefficient of variation of minor axis diameter, and ratio of conductive fibers (silver nanowires) having an aspect ratio of 10 or more of the obtained silver nanowire dispersion (3) are silver nanowires. Measurements were made in the same manner as (1), and the results are shown in Table 1.

(Preparation example 4 of silver nanowire dispersion)
In Preparation Example 1 of the silver nanowire dispersion, in addition to the addition liquid A, the addition liquid G, and the addition liquid H, the same procedure as in Preparation Example 1 of the silver nanowire dispersion was performed except that 10.4 ml of cyclohexanol was added. A silver nanowire dispersion (4) was obtained. At this time, the obtained silver nanowire particles were in the form of a wire having an average minor axis length of 42 nm and an average major axis length of 29 μm. The average minor axis diameter, average major axis diameter, coefficient of variation of minor axis diameter, and ratio of conductive fibers (silver nanowires) having an aspect ratio of 10 or more of the obtained silver nanowire dispersion (4) are silver nanowires. Measurements were made in the same manner as (1), and the results are shown in Table 1.

(Preparation example 5 of silver nanowire dispersion)
In Preparation Example 1 of the silver nanowire dispersion, in addition to the addition liquid A, the addition liquid G, and the addition liquid H, except that 19.6 ml of cyclohexanol was added, the same procedure as in Preparation Example 1 of the silver nanowire dispersion was performed. A silver nanowire dispersion (5) was obtained. At this time, the obtained silver nanowire particles were in the form of a wire having an average minor axis length of 56 nm and an average major axis length of 22 μm. The average minor axis diameter, average major axis diameter, coefficient of variation of minor axis diameter, and ratio of conductive fibers (silver nanowires) having an aspect ratio of 10 or more of the obtained silver nanowire dispersion (5) are silver nanowires. Measurements were made in the same manner as (1), and the results are shown in Table 1.

In Table 1, “a ratio of conductive fibers” represents a ratio of conductive fibers (silver nanowires) having an aspect ratio of 10 or more.

Example 1
-Production of transparent conductor 1-
Stirrer so that the content ratio of silver nanowire dispersion (1), water-insoluble polymer (1) and dispersant (1) (silver nanowire / water-insoluble polymer / dispersant) is 100/100/5 The conductive composition 1 was prepared by mixing with stirring. It was 0.27% when content of the silver nanowire contained in this electrically conductive composition 1 was measured in ICP (high frequency inductively coupled plasma; Shimadzu Corporation make, ICPS-1000IV).
Using a doctor coater on the surface of a commercially available glass substrate of 100 mm × 100 mm × 0.7 mm (manufactured by Asahi Glass Co., product number AN-100), the conductive composition 1 was applied so that the average thickness was 15 μm. The transparent conductor 1 was produced by drying under conditions of a temperature of 25 ° C. and a humidity of 55%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 1 was measured with the fluorescent X-ray analyzer (the product made by SII, SEA1100).

(Example 2)
-Production of transparent conductor 2-
In Example 1, the conductive composition 2 and the transparent conductor 2 were obtained like Example 1 except having replaced the silver nanowire dispersion (1) with the silver nanowire dispersion (2). In addition, when the amount of silver nanowires contained in the conductive composition 2 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV), it was 0.27%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 2 was measured with the fluorescent-X-ray-analysis apparatus (SII company make, SEA1100).

(Example 3)
-Production of transparent conductor 3-
In Example 1, the electroconductive composition 3 and the transparent conductor 3 were obtained like Example 1 except having replaced the silver nanowire dispersion (1) with the silver nanowire dispersion (3). In addition, when the amount of silver nanowires contained in the conductive composition 3 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV), it was 0.27%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 3 was measured with the fluorescent X ray analyzer (the product made by SII, SEA1100).

Example 4
-Production of transparent conductor 4-
In Example 1, the electroconductive composition 4 and the transparent conductor 4 were obtained like Example 1 except having replaced the silver nanowire dispersion (1) with the silver nanowire dispersion (4). In addition, when the amount of silver nanowires contained in the conductive composition 4 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV), it was 0.27%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 4 was measured with the fluorescent X-ray analyzer (the product made by SII, SEA1100).

(Example 5)
-Production of transparent conductor 5-
In Example 1, the electroconductive composition 5 and the transparent conductor 5 were obtained like Example 1 except having replaced the silver nanowire dispersion (1) with the silver nanowire dispersion (5). In addition, when the amount of silver nanowires contained in the conductive composition 5 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV), it was 0.27%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 5 was measured with the fluorescent X ray analyzer (the product made by SII, SEA1100).

(Example 6)
-Production of transparent conductor 6-
In Example 1, except having replaced the dispersing agent (1) with the dispersing agent (2), it carried out similarly to Example 1, and obtained the conductive composition 6 and the transparent conductor 6. FIG. In addition, when the amount of silver nanowires contained in the conductive composition 6 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV), it was 0.27%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 6 was measured with the fluorescent X-ray analyzer (the product made by SII, SEA1100).

(Example 7)
-Production of transparent conductor 7-
In Example 1, except having replaced the dispersing agent (1) with the dispersing agent (3), it carried out similarly to Example 1, and obtained the conductive composition 7 and the transparent conductor 7. FIG. In addition, it was 0.27% when the amount of silver nanowire contained in the conductive composition 7 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV). It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 7 was measured with the fluorescent X ray analyzer (the product made by SII, SEA1100).

(Example 8)
-Production of transparent conductor 8-
In Example 1, except having changed the dispersing agent (1) into the dispersing agent (4), it carried out similarly to Example 1, and obtained the conductive composition 8 and the transparent conductor 8. In addition, when the amount of silver nanowires contained in the conductive composition 8 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV), it was 0.27%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 8 was measured with the fluorescent X ray analyzer (the product made by SII, SEA1100).

Example 9
-Production of transparent conductor 9-
In Example 1, except having replaced the dispersing agent (1) with the dispersing agent (5), it carried out similarly to Example 1, and obtained the conductive composition 9 and the transparent conductor 9. In addition, when the amount of silver nanowires contained in the conductive composition 9 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV), it was 0.27%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 9 was measured with the fluorescent X-ray analyzer (the product made by SII, SEA1100).

(Example 10)
-Production of transparent conductor 10-
In Example 1, the conductive composition 10 and the transparent conductor 10 were obtained like Example 1 except having changed the weight average molecular weight of the dispersing agent (1) from 100,000 to 4,600. In addition, when the amount of silver nanowires contained in the conductive composition 10 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV), it was 0.27%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 10 was measured with the fluorescent X ray analyzer (the product made by SII, SEA1100).

(Example 11)
-Production of transparent conductor 11-
In Example 1, the conductive composition 11 and the transparent conductor 11 were obtained in the same manner as in Example 1 except that the weight average molecular weight of the dispersant (1) was changed from 100,000 to 1,300,000. It was. In addition, when the amount of silver nanowires contained in the conductive composition 11 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV), it was 0.27%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 11 was measured with the fluorescent X-ray analyzer (the product made by SII, SEA1100).

(Example 12)
-Production of transparent conductor 12-
In Example 1, except that the content of the dispersant (1) was changed from 0.05 parts by mass to 0.005 parts by mass, the conductive composition 12 and the transparent conductor 12 were changed in the same manner as in Example 1. Obtained.

(Example 13)
-Production of transparent conductor 13-
In Example 1, the conductive composition 13 and the transparent conductor 13 were obtained like Example 1 except having changed the content of the dispersing agent (1) from 0.05 mass part to 32 mass parts. .

(Example 14)
-Production of transparent conductor 14-
In Example 1, the electroconductive composition 14 and the transparent conductor 14 were obtained like Example 1 except having replaced the water-insoluble polymer (1) with the water-insoluble polymer (2). In addition, when the amount of silver nanowires contained in the conductive composition 14 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV), it was 0.27%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 14 was measured with the fluorescent X ray analyzer (the product made by SII, SEA1100).
(Example 15)
-Production of transparent conductor 15-
In Example 1, except that the water-insoluble polymer (1) was replaced with polymethyl methacrylate (SP value 18.5 MPa ^1/2 ) as the water-insoluble polymer (3), the same as in Example 1, The conductive composition 15 and the transparent conductor 15 were obtained. In addition, when the amount of silver nanowires contained in the conductive composition 15 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV), it was 0.27%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 15 was measured with the fluorescent X ray analyzer (the product made by SII, SEA1100).
(Example 16)
-Production of transparent conductor 16-
In Example 1, except that the water-insoluble polymer (1) was replaced with the polyisobutylene SP value of 15.8 MPa ^1/2 as the water-insoluble polymer (4), the conductive composition was the same as in Example 1. 16 and transparent conductor 16 were obtained. In addition, when the amount of silver nanowires contained in the conductive composition 16 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV), it was 0.27%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 16 was measured with the fluorescent X-ray analyzer (the product made by SII, SEA1100).

(Comparative Example 1)
-Production of transparent conductor 17-
In Example 1, the conductive composition 17 and the transparent conductor 17 were obtained like Example 1 except having changed the dispersing agent (1) into Solsperse 24000 (made by Lubrizol). In addition, when the amount of silver nanowires contained in the conductive composition 17 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV), it was 0.27%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 17 was measured with the fluorescent X ray analyzer (the product made by SII, SEA1100).

(Comparative Example 2)
-Production of transparent conductor 18-
In Example 1, when the dispersant (1) was replaced with CTAB (cetyltrimethylammonium bromide) (manufactured by Wako Pure Chemical Industries, Ltd.), aggregation occurred when propylene glycol monomethyl ether was added, and further evaluation was impossible. Met.

(Comparative Example 3)
-Production of transparent conductor 19-
In Example 1, the conductive composition 19 and the transparent conductor 19 were obtained like Example 1 except having changed the dispersing agent (1) into DISPERBYK-2091 (made by Big Chemie). In addition, when the amount of silver nanowires contained in the conductive composition 19 was measured by ICP (high frequency inductively coupled plasma; manufactured by Shimadzu Corporation, ICPS-1000IV), it was 0.27%. It was 0.04 g / m < ² > when the amount of silver nanowire contained in the transparent conductor 19 was measured with the fluorescent X ray analyzer (the product made by SII, SEA1100).

(Reference Example 1)
-Production of transparent conductor 20-
In Example 1, when water-insoluble polymer (1) was replaced with hydroxypropylethylcellulose which is a water-soluble polymer, aggregation occurred and evaluation beyond that was impossible.

(Evaluation)
Conductivity when dried at room temperature in Examples 1 to 16, Comparative Example 1 and Comparative Example 3 (hereinafter referred to as “low temperature conductivity”) Conductivity after firing at 150 ° C. for 30 minutes (hereinafter referred to as “low temperature conductivity”) "High temperature conductivity"), solvent dispersibility, total light transmittance, haze, durability, and flexibility were evaluated as follows. The results are shown in Table 2.

<Low temperature conductivity>
The low-temperature conductivity was evaluated for conductivity when dried at room temperature. The measurement was performed by measuring the surface resistance (Ω / □) using Loresta-GP MCP-T600 (manufactured by Mitsubishi Chemical Corporation).

<High temperature conductivity>
The high-temperature conductivity was evaluated after conducting baking at 150 ° C. for 30 minutes. The measurement was performed by measuring the surface resistance (Ω / □) using Loresta-GP MCP-T600 (manufactured by Mitsubishi Chemical Corporation).

<Solvent dispersibility>
In the preparation of the conductive fiber solvent dispersion, when propylene glycol monomethyl ether acetate was added, the evaluation was made as follows.
[Evaluation criteria]
○: There is no occurrence of aggregates visually.
X: Agglomerates were observed or aggregates were generated at the stage of preparation.

<Total light transmittance of transparent conductive layer>
The total light transmittance (%) of each obtained sample was measured using a Gardner Haze Guard Plus.

<Haze of transparent conductive layer>
Using a haze guard plus manufactured by Gardner, the haze (%) of each obtained sample was measured.

<Damp heat aging durability of transparent conductive layer>
As a durability evaluation, a wet heat aging test was conducted. After transparent conductor 1 to transparent conductor 10 were aged for 250 hours at a temperature of 80 ° C. and a humidity of 85% RH, surface resistance (Ω / □) was measured using Loresta-GP MCP-T600 (manufactured by Mitsubishi Chemical Corporation). And it evaluated by the following determinations.
R1 (Resistivity after aging) / R0 (Resistivity before aging) × 100 = Resistivity change (%)
[Evaluation criteria]
1. The resistivity change is 300% or more, which is a practically problematic level.
2. The resistivity change is less than 300% and 200% or more, which is a practically problematic level.
3. The resistivity change is less than 200% and 150% or more, which is a practically problematic level.
4). The resistivity change is less than 150% and 110% or more, which is a practically acceptable level.
5). The resistivity change is less than 110%, which is a level that causes no problem in practical use.

<Flexibility of transparent conductive layer>
The surface to which the conductive layer of each obtained sample was applied was turned outside, wound around a metal rod having a diameter of 9 mm, and allowed to stand for 15 seconds. The surface resistance of each sample before and after winding was measured with a digital multimeter 7555 (trade name, manufactured by Yokogawa Electronics Corporation), and the change was (after winding) / (before winding) × (100% ) = Resistivity change (%) and evaluated according to the following criteria. In addition, flexibility shows that it is excellent, so that a number is large.
[Evaluation criteria]
1. The resistivity change is 300% or more, which is a practically problematic level.
2. The resistivity change is less than 300% and 150% or more, which is a practically problematic level.
3. The resistivity change is less than 150% and 130% or more, which is a level with no practical problem.
4). The resistivity change is less than 130% and 115% or more, which is a level with no practical problem.
5). The resistivity change is less than 115%, and there is no practical problem.

(In the table, “OL” means that the surface resistance value was 10 ⁷ Ω / □ or more.)

  From Table 2, Examples 1 to 16 are excellent in low-temperature conductivity and excellent in all of haze, durability and flexibility, whereas Comparative Examples 1 to 3 are high-temperature. It can be seen that although the conductivity is excellent, there is no low-temperature conductivity.

(Production of touch panel)
The transparent conductor in Example 1 to Example 16 has high transmittance at a long wavelength, and thus when the touch panel created using the transparent conductor of Example 1 to Example 16 is used, the transmittance is improved. It has been found that a touch panel that is excellent in visibility and excellent in responsiveness to input of characters and the like or screen operation by at least one of bare hands, hands wearing gloves, and pointing tools by improving conductivity can be produced. The touch panel includes a so-called touch sensor and a touch pad.
For the production of touch panels, "latest touch panel technology" (issued July 6, 2009, Techno Times), supervised by Yuji Mitani, "Touch Panel Technology and Development", CM Publishing (2004, 12), FPD A publicly known method described in International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. was used.

(Production of integrated solar cells)
<Production Example 1>
-Fabrication of amorphous solar cells (super straight type)-
On the glass substrate, the conductive composition 1 of Example 1 was applied and dried under conditions of a temperature of 25 ° C. and a humidity of 55%, thereby forming the transparent conductor 1. It was 0.06 g / m < ² > when the amount of silver in this transparent conductor 1 was measured with the fluorescent X ray analyzer (the product made by SII, SEA1100). A p-type film having a thickness of about 15 nm is formed thereon by plasma CVD, an i-type film having a thickness of about 350 nm is formed on the p-type, and an n-type amorphous silicon film having a thickness of about 30 nm is formed on the i-type. A gallium-doped zinc oxide layer having a thickness of 20 nm was formed on the upper surface of the gallium-doped zinc oxide layer, and a silver layer having a thickness of 200 nm was formed on the gallium-doped zinc oxide layer, thereby producing a photoelectric conversion element 1A.

<Production Examples 2 to 15, 17>
-Fabrication of amorphous solar cells (super straight type)-
In Production Example 1, photoelectric conversion elements 2A to 15A and 17A were produced in the same manner as in Production Example 1 except that the transparent conductor 1 was replaced with transparent conductors 2 to 15 and 17, respectively, as shown in Table 3. .

<Production Example 19>
-Fabrication of CIGS solar cells (substrate type)-
A molybdenum electrode having a thickness of about 500 nm is formed on a glass substrate by a direct current magnetron sputtering method, and Cu (In _0.6 Ga _0.4 ) which is a chalcopyrite semiconductor material having a thickness of about 2.5 μm is formed on the electrode by a vacuum deposition method. A cadmium sulfide thin film having a thickness of about 50 nm is formed on the Se ₂ thin film and the Cu (In _0.6 Ga _0.4 ) Se ₂ thin film by a solution deposition method, and the conductivity of Example 1 is formed on the cadmium sulfide thin film. The transparent conductor 1 was formed by applying the composition 1 and drying it under the conditions of a temperature of 25 ° C. and a humidity of 55%. It was 0.06 g / m < ² > when the silver in this transparent conductor 1 was measured with the fluorescent-X-ray-analysis apparatus (the product made by SII, SEA1100). A boron-doped zinc oxide thin film (transparent conductive layer) having a thickness of about 100 nm was formed on the transparent conductor 1 by DC magnetron sputtering to produce a photoelectric conversion element 1B.

<Production Examples 20 to 33, 35>
-Fabrication of CIGS solar cells (substrate type)-
In Production Example 19, photoelectric conversion elements 2B to 15B and 17B were produced in the same manner as in Production Example 19 except that the transparent conductor 1 was replaced with transparent conductors 2 to 15 and 17, respectively, as shown in Table 4. .

(Evaluation of solar cell characteristics (conversion efficiency))
About each solar cell, the solar cell characteristic (conversion efficiency) was measured and evaluated by irradiating simulated sunlight of AM1.5 and 100 mW / cm < ² >. Table 3 shows the results of the amorphous solar cell, and Table 4 shows the results of the CIGS solar cell.

  From Tables 3 and 4, the solar cells using the transparent conductors of Examples 1 to 14 have extremely high conversion efficiency, whereas the solar cells using the transparent conductors of Comparative Examples 1 and 3 are It turns out that conversion efficiency is inferior compared with Examples 1-14. This is presumably because the use of the dispersant (1) to the dispersant (5) decreased the moisture content in the film and improved the transmittance in the long wavelength region.

Since the conductive composition of the present invention has excellent conductivity and transmittance, haze, durability, and flexibility, for example, touch panel, antistatic for display, electromagnetic wave shield, organic or inorganic EL display It can be widely used for electrodes, electronic paper, electrodes for flexible displays, antistatics for flexible displays, solar cells, and other various devices.
In addition, since the conductive composition of the present invention has conductivity even if it is not baked, it can be used when wiring to a flexible substrate or the like that cannot be heated.

DESCRIPTION OF SYMBOLS 10 Touch panel 20 Touch panel 30 Touch panel 11 Transparent substrate 21 Transparent substrate 31 Transparent substrate 12 Transparent conductive film 13 Transparent conductive film 22 Transparent conductive film 23 Transparent conductive film 32 Transparent conductive film 33 Transparent conductive film 24 Insulating layer 25 Insulating cover layer 14 Protective layer 17 Protective film 15 Intermediate protective film 16 Antiglare film 18 Electrode terminal 33 Spacer 34 Air layer 35 Transparent film 36 Spacer

Claims (15)

Conductive fibers;
A conductive composition comprising at least a dispersant containing a repeating unit represented by the following general formula (1) for dispersing the conductive fiber.
However, in the general formula (1), ^{R 1} represents a hydrogen atom or a methyl group. J ^{is, -CO -, - COO -,} - CONR 10 -, - OCO-, a methylene group, a phenylene group, or _-C 6 _H 4 CO-. R ¹⁰ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. W represents a single bond or a divalent linking group. P represents a heterocyclic group. 2. The conductive composition according to claim 1, wherein P in the general formula (1) is a substituent represented by the following general formula (2) or a tautomer structure thereof.
However, in General Formula (2), R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ³ represents a hydrogen atom or a substituent represented by the following general formula (3).
However, in General Formula (3), R ²³ represents a substituted or unsubstituted aromatic ring or a heteroatom-containing heterocyclic ring.   The conductive composition according to claim 1, wherein the dispersant is a graft copolymer further containing a polymerizable oligomer having an ethylenically unsaturated double bond at a terminal as a copolymer unit. The conductive composition according to claim 3, wherein the polymerizable oligomer is represented by the following general formula (4).
However, in General Formula (4), R ⁴ represents a hydrogen atom or a methyl group. X represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and L represents a single bond or a divalent organic linking group. R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. m represents an integer of 0 to 100, and n represents an integer of 1 to 100. SP ^value, a conductive composition according to any one of claims 1, further comprising a non-water-soluble binder which is 18MPa ^1/2 ~30MPa 1/2 4.   The conductive composition according to claim 1, wherein the conductive fiber is a metal nanowire.   The conductive composition according to claim 6, wherein the metal nanowire is made of any one of silver and an alloy of silver and a metal other than silver.   The conductive composition according to claim 7, wherein the metal other than silver is at least one selected from gold, palladium, iridium, platinum and osmium.   The conductive composition according to claim 1, wherein the conductive fiber has an average major axis diameter of 1 μm to 40 μm.   The conductive composition according to any one of claims 1 to 9, wherein the content of the dispersant represented by the general formula (1) is 0.01 to 30 parts by mass with respect to 100 parts by mass of the conductive fiber. object.   The conductive composition according to any one of claims 1 to 10, wherein the dispersant represented by the general formula (1) has a weight average molecular weight of 5,000 to 1,000,000.   A transparent conductor comprising the conductive composition according to claim 1. The transparent conductor according to claim 12, wherein the amount of conductive fibers in the transparent conductor is 0.005 g / m ^{2 to} 0.5 g / m ² .   A touch panel comprising the conductive composition according to claim 1.   An integrated solar cell comprising the conductive composition according to claim 1.